KR20150030645A - Epoxy resin composition, cured product thereof, and curable resin composition - Google Patents

Abstract

[식 중, 복수 존재하는 R은 각각 독립적으로 수소원자, 탄소수 1∼6의 알킬기, 또는 탄소수 1∼6의 알콕시기를 나타낸다.]An epoxy resin composition comprising an epoxy resin represented by the following formula (2), a phenol resin and / or a cationic polymerization catalyst, wherein the epoxy resin has a hue of 2 or less in a Gardner colorimetric method (40% MEK solution) (2), and a phenol resin and / or a polymerization catalyst.

Wherein the plurality of R's present 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.

Description

EPOXY RESIN COMPOSITION, CURED PRODUCT THEREOF, AND CURABLE RESIN COMPOSITION [0002]

TECHNICAL FIELD The present invention relates to an epoxy resin composition, and a cured product thereof, which are suitable for use in electric and electronic materials, particularly optical materials. Another aspect of the present invention relates to a curable resin composition suitable for use in electrical and electronic materials requiring heat resistance and flame retardancy.

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

As described above, the bisphenol A type epoxy resin has general versatility as an optical resin. However, these resins are generally in a liquid form, and have problems such as viscous property in sheeting or prepreg molding. In addition, So that the cured product is too soft and the heat resistance is hard to come out.

On the other hand, as a transparent material, development of a technology for producing a substitute product of glass by impregnating glass crossover and curing has been proceeding. It is known that various epoxy resin compositions can be used as substitutes for glass. In the case of conventional epoxy resins, when the difference in refractive index from the glass cloth is large, or when the birefringence is high, the visibility is deteriorated due to diffuse reflection, It has been difficult to use it as deflected light. Particularly, a transparent substrate such as a glass substitute epoxy resin for LCD using deflection is strongly required to have a low refractive index.

Thus, there has been a strong demand for the development of an epoxy resin for optical materials which satisfies the above-mentioned required characteristics.

Apart from the above, the curable resin composition is widely used in the fields of electric and electronic parts, structural materials, adhesives, paints and the like due to workability and excellent electrical properties, heat resistance, adhesiveness, moisture resistance (water resistance) .

In recent years, however, in the field of electric and electronic fields, in accordance with the development of the resin composition, the viscosity of the resin composition has been increased, and the viscosity, adhesiveness, dielectric properties, low viscosity for high filling of the filler (inorganic or organic filler) And improvement of various properties such as the improvement of the quality of the product. In addition, as a structural material, a lightweight material having excellent mechanical properties is required for use in aerospace materials, leisure sports equipment, and the like. Particularly, in the field of semiconductor encapsulation and the substrate (substrate itself or peripheral materials thereof), demand characteristics such as a very high level of heat resistance and high fluidity are required in accordance with the transition of the semiconductor, which is complicated by thinning, stacking, . Particularly, in accordance with the expansion of use of a plastic package in a vehicle, the demand for improvement of heat resistance is becoming more strict, and it is a resin having a low linear expansion coefficient at a high Tg, and naturally it is necessary to respond to solder reflow, , Or maintenance of the apparatus. In recent years, halogen-based epoxy resins and antimony trioxide have been widely used as flame retardants for electric and electronic parts as environmental flame retardants. However, it is pointed out that products using these products contribute to the generation of toxic substances such as dioxins by improper treatment after disposal .

Japanese Patent Application Laid-Open No. 07-157536 Japanese Patent Application Laid-Open No. 2005-082798 Japanese Patent Application Laid-Open No. 2007-284680

 "Seminar on Semiconductor Technology Roadmap 2008, JEITA Semiconductor Technology Roadmap Expert Committee, [Semiconductor Technology Roadmap 2008, 2008, STRJ Report Semiconductor Roadmap Expert Committee 2008 Report", Chapter 8, p1-17, [online] Search May 30th], <http://strj-jeita.elisasp.net/strj/nenjihoukoku-2008.cfm>  Takakura Nobuyuki et al., Matsushita TENKO Symbol-related device technology High-temperature operation IC for vehicle use, No. 74, May 31, 2001, pages 35-40

For the problem of the use of optical materials as described above, Purine Tec VG3105, which is an epoxy resin of a trisphenol compound having a structure which does not have the same benzylmethylene bond as the bisphenol A type epoxy resin, is used. However, they have an initial coloration, and a certain degree of transparency is required for use as an optical material.

As a method for solving such a problem, application of an epoxy resin having a silsesquioxane structure or an alicyclic epoxy resin has been studied. However, an epoxy resin having a silsesquioxane structure has a high heat resistance, but has a pronounced drift and a high coefficient of linear expansion And the refractive index is lowered. In addition, the alicyclic epoxy resin also has an improved heat resistance because it is a glass transition point, but it has a problem of low viscosity and low refractive index, and an aromatic glycidyl ether compound having good optical properties and high toughness is required.

In addition, as one of the methods for solving the problems in the use in the electric and electronic fields, an epoxy resin having a phosphorus atom skeleton has been proposed. Particularly, since a phosphate ester type compound has low stability, a cyclic phosphate ester compound having good stability is used. Further, by selecting a resin skeleton without using a phosphoric acid ester compound, excellent flame retardancy has been developed as compared with a conventional epoxy resin. However, at present, particularly in the field of semiconductor encapsulation materials, development of a system capable of flame retardation without using a phosphorus-based flame retardant has been studied, and flame retardancy generally called nonhalogen, nonantimony, or nonane is required.

Therefore, the first aspect of the present invention is to provide an epoxy resin composition which is excellent in transparency and heat resistance, has high refractive index, low birefringence and low retardation and is applicable to optical members requiring high optical properties The purpose is to provide.

The second object of the present invention is to provide a curable resin composition which can achieve both high heat resistance and flame retardancy and is advantageous for applications in the field of electricity and electronics.

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

That is, the present invention relates to the following (1) to (11).

(One)

An epoxy resin composition comprising an epoxy resin obtained by the reaction of a phenolic resin represented by the following formula (1) with epihalohydrin and a carboxylic acid and / or a cationic polymerization catalyst, wherein the epoxy resin is obtained by a Gardner colorimetric method (40 % MEK solution) having a hue of 2 or less.

(Wherein the plurality of Rs present 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)

(2)

The epoxy resin composition according to the above (1), wherein the amount of the 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 (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 the above (3), which contains a transition metal salt.

(5)

The epoxy resin composition according to the above (3), which contains a quaternary phosphonium salt.

(6)

The epoxy resin composition according to the above (3), which contains a cationic polymerization initiator.

(7)

An epoxy resin cured product obtained by curing the epoxy resin composition according to any one of (4) to (6) above.

(8)

The epoxy resin composition for glass substitution according to any one of (1) to (6) above.

(9)

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

(Wherein the plural Rs present 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 the above (9), wherein the phenol resin is a phenol aralkyl resin (a resin having an aromatic alkylene structure).

(11)

The curable resin composition according to the above (9), wherein the polymerization catalyst is a cationic polymerization catalyst.

(Effects of the Invention)

The first epoxy resin composition of the present invention can be applied to optical members requiring high optical properties because of excellent transparency and heat resistance, high refractive index and low birefringence.

The second curable resin composition of the present invention is an epoxy resin that exhibits flame retardancy even when a flame retardant and a phosphorus compound are not used while ensuring sufficient curability and contributes to reduction of flame retardant and phosphorus compound in the composition, And various laminated materials (printed wiring boards, build-up substrates and the like), CFRP and the like, adhesives, paints and the like. And is particularly useful for semiconductor sealing materials and substrate materials for protecting semiconductor devices.

The first aspect of the present invention (hereinafter also referred to as &quot; first invention &quot;) is an epoxy resin obtained by the reaction of a phenolic resin represented by the following formula (1) with epihalohydrin and a carboxylic acid and / An epoxy resin composition containing a catalyst, wherein the epoxy resin is an epoxy resin composition having two or less hues in a Gardner colorimetric method (40% MEK solution).

(Wherein the plurality of Rs present 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 second aspect of the present invention (hereinafter also referred to as &quot; second invention &quot;) is a curable resin composition containing an epoxy resin represented by the following formula (2) and a phenol resin and / or a polymerization catalyst.

(Wherein the plural Rs present 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 of each of the first and second inventions is an epoxy resin having a phenol phthalimide 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), Color Gardner 8 (40% in methyl glycol), softening point 66 ° C (kolfer heater) and chlorine content 2.2% Lt; / RTI &gt; Also disclosed is a curing property with DDS (diaminodiphenylsulfone).

In this state, development to an optical material is difficult, and a resin having higher transparency is required.

In addition, the resin based on the data of Patent Document 4 has a very large amount of chlorine, which is not suitable for use in electronic materials, and is highly colored, suggesting that it is difficult to use in applications requiring colorimetry. It is also suggested that epoxy equivalent is 294 g / eq., Which is larger than the theoretical value (252.7 g / eq.), And that the epihalohydrin structure remaining in the epoxy resin is not contained in the epichlorohydrin structure. However, if the epoxy ring is not completely formed, crosslinking does not proceed well, and curing with a phenol resin, anion polymerization with a basic catalyst such as imidazole, and cation polymerization with an onium salt or the like are carried out In many cases, problems arise in the characteristics of mechanical properties and absorbency. Particularly in the use of electronic materials, not only these curing but also amine curing are expected to cause corrosion of wiring caused by free glass of curing at the time of curing, which is a factor of deteriorating electrical reliability.

In recent years, copper wires have been used more particularly for bonding semiconductor chips and substrates, and the problem of such corrosion has become more important and a problem to be solved.

In addition, the Patent Document 4 does not disclose flame retardancy.

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

(Wherein, in the formulas, R represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms), epoxy resin obtained by reaction of epihalohydrin with a phenol resin (2) &quot;

(Wherein, in the formulas, each R is independently an hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms).

The epoxy resin used in the epoxy resin composition of the first aspect of the invention is an epoxy resin preferably containing 70 to 95% (gel permeation chromatography area%), more preferably 70 to 93%, of the epoxy compound. Here, when an epoxy resin having a purity of more than 95% of the epoxy compound content is synthesized, it may have energetic energy. When the purity is too high, there is a possibility that the crystallinity is increased and the toughness is lowered There is a job to lose. If it is less than 70%, the ring of the epoxy may not be completely ring closed, and a large amount of the compound having no functional group may be contained. Most of these compounds which are not completely closed include chlorine in many cases. As a result, there is a concern that the use of chlorine ions under high temperature and high humidity conditions and the corrosion of the wiring due to the high temperature and high humidity conditions are concerned.

When the epoxy resin having a phenolphthalein structure remains in the present epoxy resin, the residual of the epoxy resin having a phenolphthalein structure is not preferable from the standpoint of deterioration of electric reliability and large coloring, preferably 2% or less Is less than 1%. The epoxy resin having the phenolphthalein structure is largely influenced by impurities derived from the raw material. If it exceeds 2%, coloring becomes particularly strong, which is not preferable.

In the above 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 straight, branched or cyclic alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group and hexyl group. Here, R is preferably a methyl group or an ethyl group, and a methyl group is particularly preferable.

Examples of the alkoxy group having 1 to 6 carbon atoms represented by R include straight, branched or cyclic alkoxy groups such as methoxy, ethoxy, propoxy and butoxy groups. Here, R is preferably a methoxy group, an ethoxy group or a propoxy group, and a methoxy group is particularly preferable.

Preferable resin characteristics of the epoxy resin of the formula (2) are 1.02 to 1.13 times the epoxy equivalent weight (252.7 g / eq.) Of the epoxy equivalent. More preferably, it is 1.03 to 1.10 times. If it is less than 1.02 times, the cost for synthesizing and refining epoxy is increased, which is industrially undesirable. If it exceeds 1.13 times, problems due to the same amount of chlorine as mentioned above are concerned.

The total chlorine remaining in the obtained epoxy resin is preferably 5000 ppm or less, more preferably 3,000 ppm or less, particularly preferably 2,000 ppm or less. The adverse effects due to the chlorine amount are the same as described above. The content of the chlorine ion and the sodium ion is preferably 5 ppm or less, more preferably 3 ppm or less. The chlorine ion does not need to be mentioned in the foregoing description, but the cation such as the sodium ion becomes a factor particularly important for the power device application, and becomes a member of the failure mode when the high voltage is applied.

Here, the theoretical epoxy equivalent represents the epoxy equivalence calculated when the phenolic hydroxyl group of the phenol compound of the formula (1) is glycidylated without excess.

The specific epoxy equivalent value is preferably 257.8 g / eq. To 285.6 g / eq., More preferably 260.3 g / eq. To 278.0 g / eq. 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 (also referred to simply as &quot; the epoxy resin of the present invention &quot;) used in the resin composition of the present invention has a resinous form having a softening point. Here, the softening point is preferably 70 to 130 占 폚, more preferably 80 to 120 占 폚. Particularly preferably 70 to 120 캜, more preferably 80 to 110 캜, when the substituent R is a hydrogen atom. If the softening point is too low, blocking at the time of storage becomes a problem, and there are many problems such as handling at low temperatures. On the contrary, when the softening point is too high, there arises a problem that the handling becomes poor when the resin is kneaded with another resin. The melt viscosity is preferably 1 Pa · s (ICI melt viscosity 150 ° C cone plate method) or less. When an inorganic material (filler or the like) is mixed and used, the fluidity may be deteriorated. In addition, the glass cloth or the like may be made finer and the impregnability may be deteriorated.

The epoxy resin used in the first invention is excellent in transparency (color). And a Gardner colorimetric method (40% methyl ethyl ketone solution in water) of 2 or less, preferably 1.5 or less. Particularly, in general PCB substrates and the like as well as development in optical materials, it is required to have little coloring because it affects the color of the substrate.

The epoxy resin used in the second invention need not be excellent in transparency (color) as described above, but it is preferable that the epoxy resin is similarly excellent.

The epoxy resin of the present invention has a high refractive index. Preferably 1.61 or more, more preferably 1.62 or more, and particularly preferably 1.62 to 1.65. Especially in the field where the refractive index adjustment is required, if the refractive index is high, the directional exchange rate of the composition to be used can be reduced, contributing to the improvement of the light resistance characteristic. Further, in applications such as lenses, a lens having a smaller deformation than that of a high refractive index can be prepared, which is preferable.

Hereinafter, a method for producing an epoxy resin of the present invention will be described.

The compound of the above formula (2) is obtained by the reaction of a phenol compound (DPPI) synthesized from a phenolphthalein derivative and an aminobenzene derivative (for example, JP 2005-290378 A) and epihalohydrin Loses. A specific example of the production method of the epoxy resin of the present invention is shown below.

It is known that phenolphthalein derivatives can be synthesized with phthalic acid and corresponding various phenols. If the phenol used is phenol, phenolphthalein is obtained, and when cresol is used, cresol phthalylene is obtained.

Examples of the various phenols include phenol, cresol, ethyl phenol, propyl phenol, xylenol and methyl butyl phenol.

As the phenolphthalein derivative obtained by the above reaction, for example, the following structure can be mentioned.

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

Examples of the aminobenzene derivative include the following structures.

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

The amount of the 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 Gt; When this phenolphthalein derivative remains, the coloration tends to increase during the reaction. The same applies to aminobenzene derivatives. The remaining amount of iron (ICP emission analysis) is also one of the factors due to coloring. The residual iron content is preferably 100 ppm or less, more preferably 50 ppm or less, particularly preferably 10 ppm or less. The main phenolic compound (DPPI) requires a purity of 98% or more.

The amount of residual phenolphthalein derivative can be adjusted by purification (cleaning, recrystallization, re-precipitation, etc.) of DPPI.

As the epihalohydrin in the reaction for obtaining the epoxy resin of the present invention, epichlorohydrin which is industrially available is preferable. The amount of the epihalohydrin to be used is generally 3.0 to 15 mol, preferably 3.0 to 10 mol, more preferably 3.5 to 8.5 mol, particularly preferably 5.5 to 8.5 mol per mol of the hydroxyl group of the phenol compound (DPPI) It is mall.

When the amount is less than 3.0 moles, the epoxy equivalent may be increased, and the workability of the produced epoxy resin may be deteriorated. When it exceeds 15 moles, the amount of the solvent becomes large.

In the reaction of the phenolic resin and the epihalohydrin, an alkali metal hydroxide can be used. As the alkali metal hydroxide to be used, sodium hydroxide, potassium hydroxide and the like can be used, and a solid material may be used, However, in the present invention, it is particularly preferable to use a solid material molded in a frictional form in terms of solubility and handling.

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

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

In the present reaction, it is preferable to use a nonpolar proton solvent (dimethylsulfoxide, dioxane, dimethylimidazolidinone, etc.) or an alcohol having 1 to 5 carbon atoms in addition to the epihalohydrin. Examples of the alcohol having 1 to 5 carbon atoms include alcohols such as methanol, ethanol and isopropyl alcohol. The amount of the nonpolar proton solvent or the alcohol having 1 to 5 carbon atoms is usually 2 to 50% by weight, preferably 4 to 25% by weight based on the amount of epihalohydrin used. It is also possible to conduct the exocytosis while controlling moisture in the system by a method such as azeotropic dehydration.

When the water content in the system is large, the electrical reliability of the epoxy resin obtained deteriorates, which is not preferable. It is preferable to control the water content to 5% or less to synthesize the epoxy resin. In addition, when an epoxy resin is obtained by using a nonpolar proton solvent, an epoxy resin having excellent electrical reliability can be obtained, so that a nonpolar proton solvent can be suitably used.

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

After removing the epihalohydrin, solvent and the like from the reaction product of the epoxidation reaction under heating and decompression after washing with water or without washing with water. The epoxy resin thus recovered may be a ketone compound having 4 to 7 carbon atoms (for example, methyl isobutyl ketone, methyl ethyl ketone, cyclopentanone, cyclohexanone, etc.) in order to obtain an epoxy resin having less hydrolyzable halogen. ) Is dissolved as a solvent, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is further added to carry out the reaction, whereby the closed ring can be made definite. In this case, the amount of the alkali metal hydroxide to be used is usually 0.01 to 0.3 mol, preferably 0.05 to 0.2 mol, based on 1 mol of the hydroxyl group of the starting phenol mixture used for the epoxidation. The reaction temperature is usually from 50 to 120 캜, and the reaction time is usually from 0.5 to 2 hours.

Further, in the reaction with epihalohydrin, it is preferable to be substituted with an inert gas such as nitrogen from the beginning of the reaction, and the oxygen concentration in the syngas is preferably 10% or less. Residual oxygen affects the coloring. As the method, an inert gas such as nitrogen is blown (in the air or in the liquid) before the introduction of the phenol compound (DPPI), or a once-reduced vacuum is introduced and then the inert gas is substituted. In the case where there is no substitution in the inert gas, the resultant resin may be colored. When the inert gas is blown, the amount of the inert gas differs depending on the volume of the kiln, but it is preferable to inject the inert gas in an amount capable of displacing 1 to 3 times the volume of the kiln in 0.5 to 10 hours.

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

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

The epoxy resin composition of the first invention (hereinafter also referred to as &quot; curable resin composition &quot;) contains the epoxy resin of the present invention as an essential component.

In the curable resin composition of the first aspect of the invention, the curing of the cationic curing (curable resin composition B) using a curing agent (curable resin composition A) comprising a carboxylic acid as an essential component and a cationic polymerization catalyst such as an acid as a curing catalyst You can adapt the species method.

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

Examples of other epoxy resins which can be used in combination with the epoxy resin of the present invention include novolak type epoxy resins, bisphenol type epoxy resins, biphenyl type epoxy resins, triphenylmethane type epoxy resins and phenol aralkyl type epoxy resins. Specific examples thereof include bisphenol A, bisphenol S, thiodiphenol, fluorene bisphenol, terpenediphenol, 4,4'-biphenol, 2,2'-biphenol, 3,3 ', 5,5'- (1,1'-biphenyl) -4,4'-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis Hydroxyphenyl) ethane, phenols (phenol, alkyl substituted phenol, naphthol, alkyl substituted naphthol, dihydroxybenzene, dihydroxynaphthalene and the like) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o- Benzoyl peroxide, benzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4'-bis (chloromethyl) -1,1'- (Methoxymethyl) -1,1'-biphenyl, 1,4-bis (chloromethyl) benzene or 1,4-bis (methoxymethyl) benzene and their modifications, tetrabromobisphenol A And halogenated bisphenols such as Glycidyl ether epoxy resins, glycidyl ester epoxy resins, silsesquioxane epoxy resins (chain, cyclic, ladder, or a mixture thereof) derived from alcohols, glycidyl ethers derived from alcohols, alicyclic epoxy resins, glycidylamine- Or an epoxy resin having a glycidyl group and / or an epoxy cyclohexane structure in a siloxane structure having at least two or more mixed structures), and the like, but are not limited thereto.

In particular, when the curable resin composition of the present invention is used for optical use, it is preferable to use the epoxy resin of the present invention in combination with an alicyclic epoxy resin or an epoxy resin having a silsesquioxane structure. Especially, in the case of alicyclic epoxy resin, a compound having an epoxy cyclohexane 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.

Examples of the compound having a cyclohexene structure include an esterification reaction of cyclohexenecarboxylic acid with alcohols or an esterification reaction of cyclohexene methanol with carboxylic acids (Tetrahedron vol.36 p.2409 (1980), Tetrahedron Letter p.4475 (1980) (Described in JP-A-2003-170059 and JP-A-2004-262871) of cyclohexene aldehyde and transesterification reaction of cyclohexenecarboxylic acid ester A method described in, for example, Japanese Patent Application Laid-Open No. 2006-052187).

The alcohols are not particularly limited as long as they are compounds having an alcoholic hydroxyl group, and examples thereof include ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, Diols and cyclohexanedimethanol, triols such as glycerin, trimethylol ethane, trimethylol propane, trimethylol butane and 2-hydroxymethyl-1,4-butanediol, and tetraols such as pentaerythritol And the like. Examples of the carboxylic acid include oxalic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, adipic acid, and cyclohexanedicarboxylic acid, but are not limited thereto.

As other compounds having a cyclohexene structure other than the above, there may be mentioned acetal compounds by cyclohexene aldehyde derivatives and acetal reaction of alcohols. As a reaction method, it can be prepared by applying a general acetalization reaction. For example, there can be used a method in which a reaction is carried out while azeotropically dehydrating a reaction medium with a solvent such as toluene or xylene (U.S. Patent No. 2945008) (Japanese Patent Application Laid-Open No. 48-96590), a method of using water as a reaction medium (U.S. Patent No. 3092640), a method of dissolving a polyhydric alcohol in an organic solvent (Japanese Patent Application Laid-Open No. 7-215979), a method using a solid acid catalyst (Japanese Patent Application Laid-Open No. 2007-230992), and the like. From the stability of the structure, a cyclic acetal structure is preferable.

Specific examples of these epoxy resins include ERL-4221, UVR-6105 and ERL-4299 (both trade names, all manufactured by Dow Chemical), Celloxide 2021P, Epolide GT401, EHPE3150 and EHPE3150CE (all trade names, all available from Daicel Chemical Industries) And dicyclopentadiene epoxide. However, the epoxy resin is not limited to these (refer to General Synthetic Epoxy Resin Foundation I p76-85).

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

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

Curable resin composition A (thermal curing by a curing agent)

As the 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 acid) is an essential component. The carboxylic acids are preferably carboxylic acids having 2 to 4 functional groups, more preferably polycarboxylic acids obtained by addition reaction of polyhydric alcohols having 2 to 4 functional groups with acid anhydrides. 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, an acid anhydride is used in the use of an optical material, but in the curable composition A of the present invention, a carboxylic acid is also essential as a component to suppress volatility.

The 2- to 4-functional polyhydric alcohols are not particularly limited as long as they are compounds having an alcoholic hydroxyl group, and examples thereof include ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, , 1,6-hexanediol, cyclohexanedimethanol, 2,4-diethylpentanediol, 2-ethyl-2-butyl-1,3-propanediol, neopentyl glycol, tricyclodecanedimethanol, Diols, glycerin, trimethylol ethane, trimethylol propane, trimethylol butane, 2-hydroxymethyl-1,4-butanediol and the like, and tetraols such as pentaerythritol and dimethylol propane have.

Particularly preferable examples thereof include branched or cyclic compounds such as cyclohexane dimethanol, 2,4-diethylpentanediol, 2-ethyl-2-butyl-1,3-propanediol, neopentyl glycol, tricyclodecane dimethanol, Of polyhydric alcohols.

Examples of the acid anhydrides include methyl tetrahydrophthalic anhydride, methylnadic acid anhydride, nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butanetetracarboxylic acid anhydride, bicyclo [2,2,1] 3-dicarboxylic acid anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, cyclohexane-1,3,4-tricarboxylic acid-3,4- .

Particularly preferably,

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

Examples of the curing agent that can be used in combination with these carboxylic acids include amine compounds, acid anhydride compounds, amide compounds, phenol compounds and the like. Specific examples of the curing agent that can be used include a polyamide resin synthesized from diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, linolenic acid dimer and ethylene diamine Nitrogen-containing compounds (amines, amide compounds); Examples thereof include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, anhydrous nadic acid, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, Carboxylic acid anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, cyclohexane Acid anhydrides such as 1,3,4-tricarboxylic acid-3,4-anhydride; A carboxylic acid resin obtained by an addition reaction of various alcohols, carbinol-modified silicon and the above-mentioned acid anhydride; Bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, terpendiphenol, 4,4'-biphenol, 2,2'-biphenol, 3,3 ', 5,5'-tetramethyl- [1,1 (4-hydroxyphenyl) -4,4'-diol, hydroquinone, resorcin, naphthalene diol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis Ethane, phenols (phenol, alkyl substituted phenol, naphthol, alkyl substituted naphthol, dihydroxybenzene, dihydroxynaphthalene and the like) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, Bis (chloromethyl) -1,1'-biphenyl, 4,4'-bis (methoxymethyl) biphenyl, dihydroxyacetophenone, dicyclopentadiene, furfural, Polycondensates such as 1,1'-biphenyl, 1,4'-bis (chloromethyl) benzene or 1,4'-bis (methoxymethyl) benzene and their modified products, tetrabromobisphenol A Halogenated bisphenols, terpenes and phenols Polyphenols such as condensates; Imidazole, trifluoroborane-amine complexes, and compounds of guanidine derivatives, but are not limited thereto. These may be used singly or two or more of them may be used.

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

In the curable resin composition A of the present invention, a curing accelerator (curing catalyst) may be used together with the curing agent. Specific examples of the curing accelerator which can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole and 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) Tertiary amines such as diazabicyclo (5,4,0) undecene-7, phosphines such as triphenylphosphine, tetrabutylammonium salts, triisopropylmethylammonium salts, trimethyldecanylammonium salts, cetyltrimethylammonium salts, Quaternary ammonium salts such as hexadecyltrimethylammonium hydroxide, quaternary phosphonium salts such as triphenylbenzylphosphonium salts, triphenylethylphosphonium salts and tetrabutylphosphonium salts (the counter ions of the quaternary salts include halogens, organic acid ions , Zinc oxide (zinc oxide, zinc stearate, zinc myristylate), zinc oxide (zinc oxide), zinc oxide (zinc oxide) Phosphate ester And the like can be opened (octyl zinc phosphate, stearyl phosphate and zinc), a transition metal compound such as zinc compounds, such as (a transition metal salt). The curing accelerator is used in an amount of 0.01 to 5.0 parts by weight based on 100 parts by weight of the epoxy resin.

In the present invention, it is particularly preferable to use a quaternary phosphonium salt or a transition metal compound (transition metal salt) in order to maintain optical characteristics.

The curable resin composition A of the present invention may contain a phosphorus-containing compound as a flame retardance imparting component. The phosphorus-containing compound may be of reaction type or of addition type. Specific examples of the phosphorus-containing compound include trimethyl phosphate, triethyl phosphate, tricresyl phosphate, trixylallylenyl phosphate, cresyldiphenyl phosphate, cresyl-2,6-dicyclylenyl phosphate, Dicyclylenylenylphosphate), 1,4-phenylenebis (dicyclylenylenylphosphate), and 4,4'-biphenyl (diccyllyenylphosphate); 10,10-dihydro-9-oxa-10-phosphapenanthrene-10-oxide or 10 ; Containing epoxy resin obtained by reacting an epoxy resin with active hydrogens of the above-mentioned phosphates, and the like. Of these, phosphoric acid esters, phosphates or phosphorus-containing epoxy resins are preferable, and 1,3-phenylene bis (Dicyclylrenylphosphate), 4,4'-biphenyl (dicyclylenylphosphate) or a phosphorus-containing epoxy resin are particularly preferable. The content of the phosphorus-containing compound is preferably 0.6 or less times the total amount of the epoxy resin component in the curable resin composition A of the present invention. If it exceeds 0.6 times, the hygroscopicity and dielectric properties of the cured product may be adversely affected.

An antioxidant may be added to the curable resin composition A of the present invention if necessary. Examples of the antioxidant that can be used include phenol-based, sulfur-based, and phosphorus-based antioxidants. The antioxidant may be used alone or in combination of two or more. The amount of the antioxidant to be used is usually 0.008 to 1 part by weight, preferably 0.01 to 0.5 part by weight based on 100 parts by weight of the resin component A in the curable resin composition of the present invention.

Specific examples of the phenolic antioxidant include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6- Di-t-butyl-4-hydroxyphenyl) propionate, isooctyl-3- (3,5- Bis (n-octylthio) -6- (4-hydroxy-3,5-di-t-butyl anilino) -1,3,5-triazine, 2,4- ] -o-cresol; (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl- Butylphenol), 4,4'-butylidenebis (3-methyl-6-t-butylphenol), triethylene glycol-bis [3- (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 1,6-hexanediol- (3,5-di-t-butyl-4-hydroxy-hydrosinnamamide), 2,2-thio-diethylenebis [3- Hydroxyphenyl) propionate], 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, 3,9-bis [1,1- Propyloxy} ethyl] 2,4,8,10-tetraoxaspiro [5,5] undecane, bis (3,5-di-t-butyl- Butyl-4-hydroxybenzylsulfonic acid ethyl) calcium; Methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane, bis [3,3' (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, bis- (4'- Dihydroxybenzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione, 3,3,5-tris Phenol, and the like.

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

Specific examples of the phosphorus antioxidant include triphenyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, tris (nonylphenyl) phosphite, diisodecyl pentaerythritol phosphite, tris (2,4-di (2,4-di-t-butylphenyl) phosphite, cyclic neopentane tetraylbis (octadecyl) phosphite, cyclic neopentanetetraylbis (2,4-di-t-butyl-4-methylphenyl) phosphite, bis [2-t-butyl-6-methyl-4- {2- (octadecyloxycarbonyl) ethyl} phenyl] Phosphites such as fite; 10,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (3,5- Oxa-10-phosphaphenanthrene-10-oxide, 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10- And the like.

These antioxidants may be used alone, but two or more antioxidants may be used in combination. Particularly, in the present invention, an antioxidant of phosphorus is preferable.

Further, a light stabilizer may be added to the curable resin composition A of the present invention if necessary.

As the light stabilizer, a hindered amine light stabilizer, particularly HALS, is preferred. The HALS is not particularly limited, but typical examples thereof include dibutylamine, 1,3,5-triazine, N, N'-bis (2,2,6,6-tetramethyl- A polycondensation product of 6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine, dimethyl succinate-1- (2-hydroxyethyl) -4- 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} (1,1-dimethylethyl) -4-hydrxyphenyl] methyl] butyl malonate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis Oxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, 2- (3,5-di- (1,2,2,6,6-pentamethyl-4-piperidyl), etc. The HALS may be used alone or in combination of two or more.

A binder resin may be added to the curable resin composition A of the present invention as required. As the binder resin, a butyral resin, an acetal resin, an acrylic resin, an epoxy-nylon resin, an NBR-phenol resin, an epoxy -NBR resin, a polyamide resin, a polyimide resin, But are not limited thereto. The blending amount of the binder resin is preferably within a range that does not impair the flame retardancy and heat resistance of the cured product and is usually 0.05 to 50 parts by weight per 100 parts by weight of the resin component (the total amount of the epoxy resin and the binder resin) in the curable resin composition A of the present invention , Preferably 0.05 to 20 parts by weight, is used as needed.

An inorganic filler may be added to the curable resin composition A of the present invention, if necessary. Examples of the inorganic filler include powders such as crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, forsterite, stearate, spinel, titania and talc, Beads, and the like. However, the present invention is not limited thereto. These may be used singly or two or more of them may be used. The content of these inorganic fillers in the curing resin composition of the present invention in an amount of 95% by mass or less in A is used. Further, the curable resin composition A of the present invention may contain a silane coupling agent, stearic acid, palmitic acid, calcium stearate, zinc carboxylate (zinc 2-ethylhexanoate, zinc stearate, zinc behenate, zinc misstylate) Zinc, stearyl phosphate, etc.), various compounding agents such as surfactants, dyes, pigments, ultraviolet absorbers, and various thermosetting resins may be added.

When the curable resin composition A of the present invention is used for a photosemiconductor encapsulant, a phosphor may be added as needed. The phosphor has a function of absorbing a part of blue light generated from the blue LED element and forming white light by emitting wavelength-converted yellow light, for example. The phosphor is previously dispersed in the curable resin composition, and then the optical semiconductor is sealed. The phosphor is not particularly limited and conventionally known phosphors can be used. Examples of the phosphor include aluminates, thioglycates, and orthosilicates of rare earth elements. Specific examples of the phosphor include fluorescent materials such as a YAG fluorescent material, a TAG fluorescent material, an orthosilicate fluorescent material, a thiogallate fluorescent material, and a sulfide fluorescent material. 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 . As the particle diameter of such a fluorescent substance, those having a particle diameter known in the art are used, but the average particle diameter is preferably 1 to 250 mu m, particularly preferably 2 to 50 mu m. When these phosphors are used, the amount thereof is preferably 1 to 80 parts by weight, particularly preferably 5 to 60 parts by weight, per 100 parts by weight of the resin component.

The curable resin composition A of the present invention is obtained by uniformly mixing the above components. The curable resin composition A of the present invention can be easily made into the cured product by the same method as the conventionally known method. For example, the epoxy resin and the curing agent of the present invention and, if necessary, the curing accelerator, the phosphorus-containing compound, the binder resin, the inorganic filler and the compounding agent are mixed sufficiently by using an extruder, a kneader, The curable resin composition is molded and molded by using a mold or a transfer molding machine after potting and melting (in the case of a liquid phase, no melting), and then heated at 80 to 200 DEG C for 2 to 10 hours to obtain a cured product Can be obtained.

If necessary, the curable resin composition A of the present invention may be mixed with other components such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, N, N-dimethylformamide, N, N- To obtain a curable resin composition varnish and impregnating the glass fiber, the carbon fiber, the polyester fiber, the polyamide fiber, the alumina fiber and the paper into a base material and heating and drying the resulting prepreg, A cured product of the curable resin composition A may be used. The amount of the solvent used is usually from 10 to 70 mass%, preferably from 15 to 70 mass%, in the mixture of the curable resin composition A of the present invention and the above-mentioned solvent. Further, if the liquid composition is used, an epoxy resin cured product containing carbon fibers can be obtained, for example, by the RTM method.

In addition, when the curable resin composition A of the present invention is used in the form of a film or a sheet, it has a property that the flexibility and the like in the B stage are excellent. Such a film or sheet-like resin composition is obtained by applying the curable resin composition A of the present invention as a cured resin composition varnish on a release film, removing the solvent under heating, and then carrying out B staging. The resin composition on the film or sheet can be used as an adhesive (interlayer insulating layer) in a multilayer substrate or the like.

Curable resin composition B (cation curing by acidic curing catalyst)

The curable resin composition B of the present invention which is cured by using an acidic curing catalyst (cationic polymerization catalyst) contains a photopolymerization initiator or a thermal polymerization initiator as an acidic curing catalyst. Further, it may contain various known compounds and materials such as a diluent, a polymerizable monomer, a polymerizable oligomer, a polymerization initiator, and a photosensitizer. In addition, various known additives such as an inorganic filler, a coloring pigment, an ultraviolet absorber, an antioxidant, and a stabilizer may be contained as desired.

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

Examples of the cationic polymerization initiator that initiates the cationic polymerization of the curable resin composition B of the present invention by irradiation with an active energy ray include a diazonium salt, an iodonium salt, a sulfonium salt, a selenium salt, a pyridinium salt, a peloseminium salt, a phosphonium salt, And the like. Of these, diiodonium iodonium salts and dialkylphenacylsulfonium salts are preferable, and diaryliodonium salts are particularly preferably used.

(BF ₄ ^- , AsF ₆ ^- , SbF ₆ ^- , PF ₆ ^- , and B (C ₆ F ₅ ) are used as the anion when a cationic ionic polymerization initiator such as an iodonium salt and a sulfonium salt is used in the cationically curable resin composition B of the present invention. 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 photocationic polymerization initiator include bis (dodecylphenyl) iodonium hexafluoroantimonate (main component of UV-9380C manufactured by GE Toshiba Silicone Co., Ltd.), tolylcumyl iodonium tetrakis (pentafluorophenyl) (PHOSOILITIATOR 2074 manufactured by Rhodia), bis (alkyl (C = 10 to 14) phenyliodonium) hexafluoroantimonate (Wakayama Ion Polymerization Initiator WPI-016 manufactured by Wako Pure Chemical Industries, Ltd.).

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

Further, a sensitizer may be further added to the curable resin composition B of the present invention in order to improve the activity of the photocationic polymerization initiator, if necessary. As a sensitizer that can be used in the present invention, it is possible to use, for example, a compound disclosed in Adv. In Plymer Sci., 62, 1 (1984), which is Crybellogaster. Specific examples thereof include pyrene, perylene, acridine orange, thioxanthone, 2-chlorothioxanthone, and pentoflavin. Further, a compound widely used as a photo radical polymerization initiator can also be used. Specific examples thereof include benzophenone, 2,4-diethyl thioxanthone, 2-isopropyl thioxanthone, 2,4- Benzoin ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether; benzyl dimethyl ketal such as 2,2-dimethoxy-1,2-diphenyl ethane-1-one; 2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy- And? -Dicarbonyl compounds such as camphorquinone, and the like. In the present invention, thioxanthones and? -Hydroxyalkylphenols are particularly preferably used.

The blending amount of the cationic polymerization initiator in the curable resin composition B of the present invention can be suitably adjusted in accordance with the kind of the active energy ray and the irradiation amount. For example, in the case of ultraviolet rays, the amount is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts, and still more preferably 1 to 3 parts based on 100 parts by mass of the total amount of the cationically curable resin composition B. When the amount of the cationic polymerization initiator is less than 0.1 part, the curability may be poor. On the contrary, when the amount is more than 10 parts by weight, the amount of the component that is required for curing is decreased to decrease the physical properties of the cured product, There is work.

When the sensitizer is added to the curable resin composition B of the present invention, the compounding amount can be appropriately adjusted according to the kind of the active energy ray and the irradiation amount. For example, in the case of ultraviolet rays, it is preferably 5 parts by mass or less, more preferably 0.2 to 2 parts by mass with respect to 100 parts by mass of the total amount of the curable resin composition B. When the blending amount of the sensitizer is more than 5 parts by mass, there is a case where the hardness of the cured product is lowered by decreasing the components required for the cured product.

When the active energy ray is an ultraviolet ray or a visible light ray, the cationically curable resin composition is exposed to air, but the humidity of the atmosphere is preferably low, more preferably 80% RH or less and 70% RH or less. Here, when ultraviolet light or visible light is installed in the production line, a method of sending dry air to the front of the light irradiation device or a method of lowering the humidity by attaching a heating device may be adopted.

A compound which is activated by heat to initiate cationic polymerization, that is, a thermal cationic polymerization initiator may be used in the curable resin composition B of the present invention. Examples thereof include various onium salts such as quaternary ammonium salts, phosphonium salts and sulfonium salts, combinations of alkoxysilane and aluminum complexes, and the like. Examples of commercially available products include ADEKA OPTON CP-66 and ADEKA OPTON CP-77 (all trade names, manufactured by Asahi Denka Kogyo Co., Ltd.), Sun Aid SI-60L, Sun Aid SI-80L and Sun Aid SI- , Manufactured by SANSHIN KAGAKU KOGYO CO., LTD.), And CI series (manufactured by Nippon Soda Co., Ltd.).

The mixing 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, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the cationic curable resin composition, Is 0.5 to 3 parts. When the compounding ratio is less than 0.01 part by mass, the ring-opening reaction of the ring-opening polymerizable group can not sufficiently proceed even if the compound is activated by the action of heat. Further, even if it is blended in an amount exceeding 10 parts by mass, the action of progressing the polymerization does not become higher, and the physical properties of the cured product are lowered, which is not preferable.

In the curable resin composition B of the present invention, various additives such as inorganic fillers, silane coupling agents, release agents and pigments, and various compounding agents of various thermosetting resins may be added, if necessary. Specific examples thereof are as described above.

The curable resin composition B of the present invention is obtained by uniformly mixing each component. It is also possible to dissolve the curable resin composition B of the present invention uniformly in an organic solvent such as polyethylene glycol monoethyl ether, cyclohexanone or? -Butyrolactone, and then remove the solvent by drying. The solvent at this time is usually 10 to 70 mass%, preferably 15 to 70 mass%, in the mixture of the curable resin composition B of the present invention and the above-mentioned solvent.

The curable resin composition B of the present invention can be cured by heating and / or irradiation with ultraviolet rays (for example, Reference: General Synthetic Epoxy Resin Volume I, Fundamentals I p82-84), and the amount of heat and / The curing conditions are determined according to the respective compositions because they depend on the composition of the curable resin composition B. Basically, it is sufficient that the cured product is capable of exhibiting the strength required for the purpose of use. Generally, it is difficult to completely cure these curable resin compositions only by light irradiation. Therefore, in applications requiring heat resistance, it is necessary to complete the reaction completely by heating after light irradiation. In addition, since it is necessary to transmit the irradiating light at the time of photo-curing to detail, the epoxy resin and the curable resin composition B of the present invention require a compound and a composition having high transparency.

In the case of heating after the light irradiation, the curing can be performed in the curing temperature range of the general curable resin composition B. For example, a range of from room temperature to 150 DEG C for 30 minutes to 7 days is preferable. And the curable resin composition B, it is effective for accelerating the curing after the light irradiation to some extent, particularly in a high temperature range, and is effective for a short time heat treatment. If the temperature is low, a long heat treatment is required to some extent. This thermal after-cure also provides an effect of aging processing.

Further, the shape of the cured product obtained by curing these curable resin composition B can be variously selected depending on the use, and thus it is not particularly limited, but it can be, for example, a film, a sheet, or a bulk. The casting method varies depending on the site and member to be adapted. Examples of the molding method include a casting method, a casting method, a screen printing method, a spin coating method, a spraying method, a transfer method and a dispenser method. A suitable method may be employed to obtain the shape. A polishing glass, a hard stainless abrasive plate, a polycarbonate plate, a polyethylene terephthalate plate, a polymethylmethacrylate plate, or the like can be used as the mold. Further, a polyethylene terephthalate film, a polycarbonate film, a polyvinyl chloride film, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a polyimide film and the like can be used for improving the releasability of the mold and the curable resin composition B have.

For example, when used in a cation-curable resist, first, a curable resin composition B dissolved in an organic solvent such as polyethylene glycol monoethyl ether, cyclohexanone, or? -Butyrolactone is applied to a substrate such as a copper clad laminate, a ceramic substrate, By a screen printing method, a spin coating method or the like, and the coating film is preliminarily dried at 60 to 110 占 폚. (For example, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon or the like, laser light or the like) is passed through the obtained curable resin composition B on the substrate with a desired pattern drawn thereon and then exposed at 70 to 120 占 폚 Baking treatment is performed. Thereafter, the unexposed portion is dissolved and removed (developed) with a solvent such as polyethylene glycol monoethyl ether and, if necessary, sufficient by irradiation with ultraviolet rays and / or heating (for example, at 100 to 200 ° C for 0.5 to 3 hours) Curing is carried out to obtain a cured product. In this way, a printed wiring board can be obtained. Further, although the above method is the case of the negative type resist, the curable resin composition B of the present invention can also be used as the positive type 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 purposes including optical component materials. An optical material is a general material used for the purpose of passing light such as visible light, infrared light, ultraviolet light, X-ray, and laser through the material. More specifically, in addition to sealing materials for LEDs such as a lamp type and an SMD type, display materials are used in liquid crystal displays including liquid crystal display substrate materials, light guide plates, prism sheets, deflection plates, retardation plates, viewing angle correcting films, adhesives, Film and the like are used as the sealing material for color PDP (Plasma Display), antireflection film, optical compensation film, housing material, protective film for front glass, substitute material for front glass and adhesive agent which are expected as next generation flat panel displays A light guide plate, a prism sheet, a deflecting plate, a retardation plate, a polarizing plate, and the like in a plasma addressed liquid crystal (PALC) display, A viewing angle correcting film, an adhesive, and a polarizer protective film in an organic EL (electroluminescence) display A protection film, front glass substitution material and the adhesive or the like of the windshield, there may be mentioned various kinds of film substrate, front glass protection film, front glass substitution material and the adhesive or the like according to the transmission display (FED) in a field. In the field of optical recording, a disc substrate material for a VD (video disc), a CD / CD-ROM, a CD-R / RW, a DVD-R / DVD-RAM, a MO / MD, a PD , A protective film, a sealing material, and an adhesive.

In the field of optical instruments, a lens material for a still camera, a finder prism, a target prism, a finder cover and a light receiving sensor unit, a photographing lens of a video camera, a finder and the like are used as a projection lens, a protective film, Etc., materials for lenses of optical sensing devices, sealing materials, adhesives, and films. BACKGROUND ART In the field of optical components, optical fiber materials, ferrules, sealing materials and adhesives around optical connectors, fiber materials around optical switches, lenses, waveguides, sealing materials and adhesives of devices around optical switches, A lens, a waveguide, a sealing material for an LED, a sealing material for a CCD, an adhesive and the like, a substrate material around the optoelectronic integrated circuit (OEIC), a fiber material, a sealing material for the device and an adhesive. In the field of optical fibers, there are illuminations and light guides for decorative displays, sensors for industrial use, displays and signs, optical fibers for communication infrastructures and connecting digital devices in the home. In a semiconductor integrated circuit peripheral material, a resist material for microlithography for an LSI or a super LSI material can be given. In the field of automobiles and transportation vehicles, lamp reflector, bearing retainer, gear part, corrosion coat, switch part, head lamp, engine parts, electric parts, various internal and external parts, driving engine, brake oil tank, Panel glass, interior materials, wire harnesses for protection and binding, fuel hoses, automobile lamps and glass substitute products, and double-layer glass for railway vehicles, toughening agents for structural members of aircrafts, members around engines, wire harnesses for protection and binding, Coat and the like. In the field of construction, materials for interior and processing, electric covers, sheets, glass interlayers, glass substitutes, and solar cell materials are examples. In agricultural use, a house coating film and the like can be mentioned. As a next-generation optoelectronic functional organic material, organic EL device peripheral materials, organic photorefractive devices, optical amplifiers as optical-to-optical conversion devices, optical computing devices, substrate materials around organic solar cells, And adhesives.

Examples of the encapsulant include potting, dipping and transfer mold sealing used in capacitors, transistors, diodes, light emitting diodes, ICs and LSIs, underfills used in potting seals and flip chips used for COB, COF and TAB in IC and LSI, And sealing (reinforcement underfill) when mounting IC packages such as CSP or the like.

Examples of other uses of the optical material include general use in which the curable resin composition A or the curable resin composition B is used, and examples thereof include adhesives, paints, coating agents, molding materials (including sheets, films, FRP and the like) Materials (including printed boards, wire coatings, etc.), sealants, and additives to other resins. When the curable resin composition A or the curable resin composition B of the present invention is used as an additive to pavement paper, for example, it can be used as a curing agent in a cyanate resin composition for a sealing material or a substrate or in an acrylic ester resin as a curing agent for a resist . Examples of adhesives include civil engineering, construction, automotive, general office, medical and electronic materials. Among these, adhesives for electronic materials include adhesives for semiconductors such as build-up substrates, interlayer adhesives for multilayer boards, die bonding agents and underfills, BGA reinforcing underfills, anisotropic conductive films (ACF), and anisotropic conductive pastes Adhesive for mounting, and the like.

The curable resin composition of the second invention is described below.

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

Examples of the phenol resin contained in the second invention include bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, terpenediphenol, 4,4'-biphenol, 2,2'-biphenol, 3,3 ' -Tetramethyl- [1,1'-biphenyl] -4,4'-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2- (Phenol, alkyl substituted phenol, naphthol, alkyl substituted naphthol, dihydroxybenzene, dihydroxynaphthalene and the like) with formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde , o-hydroxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4'-bis (chloromethyl) Polycondensation products of 4'-bis (methoxymethyl) -1,1'-biphenyl, 1,4'-bis (chloromethyl) benzene and 1,4'-bis (methoxymethyl) Water, halogen such as tetrabromobisphenol A Bisphenols, there can be a polyphenol such as a condensation product of a terpene and a phenol, it is not limited to these. These may be used alone, or two or more kinds may be used.

The preferable phenol resin is a phenol aralkyl resin (a resin having an aromatic alkylene structure), particularly preferably a structure having at least one kind selected from phenol, naphthol and cresol, and the alkylene addition- A biphenyl structure, and a naphthalene structure (specifically, at least one resin selected from the group consisting of a cholesterol, a naphthol cholate, a phenol biphenylene novolac resin, a cresol-biphenylene novolak resin, a phenol- Resin and the like).

In the curable resin composition of the second invention, the amount of the curing agent containing a phenol resin is preferably 0.7 to 1.2 equivalents based on 1 equivalent of the epoxy group of the whole epoxy resin. When the amount is less than 0.7 equivalents or more than 1.2 equivalents based on one equivalent of the epoxy group, the curing is incomplete in all cases, and good curing properties may not be obtained.

As the polymerization catalyst contained in the curable resin composition of the second invention, any catalyst capable of initiating polymerization by heat or light can be used without limitation. Specifically, a curing accelerator or an acid curing catalyst can be used.

Specific examples of the curing accelerator which can be used include the same ones that can be used in the curable resin composition A of the first invention described above. When the curing accelerator is used, the amount of the curing accelerator used is the same as that of the curable resin composition A of the first invention.

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

Examples of the cationic polymerization initiator that initiates the cationic polymerization of the curable resin composition 2B of the present invention described later by irradiation of an active energy ray include the same ones that can be used in the curable resin composition B of the first invention described above.

A compound which activates by heat to initiate cationic polymerization, that is, a thermal cationic polymerization initiator, may be used for the curable resin composition 2B of the present invention. This also includes the same ones that can be used in the above-mentioned curable resin composition B of the first invention.

The use of a polymerization catalyst as an essential component in the curable resin composition of the second aspect of the present invention is accomplished by two methods of thermal curing (curable resin composition 2A) using a curing agent and cation curing (curable resin composition 2B) using an acid as a curing catalyst You can adapt.

The epoxy resin of the present invention can be used alone or in combination with another epoxy resin in the curable resin composition 2A and the curable resin composition 2B as in the curable resin composition of the first invention. When used in combination, the amount of another epoxy resin that can be used in combination is the same as the specific examples of the curable resin composition of the first invention described above.

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

Thermal curing by 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 above-mentioned carboxylic acids which can be used in the curable resin composition A of the first invention described above and other curing agents which can be used in combination with the above carboxylic acids.

In the present invention, a compound having an acid anhydride structure represented by the above-mentioned acid anhydride, carboxylic acid resin, and / or carboxylic acid structure is particularly preferable.

The amount of the curing agent used in the curable resin composition 2A of the present invention is also the same as 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 together with the curing agent. Specific examples of the curing accelerator which can be used include electric curing agents. When a curing accelerator is used, its amount is the same as that of the curable resin composition A of the first invention described above.

The curable resin composition 2A of the present invention may contain a phosphorus-containing compound as a flame retardancy-imparting component in the same manner as the curable resin composition A of the first invention described above. The specific examples of the phosphorus-containing compound and the amount thereof to be used are the same as those of the curable resin composition A of the first invention described above.

In addition, antioxidants may be added to the curable resin composition 2A of the present invention as necessary in the same manner as the curable resin composition A of the first invention described above. Specific examples of the antioxidant and the amount of the antioxidant which can be used are the same as those of the curable resin composition A of the first invention described above.

In addition, a light stabilizer may be added to the curable resin composition 2A of the present invention as necessary in the same manner as the curable resin composition A of the first invention described above.

Specific examples of the light stabilizer are the same as the curable resin composition A of the first invention described above.

In the curable resin composition 2A of the present invention, a binder resin may be blended as necessary in the same manner as the curable resin composition A of the first invention described above. Specific examples of the binder resin and the amount thereof to be used are the same as those of the curable resin composition A of the first invention described above.

An inorganic filler may be added to the curable resin composition 2A of the present invention as necessary in the same manner as the curable resin composition A of the first invention described above. Specific examples of the inorganic filler and the amount of the inorganic filler are 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 in a photosemiconductor encapsulant, a phosphor may be added as required in the same manner as the curable resin composition A of the first invention described above. Specific examples of the phosphor and the amount of the phosphor are 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 in the same manner as the curable resin composition A of the first invention described above, and can be easily made into the cured resin by a method similar to a conventionally known method.

The curable resin composition A of the present invention can be made into a cured product by the same method as the above-mentioned curable resin composition A of the first invention.

Curable resin composition 2B (cation curing by acidic curing catalyst)

The curable resin composition 2B of the present invention which is cured using an acidic curing catalyst contains a photopolymerization initiator or a thermal polymerization initiator as an acid curing catalyst as in the curable resin composition B of the first invention described above and further contains a diluent, Various kinds of known compounds such as a polymerizable oligomer, a polymerization initiator, and a photosensitizer may be contained, and if desired, various kinds of known additives such as an inorganic filler, a coloring pigment, an ultraviolet absorber, an antioxidant, Maybe.

As with the curable resin composition B of the first invention described above, a cationic polymerization initiator is preferable as the acidic curing catalyst, and a light or thermal cationic polymerization initiator is particularly preferable. Can be used as the curable resin composition 2B by blending a cation polymerization initiator activated by an active energy ray and / or a cation polymerization initiator activated by heat.

Examples of the cationic polymerization initiator that initiates the cationic polymerization of the curable resin composition 2B of the present invention by irradiation with active energy rays include the same ones that can be used in the curable resin composition B of the first invention described above.

The active energy ray when curing the curable resin composition 2B of the present invention is the same as that of the curable resin composition B of the first invention described above.

Further, a sensitizer may be further added to the curable resin composition 2B of the present invention in the same manner as the curable resin composition B of the first invention described above, if necessary, to improve the activity of the photocationic polymerization initiator. Examples of the sensitizer that can be used in the present invention include the same ones that can be used in the curable resin composition B of the first invention described above and can be suitably used as well as the curable resin composition of the first invention B is the same.

The blending amount when the sensitizer is added to the curable resin composition 2B of the present invention and the irradiation conditions of the active energy ray are the same as those of the curable resin composition B of the first invention described above.

A compound capable of being activated by heat to initiate cationic polymerization, that is, a thermal cationic polymerization initiator, may be used in the curable resin composition 2B of the present invention. However, even in this case, the specific examples and the compounding ratios are the same as those of the curable resin composition B of the first invention .

The curable resin composition 2B of the present invention may contain various additives such as inorganic filler, silane coupling agent, releasing agent and pigment as described above and various thermosetting resins in addition to the curable resin composition B of the first invention described above can do.

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

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 purposes.

A coating material, a molding material (including a sheet, a film, an FRP, and the like), an insulating material (a printed board, a wire cover Etc.), additives for other resins in addition to a sealant, and the like. Examples of the adhesive include adhesives for civil engineering, construction, automobile, general office and medical use, as well as adhesives for electronic materials. Among these, adhesives for electronic materials include adhesives for semiconductors such as die-bonding agents and underfills, underfill for BGA reinforcement, anisotropic conductive films (ACF), and anisotropic conductive pastes (ACP) Adhesive for mounting, and the like.

As sealant and substrate, there are potting, dipping, transfer mold sealing for capacitors, transistors, diodes, light emitting diodes, ICs and LSIs, potting seals for COBs, COFs and TABs for ICs and LSIs, (Including underfill for reinforcement) and package substrates for mounting IC packages such as underfill, QFP, BGA, and CSP. It is also preferable to use a network substrate or a module substrate which requires a function as a module substrate.

Example

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. The physical properties in Examples were measured by the following methods.

Various analytical methods used in the examples are described below.

Epoxy equivalent: according to JIS K 7236 (ISO 3001)

ICI melt viscosity: according to JIS K 7117-2 (ISO 3219)

Softening point: according to JIS K 7234

Total chlorine: According to JIS K 7243-3 (ISO 21672-3)

Chloride ion: According to JIS K 7243-1 (ISO 21672-1)

Sodium ion: Determined by ion chromatography

Iron: ICP emission spectrometric analysis

Refractive index: according to ISO 5661

Gardner Colors: ISO 4630-1 compliant

GPC: Column (Shodex KF-603, KF-602x2, KF-601x2)

The connecting eluent was tetrahydrofuran

The flow rate is 0.5 ml / min.

The column temperature was 40 [

Detection: RI (differential refraction detector)

Synthesis Example 1

A flask equipped with a stirrer, a reflux condenser and an agitator was evacuated once and purged with nitrogen, and then a nitrogen purge (2 L / hr) was carried out to obtain a phenol compound (DPPI1) Compound SABIC PPPBP having a purity of 99% or more, 200 ppm of residual phenolphthalein, iron content <5 ppm), 842 parts of epichlorohydrin and 168 parts of methanol were added, and the water bath was heated to 75 ° C. At the time when the internal temperature exceeded 65 캜, 21 parts of sodium hydroxide on the crepe was added in portions over 90 minutes, and the reaction was further performed at 70 캜 for 1 hour. After completion of the reaction, the reaction mixture was washed with water, and a solvent such as excess epichlorohydrin was distilled off from the oil layer under reduced pressure at 140 占 폚 using a rotary evaporator. 200 parts of methyl isobutyl ketone was added to the residue and dissolved, and the temperature was raised to 70 캜. 26 parts of an aqueous solution of 30% by weight of sodium hydroxide was added under stirring, and the reaction was conducted for 1 hour. Thereafter, the reaction mixture was washed with water until the wash water became neutral, and the obtained solution was treated with methyl isobutyl Ketone and the like were distilled off to obtain 301 parts of an epoxy resin (EP1). The obtained epoxy resin had an epoxy equivalent of 266 g / eq., A softening point of 88 占 폚, an ICI melt viscosity of 0.44 Pa 占 퐏 (150 占 폚), chlorine ion of 2 ppm, sodium ion of 0.5 ppm and color of 0.2 or less (Gardner 40% THF solution). The structure of the above formula (1) was 93 area% (GPC). The refractive index was 1.63. (A typical epoxy and cresol novolak type epoxy resins have a refractive index of 1.59, which is very large).

Synthesis Example 2

A 1 L flask equipped with a stirrer, a reflux condenser and a stirrer was charged with a phenol compound (DPPI1) (the compound SABIC PPPBP having a substituent R as a whole in the above formula (1), purity 99 255 parts of residual phenolphthalein, iron content of 5 ppm), 601 parts of epichlorohydrin and 180 parts of methanol were added, and the water bath was heated to 75 占 폚. After confirming that the internal temperature exceeded 65 占 폚 after elapse of 1.5 hours (nitrogen injection of about 3 times of the flask) from the start of the nitrogen purge, 21 parts of sodium hydroxide on the flakes was dividedly added over 90 minutes. Thereafter, the reaction was further carried out at 70 DEG C for 1 hour. After completion of the reaction, the reaction mixture was washed with water, and a solvent such as excess epichlorohydrin was distilled off from the oil layer under reduced pressure at 140 占 폚 using a rotary evaporator. 200 parts of methyl isobutyl ketone was added to the residue and dissolved, and the temperature was raised to 70 캜. And 5 parts of an aqueous solution of 30% by weight of sodium hydroxide were added thereto under stirring. After the reaction was carried out for 1 hour, washing was carried out until the washing water became neutral, and the obtained solution was treated with methyl isobutyl Ketone and the like were distilled off to obtain 300 parts of an epoxy resin (EP2). The obtained epoxy resin had an epoxy equivalent of 270 g / eq., A softening point of 90 占 폚, an ICI melt viscosity of 0.46 Pa 占 퐏 (150 占 폚), chlorine ion of 2 ppm, sodium ion of 0.5 ppm and color of 0.2 or less (Gardner 40% THF solution). The structure of the above 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, 256 parts phenol compound (DPPI1) (200 ppm of residual phenolphthaleine having a purity of 99% or higher and a content of iron powder of 5 ppm) of the compound SABIC PPPBP in which all substituent groups R in the formula (1) 661 parts of epichlorohydrin and 3 parts of benzyltrimethylammonium chloride were added, and the water bath was heated to 70 占 폚. 100 parts of a 49% aqueous solution of sodium hydroxide was added dropwise thereto over 90 minutes, and the reaction was further carried out at 70 DEG C for 4 hours. After completion of the reaction, the reaction mixture was washed with water, and excess epichlorohydrin and other solvents were distilled off from the oil layer using a rotary evaporator at 140 DEG C under reduced pressure to obtain 290 parts of an epoxy resin (EP3). The obtained epoxy resin had an epoxy equivalent of 297 g / eq., A softening point of 95 占 폚, an ICI melt viscosity of 0.70 Pa 占 퐏 (150 占 폚), a total chlorine content of 10450 ppm, a hydrolyzable chlorine content of 9700 ppm, a chlorine ion content of 0.5 ppm, (Gardner 40% THF solution). The structure of the above formula (1) was 65 area% (GPC).

Synthesis Example 4

A flask equipped with a stirrer, a reflux condenser and a stirrer was charged with 15 parts of tricyclodecane dimethanol, 70 parts of methylcyclohexanedicarboxylic acid anhydride (Shin-Nippon Rika Rescad MH) , 15 parts of 2,4-tricarboxylic acid-1,2-anhydride (H-TMAn, manufactured by Mitsubishi Gas Chemical Company) were added and reacted at 40 ° C for 3 hours, followed by heating and stirring at 70 ° C for 1 hour (1% by area or less) of tricyclodecane dimethanol was confirmed.) 100 parts of curing agent composition (H-1) containing carboxylic acid and acid anhydride were obtained. The obtained curing agent composition (H-1) was a colorless liquid resin, and its purity by GPC was found to be 37% by area of carboxylic acids (formula 6), acid anhydride (cyclohexane-1,2,4-tricarboxylic acid- 1,2-anhydride) was 11% by area and acid anhydride (methylcyclohexanecarboxylic anhydride) was 52% by area. The functional group equivalent was 171 g / eq.

Example 1, Comparative Example 1

Epoxy resin (EP1) obtained in Synthesis Example 1 and bisphenol A type epoxy resin (jER828 manufactured by Mitsubishi Chemical) as comparative examples were each cocurrently cured with an alicyclic epoxy resin (Celloxide 3150 manufactured by Daicel Kogyo Kabushiki Kaisha) The catalyst (SI-150L, manufactured by SANSHIN KAGAKU KOGYO KABUSHIKI KAISHA) was blended in a ratio of 53: 47: 2 to prepare a 55% solution of methyl ethyl ketone. The resultant solution was impregnated with a glass cloth (Unitica) of E glass having a thickness of 40 microns and the solvent was volatilized at 150 DEG C for 4 minutes to prepare a prepreg. Thereafter, preheating was performed at 150 占 폚 for 1 minute, followed by compression molding at 150 占 폚 and 30 kg / cm2 for 15 minutes, and finally curing was carried out at 150 占 폚 for 3 hours. The obtained film was cut into a size of 10 x 40 mm, and retardation, which is an index of birefringence, was measured. The thickness of the film was 56 mu m.

The measurement of the retardation was carried out under the following conditions.

Measuring instrument: Ellipso M-220 (Nippon Bunko)

Incidence angle: 90 degrees

Bandwidth: 1.0nm

Measuring range: 0.1 to 0.4 kgf

Measured wavelength: 550 nm

As a result, it was found that the use of the epoxy resin EP1 exhibited retardation of 0.4 to 0.8 mu m, and the use of the comparative bisphenol A type epoxy resin showed retardation in the range of 0.7 to 1.6 mu m.

Further, the retardation is a phase difference. The smaller the smaller the retardation is, the more preferable. From this result, it can be confirmed that the epoxy resin composition of the present invention has a low retardation, that is, a low birefringence.

Examples 2, 3 and 4, Comparative Example 2

As an example, the epoxy resin (EP1) obtained in Synthesis Examples 1 and 2 and (EP2) were used as comparative examples and the epoxy resin (EP3) obtained in Synthesis Example 3 was used and blended at the blending ratios shown in Table 1 below. The obtained curable resin composition was prepared by volatilizing the solvent in a Teflon (registered trademark) plate at 80 DEG C for 20 minutes for Examples 2 and 3 and Comparative Example 2, and for the Example 4, the solvent volatilization conditions were 150 DEG C And the resulting film was cut off. The prepared film was cut out, and 0.9 g of the test piece for a test piece having a width of 7 mm and a length of 5 cm was stacked and pressed. The resultant was pressed at 150 캜 and 30 kg / cm 2 for 15 minutes, By weight. All were molded to a thickness of 0.7 to 0.8 mm. The obtained plate was evaluated for transparency. For the evaluation of transparency, COH400, a color and turbidity simultaneous measuring device manufactured by Nippon Denshoku Co., Ltd., was used and compared with 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 purged with nitrogen (oxygen concentration: 4.9%) once under vacuum, and subjected to nitrogen purge (2 L / hr) 256 parts of residual phenolphthalein having a purity of 99% or more and a residual iron content of 5 ppm), 842 parts of epichlorohydrin and 180 parts of methanol were added in the compound (1) wherein all substituents R were hydrogen atoms, and the water bath was heated to 75 캜 did. At the time when the internal temperature exceeded 65 占 폚, 21 parts of sodium hydroxide on the flakes was added in portions over 90 minutes, and the reaction was further carried out at 70 占 폚 for 1 hour. After completion of the reaction, the reaction mixture was washed with water, and a solvent such as excess epichlorohydrin was distilled off from the oil layer under reduced pressure at 140 占 폚 using a rotary evaporator. 600 parts of methyl isobutyl ketone was added to the residue and dissolved, and the temperature was raised to 70 占 폚. 26 parts of an aqueous solution of 30% by weight of sodium hydroxide was added under stirring, and the reaction was conducted for 1 hour. Thereafter, the reaction mixture was washed with water until the wash water became neutral, and the obtained solution was treated with methyl isobutyl Ketone and the like were distilled off to obtain 305 parts of an epoxy resin (EP2-1). The obtained epoxy resin had an epoxy equivalent of 266 g / eq., A softening point of 89 占 폚, an ICI melt viscosity of 0.42 Pa 占 퐏 (150 占 폚), a total chlorine content of 1600 ppm, a hydrolyzable chlorine of 1540 ppm, a chlorine ion of 2 ppm, (Gardner 40% MEK (methyl ethyl ketone) solution). The structure of the above 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 purged with nitrogen (oxygen concentration: 5.3%) once under vacuum, and subjected to nitrogen purge (2 L / hr) The reaction was carried out in the same manner as in Synthesis Example 2-1 except that the compound SABIC PPPBP having a purity of not less than 99% and 200 ppm of residual phenolphthalein, and 500 ppm of phenolphthalein in addition to iron in an amount of 5 ppm was used as the substituent R in the formula (1). The obtained epoxy resin (EP2-2) had an epoxy equivalent of 266 g / eq., A softening point of 90 占 폚, an ICI melt viscosity of 0.44 Pa 占 퐏 (150 占 폚), a total chlorine content of 2000 ppm, a hydrolyzable chlorine of 1950 ppm, a chlorine ion of 1 ppm, ppm, color 0.2 (Gardner 40% MEK solution). The structure of the above formula (1) was 93 area% (GPC).

Synthesis Example 2-3

(DPPI1) ((1)) was added to a 1 L four-necked flask equipped with a stirrer, a reflux condenser and a stirrer under nitrogen purge for 30 minutes at 4 L / h (oxygen concentration 6.5% 256 parts of a compound SABIC PPPBP having a purity of 99% or more and 200 ppm of residual phenolphthalein, iron content <5 ppm), 661 parts of epichlorohydrin and 165 parts of methanol were added in the above formula (1) It has warmed up. At the time when the internal temperature exceeded 65 占 폚, 57 parts of sodium hydroxide on the flakes was dividedly added over 90 minutes, and the reaction was further performed at 70 占 폚 for 1 hour. After completion of the reaction, the reaction mixture was washed with water, and a solvent such as excess epichlorohydrin was distilled off from the oil layer under reduced pressure at 140 占 폚 using a rotary evaporator. 600 parts of methyl isobutyl ketone was added to the residue and dissolved, and the temperature was raised to 70 占 폚. And 5 parts of an aqueous solution of 30% by weight of sodium hydroxide were added thereto under stirring. After the reaction was carried out for 1 hour, washing was carried out until the washing water became neutral, and the obtained solution was treated with methyl isobutyl Ketone and the like were distilled off to obtain 297 parts of an epoxy resin (EP2-3). The obtained epoxy resin had an epoxy equivalent of 277 g / eq., A softening point of 96 占 폚, an ICI melt viscosity of 0.62 Pa 占 퐏 (150 占 폚), a total chlorine content of 2230 ppm, a hydrolyzable chlorine content of 2100 ppm, a chlorine ion content of 0.5 ppm, (Gardner 40% MEK solution). The structure of the above formula (1) was 82 area% (GPC).

Synthesis Example 2-4

(DPPI1) (obtained in the above (1)) was introduced into a 1 L four-necked flask equipped with a stirrer, a reflux condenser and a stirrer under nitrogen purge and oxygen purge at 5.2% 256 parts of a compound SABIC PPPBP having a purity of 99% or more and 200 ppm of residual phenolphthalein, an iron content of <5 ppm), 661 parts of epichlorohydrin and 200 parts of dimethyl sulfoxide were added in the formula (1) . When the internal temperature exceeded 40 占 폚, 57 parts of sodium hydroxide on the flakes was dividedly added over 90 minutes, and the reaction was further performed at 70 占 폚 for 1 hour. After completion of the reaction, the reaction mixture was washed with water, and a solvent such as excess epichlorohydrin was distilled off from the oil layer under reduced pressure at 140 占 폚 using a rotary evaporator. 600 parts of methyl isobutyl ketone was added to the residue and dissolved, and the temperature was raised to 70 占 폚. 16 parts of an aqueous solution of 30% by weight of sodium hydroxide was added under stirring, and the reaction was carried out for 1 hour. Thereafter, the mixture was washed with water until the washing water became neutral, and the resulting solution was concentrated under reduced pressure at 180 캜 using methyl isobutyl Ketone and the like were distilled off to obtain 300 parts of an epoxy resin (EP2-4). The obtained epoxy resin had an epoxy equivalent of 270 g / eq., A softening point of 92 占 폚, an ICI melt viscosity of 0.48 Pa 占 퐏 (150 占 폚), a total chlorine content of 1050 ppm, a hydrolyzable chlorine of 960 ppm, a chlorine ion of 0.3 ppm, (Gardner 40% MEK solution). The structure of the above formula (1) was 90 area% (GPC).

Examples 2-1, 2-2, 2-3 and Comparative Example 2-1

The epoxy resin obtained above was blended according to the formulation shown in Table 2 below and cured at 120 占 폚 for 2 hours, 160 占 폚 for 2 hours and 180 占 폚 for 4 hours, and flammability test was carried out. The method of testing the flame retardancy is described below.

Flammability

Determination of flame retardancy: It was conducted in accordance with UL94. However, the sample size was 12.5 mm in width x 150 mm in length and 0.8 mm in thickness.

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

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

The present application is based on Japanese Patent Application (Japanese Patent Application No. 2012-129406 and Japanese Patent Application No. 2012-129408) filed on June 7, 2012, the entirety of which is incorporated by reference. Also, all references cited herein are incorporated by reference in their entirety.

(Industrial availability)

The epoxy resin composition of the first invention can be used for various purposes including optical component materials. The curable resin composition of the second aspect of the present invention can be applied to adhesives, paints, coatings, molding materials (including sheets, films, FRP and the like), insulating materials (including printed boards and wire coatings) Can be used.

Claims (11)

An epoxy resin composition comprising an epoxy resin obtained by the reaction of a phenolic resin represented by the following formula (1) with epihalohydrin and a carboxylic acid and / or a cationic polymerization catalyst, wherein the epoxy resin is obtained by a Gardner colorimetric method (40 % MEK solution) is not more than 2 in color.

Wherein the plurality of R's present 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 method according to claim 1,
Wherein the amount of the residual phenolphthalein derivative in the phenol resin reacted with the epihalohydrin is 2% or less. The method according to claim 1,
Wherein the residual iron content in the phenol resin reacted with epihalohydrin is 50 ppm or less. The method of claim 3,
Wherein the epoxy resin composition contains a transition metal salt. The method of claim 3,
A quaternary ammonium salt, and a quaternary phosphonium salt. The method of claim 3,
An epoxy resin composition comprising a cationic polymerization initiator. An epoxy resin cured product obtained by curing the epoxy resin composition according to any one of claims 4 to 6. 7. The method according to any one of claims 1 to 6,
Wherein the epoxy resin composition is a glass substitute. A curable resin composition characterized by containing an epoxy resin represented by the following formula (2), a phenol resin and / or a polymerization catalyst.

Wherein the plurality of R's present 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 method of claim 9,
Wherein the phenol resin is a phenol aralkyl resin (a resin having an aromatic alkylene structure). 10. The method of claim 9,
Wherein the polymerization catalyst is a cationic polymerization catalyst.