CN100513453C - Alicyclic epoxy resins, their preparation process, their compositions, epoxy resin cured product, and uses of alicyclic epoxy resin compositions - Google Patents
Alicyclic epoxy resins, their preparation process, their compositions, epoxy resin cured product, and uses of alicyclic epoxy resin compositions Download PDFInfo
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- CN100513453C CN100513453C CNB2004800265609A CN200480026560A CN100513453C CN 100513453 C CN100513453 C CN 100513453C CN B2004800265609 A CNB2004800265609 A CN B2004800265609A CN 200480026560 A CN200480026560 A CN 200480026560A CN 100513453 C CN100513453 C CN 100513453C
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Abstract
An alicyclic epoxy resin which is solid at ordinary temperature, has excellent transparency, and is suitable for use in optical materials, coating materials, etc. The alicyclic epoxy resin satisfies the following requirements (a) to (d): (a) to have an epoxy equivalent of 500 to 10,000; (b) to have a degree of nucleus hydrogenation of 96% or higher; (c) to have a softening temperature, as measured by the ring-and-ball method as provided for in JIS-K-7234, of 40 to 200 DEG C; and (d) to have a light transmittance, as measured at a wavelength of 400 nm, of 90% or higher.
Description
Technical field
The present invention relates to alicyclic epoxy resin.In detail, the present invention relates to be the method for solid alicyclic epoxy resin and this alicyclic epoxy resin by the aromatic nucleus hydrogenation of aromatic epoxy resin being made be suitable as under the normal temperature of optics with the raw material of material or coating material etc.
In addition, the present invention relates to and to have cooperated the composition epoxy resin of hardener for epoxy resin, the epoxy resin cured product that obtains with solidifying this composition epoxy resin, with the luminous element sealing material that uses this composition epoxy resin, particularly relate to, because water white transparency can be provided, resistance to cracking, the cured article of photostabilization excellence, therefore can be used in coating material, light solidified material and LED (photodiode), the relevant electric and electronic of photosemiconductors such as CCD is with material etc., particularly as the useful composition epoxy resin of sealing material of the LED of the light that sends the short wavelength, the epoxy resin cured product that obtains with solidifying this composition epoxy resin, with the luminous element sealing material that uses this composition epoxy resin.
Background technology
Because Resins, epoxy has excellent thermotolerance, cementability, water tolerance, physical strength, electrical characteristic etc., therefore be used in the various fields such as insulating material of caking agent, coating, civil construction material, electrical and electronic parts.As the Resins, epoxy that uses in these purposes, aromatic epoxy resins such as bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenolic aldehyde or cresols phenolic resin varnish type epoxy resin normally, in addition, look purposes and also use the aromatic epoxy resin that obtains by various phenoloids.
In addition, alicyclic epoxy resin can be made, use with following method: with the carbon-to-carbon double bond process for epoxidation, make the method for the pure and mild epihalohydrins of polynary ester ring type reaction, the aromatic nucleus of aromatic epoxy resin carried out the method for hydrogenation (abbreviating nuclear hydrogenation as) etc.
In alicyclic epoxy resin, the hydrogenated epoxy resin that particularly aromatic epoxy resin is carried out nuclear hydrogenation and obtain is because photostabilization, the transparency or the impurity such as cation-curable excellence, chlorine compound of cured article are few etc., therefore can expect to be used in purposes such as sealing material, optical material, coating material, caking agent, for example, be useful to sealing of luminescent materials such as photodiode etc.
As making the method for aromatic epoxy resin being carried out the pairing hydrogenated epoxy resin of nuclear hydrogenation, various schemes had been proposed in the past.Can enumerate, for example, in the presence of the hydrogenation catalyst that supports rhodium or ruthenium on the non-active carriers such as gac, carry out nuclear hydrogenation method (patent documentation 1), use the catalyzer supported the high metal of ruthenium and electronegativity carry out nuclear hydrogenation method (patent documentation 2), use in specific surface area at 5～600m
2The catalyzer that supports rhodium or ruthenium on the carbon support of the scope of/g carries out the method for nuclear hydrogenation (patent documentation 3) etc., the loss that has also proposed nuclear hydrogenation rate height and epoxy group(ing) Resins, epoxy (patent documentation 4) few (i.e. decomposition of little in the nuclear hydrogenation reaction), that cl content is low.In addition, the hydrogenated epoxy resin few about impurity, that light penetration is excellent (patent documentation 5) has also been proposed.
But these are the report about the nuclear hydrogenationization of the low-molecular-weight epoxy resin of widely used bisphenol A-type or Bisphenol F type mostly, and the hydrogenated epoxy resin that obtains is liquid at normal temperatures, mainly are to make composition to be used in liquid airproof, injection molding etc.
On the other hand, the aromatic epoxy resin that molecular weight is high is solid-state at normal temperatures, obtains being under the normal temperature solid-state hydrogenated epoxy resin during with its nuclear hydrogenation.Nuclear hydrogenationization existing enumerate (patent documentation 1,2,6) in a plurality of documents for high molecular aromatic Resins, epoxy, the nuclear hydrogenationization of high-molecular weight aromatic epoxy resin is compared with low molecular weight aromatic Resins, epoxy, reactive low, the nuclear hydrogenation difficulty.Therefore, in method in the past, in order to suppress the decomposition in the nuclear hydrogenation reaction, it is necessary reacting under high pressure, low temperature, lower concentration, in addition, Resins, epoxy uses catalyzer in a large number relatively, can not nuclear hydrogenationization if just do not react for a long time, it is expensive that the catalysis expense becomes, in addition, productivity reduces, and also is not satisfied economically.
And, in the nuclear hydrogenationization of high molecular aromatic Resins, epoxy, be difficult to obtain the general good hydrogenated epoxy resin of rerum natura such as nuclear hydrogenation rate, epoxy group(ing) conservation rate, form and aspect, in method in the past, having enumerated the nuclear hydrogenation rate is 80～96% (patent documentations 1,2,6), is the example that the high molecular aromatic Resins, epoxy more than 500 or 500 reacts with the high nuclear hydrogenation rate more than 95% or 95% but do not make epoxy equivalent (weight).In addition, about the outward appearance or the not record fully of proterties of the hydrogenated epoxy resin that obtains,, produce the bad phenomenon of the purposes that is not suitable for requiring the transparency in most cases because residual catalyzer etc. make Resins, epoxy painted.
In addition, in recent years, various display panels, image read with light source, traffic signals, giant display with unit etc. in the photosemiconductor light-emitting device major parts such as (LED) of practicability make by resin-sealed.Sealing resin used herein contains above-mentioned aromatic epoxy resin and usually as the ester ring type acid anhydrides of solidifying agent.But, the resin cured matter of these LED element sealings is ftractureed easily existing problems when under exacting terms, using owing to cold cycling.
In addition, because the rapid development of the LED of today, the high-output powerization and the short wavelengthization of LED element are carried out rapidly, particularly use the LED of nitride-based semiconductor owing to can send the light of short wavelength and high-output power, so its practicability are made progress constantly.But, when having used the LED element of nitride-based semiconductor,, therefore pass in time because aromatic nucleus absorbs short wavelength's light with above-mentioned aromatic epoxy resin sealing, cause the deterioration of the resin of sealing, produce because the problem that xanthochromia significantly descends luminosity.
Therefore, having proposed to use will be with 3,4-epoxycyclohexyl methyl-3 ', the LED (patent documentation 7, patent documentation 8) that the alicyclic epoxy resin that 4 '-epoxycyclohexane carboxylate obtains for the cyclic olefin oxidation of representative seals.But the cured article of this alicyclic epoxy resin is highly brittle, because cold cycling produces be full of cracks destruction, and wet fastness is extreme difference also, therefore is not suitable for requiring the purposes of long-term reliability easily.
Therefore, the someone has proposed hydrogenation bisphenol A type epoxy resin with liquid state as main body, cooperates alicyclic epoxy resin and phosphoric acid kind antioxidant, the LED (patent documentation 9) that uses the methylhexahydrophthalic anhydride solidifying agent to seal.But, though this epoxy resin cured product water white transparency excellence, but still embrittlement, on the purposes of the LED element that seals the special requirement resistance to cracking, be inadequate.
In addition, as the method for high-efficiency and continuous ground sealing LED, the method for using low pressure transfer mould shaper sealing LED is arranged.In the method,, therefore, compare with the method for using liquid LED sealing material owing to use the solid state LED sealing material, can be with a large amount of sealing LEDs of high productivity.In addition, owing to use high molecular expoxy resin, the curable epoxide thing that obtains is very tough, and resistance to cracking significantly improves.Usually, this solid state LED sealing material use Resins, epoxy can be by using the high-molecular weight bisphenol A type epoxy resin and making with the mixing roll continuous mixing as the anhydride compound and the curing catalyst of solidifying agent.
But therefore deterioration expects the high molecular alicyclic epoxy resin that has excellent photostability to above-mentioned aromatic epoxy resin strongly because aromatic nucleus absorbs short wavelength's light.Therefore, can consider to carry out the nuclear hydrogenationization of high molecular aromatic Resins, epoxy, obtain the high-molecular weight alicyclic epoxy resin, but, present situation is, as mentioned above, the nuclear hydrogenationization of high-molecular weight aromatic epoxy resin is very difficult, and the hydrogenated epoxy resin that obtains does not have performances such as good nuclear hydrogenation rate, epoxy group(ing) conservation rate, form and aspect.And in such colored rings epoxy resins, except the transparency, it also is inappropriate being used in the seal applications that requires sunproof luminous element.
Patent documentation 1: No. 3336241 communique of United States Patent (USP)
Patent documentation 2: the spy opens flat 10-204002 communique
Patent documentation 3: the spy opens flat 11-217379 communique
Patent documentation 4: the spy opens flat 11-199645 communique
Patent documentation 5: the spy opens the 2003-81957 communique
Patent documentation 6:EP-545154A1 communique
Patent documentation 7: the spy opens flat 9-213997 communique
Patent documentation 8: the spy opens the 2000-196151 communique
Patent documentation 9: the spy opens the 2003-12896 communique
Summary of the invention
The problem that invention will solve
Therefore, the problem that the present invention will solve is to provide a kind of alicyclic epoxy resin manufacture method and this alicyclic epoxy resin, this alicyclic epoxy resin is that aromatic epoxy resin is carried out the hydrogenated epoxy resin that nuclear hydrogenationization obtains, and nuclear hydrogenation rate height, the transparency excellent, be suitable for optical material or coating material etc. be the solid alicyclic epoxy resin at normal temperatures.
In addition, the purpose of invention is, hydrogenation rate in the time of can solving the high molecular expoxy resin nuclear hydrogenation, the problem points of form and aspect are provided, and bring the cured article of water white transparency, resistance to cracking, photostabilization, excellent heat resistance, particularly solidify and epoxy resin cure body that obtains and the luminous element sealing material that uses this composition epoxy resin as the useful composition epoxy resin that contains solid-state hydrogenated epoxy resin of the LED sealing material of the light that sends the short wavelength with this composition epoxy resin.
Solve the means of problem
The present invention includes a plurality of one group of relevant invention, the main points of each invention are as follows.
The 1st main points of the present invention are a kind of alicyclic epoxy resin, it is characterized in that, satisfy the regulation of following (a)～(d).
(a) epoxy equivalent (weight) is 500～10000;
(b) the nuclear hydrogenation rate is more than 96% or 96%;
(c) softening temperature in the ring and ball method of JIS-K-7234 is 40～200 ℃;
(d) be more than 90% or 90% at the light penetration of measuring under the wavelength 400nm.
The 2nd main points of the present invention are a kind of manufacture method of alicyclic epoxy resin, it is characterized in that, with epoxy equivalent (weight) be 500～10000, basic metal and the 15th family's element total content be 10ppm or the aromatic epoxy resin nuclear hydrogenationization below the 10ppm.
The 3rd main points of the present invention are a kind of ester ring type epoxy composite, it is characterized in that, contain above-mentioned alicyclic epoxy resin and epoxy curing agent.
The 4th main points of the present invention are a kind of epoxy resin cured product, it is characterized in that, this cured article solidifies composition epoxy resin and obtains.
The 5th main points of the present invention are a kind of electric and electronic material sealing material, it is characterized in that, contain above-mentioned Resins, epoxy or alicyclic epoxy resin compositions.
The 6th main points of the present invention are a kind of semiconductor light-emitting apparatus, it is characterized in that, have used above-mentioned sealing material.
The effect of invention
According to the present invention, what can make nuclear hydrogenation rate height, transparency excellence is the solid alicyclic epoxy resin at normal temperatures.Particularly, by using specific hydrogenation catalyst, can be cheap and efficiently with few such alicyclic epoxy resin of catalyzer usage quantity manufacturing, industrial be very favourable.
In addition, therefore the cured article of composition epoxy resin of the present invention is difficult for ftractureing in thermal cycling test owing to water white transparency excellence, resistance to cracking are also very excellent.In addition, because photostabilization, thermotolerance are also excellent, therefore, can be particularly conducive to the composition epoxy resin use of using the LED sealing material use as the transfer mould moulding of the semi-conductive LED of III group-III nitride compounds that has used the light of emitting the short wavelength in sealing.
Embodiment
Below, explain embodiment of the present invention.
[alicyclic epoxy resin and manufacture method thereof]
At first, for convenience of explanation, the manufacture method of alicyclic epoxy resin is described.The manufacture method of alicyclic epoxy resin of the present invention is characterised in that, with epoxy equivalent (weight) be 500～10000, the total content of alkali metal and periodictable the 15th family's element is 10ppm or the aromatic epoxy resin nuclear hydrogenationization below the 10ppm.
By with above-mentioned specific epoxy equivalent (weight), and the confined aromatic resin of total content of alkali metal and periodictable the 15th family's element (following sometimes they are called " specific impurities element ") can successfully carry out nuclear hydrogenationization with high hydrogenation rate as the nuclear hydrogenation raw material.By with high hydrogenation rate with such aromatic epoxy resin nuclear hydrogenationization, can obtain under the normal temperature being the excellent alicyclic epoxy resin of the solid transparency.
In the present invention, say more specifically that the alkali metal of specific impurities element is the element of selecting from lithium, sodium and potassium, the element of periodictable the 15th family is nitrogen and/or phosphorus.In addition, nuclear hydrogenationization is preferably carried out containing in the presence of the catalyzer of platinum family element, as the catalyzer that contains this platinum family element, especially preferably will support the catalyst precursor reduction of platinum family compound and the material that obtains on carrier.And, preferably make the aromatic epoxy resin coexistence during this catalyst precursor, and the nuclear hydrogenation of the reduction of catalyst precursor and aromatic epoxy resin be reflected in the same reaction system carry out simultaneously in reduction.The usage quantity of such catalyzer is 0.001～0.5 weight % with respect to the platinum family element conversion scale of aromatic epoxy resin preferably.
Like this, can make nuclear hydrogenation rate solid-state alicyclic epoxy resin high, high transparent expeditiously with few catalyzer usage quantity by using the special catalyst of specified quantitative.
The manufacture method of alicyclic epoxy resin of the present invention preferably includes: in the presence of hydrogenation catalyst, the aromatic nucleus of aromatic epoxy resin added hydrogenant nuclear hydrogenation reaction process and take out the refining step of hydrogenated epoxy resin from reaction mixture.
(supplying with the aromatic epoxy resin of nuclear hydrogenationization)
The aromatic epoxy resin of Shi Yonging is that epoxy equivalent (weight) is 500～10000, the specific impurities element in the present invention, promptly the total content of alkali metal and periodictable the 15th family's element be 10ppm or 10ppm following be the solid aromatic epoxy resin usually at normal temperatures.
If supply with that the epoxy equivalent (weight) of aromatic epoxy resin of nuclear hydrogenationization is low, during less than 500, the hydrogenated epoxy resin that obtains is for liquid, or softening temperature is low and the semi-solid that seriously is clamminess, opposite epoxy equivalent (weight) height, surpass at 10000 o'clock, because the reduction of nuclear hydrogenation rate is therefore not preferred.
The total content of the alkali metal of the aromatic epoxy resin that the present invention relates in addition, and periodictable the 15th family's element is 10ppm or below the 10ppm.Therefore, the reason of the content of the specific impurities element in the restriction aromatic epoxy resin is as follows.
That is, usually as the method for making the high-molecular weight aromatic epoxy resin, the method for (1) or (2) below carrying out, industrial, two kinds of methods all adopt.
(1) be the manufacture method (1 terrace work) of in the presence of alkali cpd bisphenol cpd and epihalohydrins being carried out condensation reaction, this method is to reduce the usage quantity of epihalohydrins with respect to bisphenol cpd, carries out the method that polymer quantizes.
(2) be that low-molecular-weight epoxy resin and the bisphenol cpd made by 1 terrace work are reacted in the presence of basic catalyst, carry out the method (2 terrace work) that polymer quantizes.
The alkali cpd that uses in 1 terrace work is inorganic alkaline compounds such as lithium hydroxide, sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood, and usually, aqueous sodium hydroxide solution uses with respect to the equivalent of epoxy group(ing) or more than the equivalent.The occasion of 1 terrace work, with respect to the reacting weight of epihalohydrins, alkali cpd uses equivalent or more than the equivalent, the alkali halide of filtering separation by-product, in addition, method such as optionally wash with water is removed salt.
On the other hand, in 2 terrace works, basic catalyst as the addition reaction that promotes epoxy group(ing) and phenol hydroxyl, can use triethylamine, Tributylamine, tertiary amines such as benzyldimethylamine, tetraethylammonium chloride, tetraethyl-ammonium bromide, quaternary ammonium salts such as bromination tetrabutylammonium, tributylphosphine, triphenylphosphine, phosphine classes such as three (Dimethoxyphenyl) phosphine, bromination Si Yi Ji Phosphonium, the Xiuization 4-butyl-phosphonium, quaternary phosphine salts such as iodate 4-butyl-phosphonium, lithium hydroxide, lithium hydroxide, potassium hydroxide, yellow soda ash, inorganic alkaline compounds such as salt of wormwood use about hundreds of ppm with respect to raw material epoxy resin.The occasion of the Resins, epoxy that obtains by 2 terrace works, usually do not separate the basic catalyst that the promotion catalyzer as addition reaction uses and make goods, this is because in order to simplify the manufacturing of Resins, epoxy, in addition, in other purposes, remaining basic catalyst can have problems hardly.
But, present inventors find, at the epoxy equivalent (weight) that will obtain with above-mentioned 1 terrace work or 2 terrace works is that 500～10000 aromatic epoxy resin is when carrying out the nuclear hydrogenation reaction as raw material, can make the nuclear hydrogenation catalyst deactivation owing to contain compound, the particularly alkaline matter of a spot of alkali metal or periodictable the 15th family's element, the nuclear hydrogenation reaction is suppressed, reaction stops, and therefore, can not improve the nuclear hydrogenation rate of Resins, epoxy.Relative therewith, for example, after above-mentioned high molecular aromatic Resins, epoxy building-up reactions is finished, refining resultant, the total content that obtains alkali metal or periodictable the 15th family's element is 10ppm or the following aromatic epoxy resin of 10ppm, by this having been reduced the aromatic epoxy resin nuclear hydrogenationization of specific impurities constituent content, can obtain the high solid-state hydrogenated epoxy resin of hydrogenation rate.
Like this, as the total content that obtains alkali metal and periodictable the 15th family's element is the method for 10ppm or the aromatic epoxy resin below the 10ppm, have no particular limits, can enumerate following method: for example, the resultant of reaction that 1 terrace work or 2 terrace works is obtained with pure water etc. clean 1 time or 2 times or 2 times with on carry out the purified method, in 2 terrace works, the resultant of reaction that 1 terrace work is obtained with pure water etc. clean again 1 time or 2 times or 2 times with on make with extra care after, carry out polymer again and quantize, once more with pure water etc. with this resultant of reaction clean 1 time or 2 times or 2 times with on carry out the purified method.In addition, also can before cleaning, aromatic epoxy resin be dissolved in the suitable organic solvent, distill the solvent of removing organic solvent then and clean with pure water.At this moment, as the organic solvent that uses, can enumerate hexone, toluene, dimethylbenzene etc.In addition, can reduce these specific impurities constituent contents by the method for using sorbent materials such as gac to carry out adsorption treatment.
Alkali metal as this specific impurities element is lithium (Li), sodium (Na), potassium (K), and periodictable the 15th family's element is nitrogen (N), phosphorus (P).In the present invention, with each content of these elements is 5ppm or below the 5ppm, total content (being the total content of Li, Na, K, N, P) is for 10ppm or below the 10ppm, 7ppm or below the 7ppm particularly, when especially the following aromatic epoxy resin of 5ppm or 5ppm is used as raw material, because the nuclear hydrogenation rate improves really, be preferred therefore.The basic metal in the Resins, epoxy or the analysis of phosphorus are by ICP luminescence analysis, ICP-MS analysis etc., and in addition, nitrogen is undertaken by known in the past methods such as total nitrogen analysis meters.
In addition, example as the aromatic epoxy resin that uses among the present invention, can enumerate bisphenol A type epoxy resin, bisphenol f type epoxy resin, 3,3 ', 5,5 '-tetramethyl--4,4 '-bisphenol-type epoxy resin, 4, the bisphenol-type epoxy resin that 4 '-bisphenol-type epoxy resin is such or bisphenol-A phenolic varnish type Resins, epoxy, naphthalene diol type Resins, epoxy etc.These aromatic epoxy resins can use a kind separately, also can mix use more than 2 kinds or 2 kinds.
Among these, as aromatic epoxy resin, preferred epoxy equivalent (weight) is 600～6000 bisphenol A type epoxy resin, bisphenol f type epoxy resin, wherein, as these aromatic epoxy resins,, therefore preferred because the resin effect of the present invention that 1 terrace work is made is remarkable.
(hydrogenation catalyst)
＜catalyst component 〉
The hydrogenation catalyst that the present invention uses preferably contains the catalyzer of platinum family element, as this platinum family element, particularly, can enumerate ruthenium, rhodium, palladium, osmium, iridium, platinum.More preferred rhodium (Rh) or ruthenium (Ru) catalyzer, the most preferred rhodium catalyst.
These catalyzer can use with the form of loose density (bulk), but usually owing to be highly active, therefore preferably platinum family element (platinum metals) or its compound are supported on the supported catalyst on the carrier.
＜carrier 〉
As carrier, can enumerate inorganic oxides such as carbon class carrier or aluminum oxide, silicon-dioxide, zeolite etc., preferred especially carbon class carrier.As the shape of carrier, powder, moulding product etc. are arranged, but more preferred fine catalyst, its particle diameter is preferred 1～1000 μ m usually, preferred especially 5～500 μ m.
As the object lesson of carbon class carrier, can enumerate gac, graphite, carbon black etc.Wherein, preferred graphite especially preferably is called as the graphite of high surface area graphite (high surface area graphite).The specific surface area of high surface area graphite carrier is generally 5～2000m
2/ g, preferred 50～600m
2/ g.
＜platinum group metal compounds 〉
As the platinum group metal compounds that uses in the hydrogenation catalyst, can enumerate platinum group metal compounds inorganic salt, organic salt, coordination compound, contain the organometallic compound of platinum metals etc., particularly, from the viewpoint of easy acquisition, the inorganic salt of preferred platinum group metal and organic salt.As object lesson, when using rhodium as the platinum metals, as the compound that contains rhodium, can enumerate, rhodium chloride, rhodium nitrate, rhodium sulfate, rhodium acetate, methyl ethyl diketone rhodium, 12 phosphinylidynes, four rhodiums (tetrarhodium dodecacarbonyl) etc., but preferred especially rhodium chloride, rhodium nitrate, rhodium acetate.
＜loading 〉
The loading of the platinum the when platinum metals is supported on the carrier is according to the kind of the compound that uses, carrier, loading method etc. and different, but convert with metal usually, with respect to carrier is 0.1～50 weight %, and preferred 0.5～20 weight % is more preferably the scope of 1～10 weight %.
＜loading method 〉
As the method that the above-mentioned compound that contains the platinum metals is supported on the carrier, can select normally used various loading method, particularly, can enumerate " Chu Mei Tone System chemistry " (Talk
The サ イ エ of society Application テ イ Off イ Network: nineteen eighty-two) methods such as p.49 middle impregnation method of putting down in writing or ion exchange method.
If enumerate an example of the method for supporting, platinum group metal compounds can be dissolved in the solvent that can dissolve it, for example water, alcohol, hydrocarbon etc., make solution, carrier is contained be immersed in this solution.In addition, if necessary,, also can use inorganic alkaline compounds such as caustic soda or ammonia, organic compounds containing nitrogen etc., the pH value is adjusted into suitable value, carry out immobilization for making metallic compound fixing more firm on carrier.At this moment, think that the platinum family compound is supported on the carrier with the state of oxyhydroxide or oxide compound.
After the impregnation, by solvent filter or vaporized distillate are gone to separate, clean with solvent and to be used in after the immobilized inorganic alkaline compound etc., optionally carry out drying, can obtain platinum group metal compounds is supported on supported catalyst.
In this reaction, this catalyzer directly can be supplied with the nuclear hydrogenation reaction, the reduction processing that perhaps also this catalyzer can be carried out following explanation resupplies reaction afterwards.In addition, think and in fact also after making catalyst reduction under the nuclear hydrogenation reaction conditions, show catalytic activity with the catalyzer of reduced state supply response not.
The reduction of＜hydrogenation catalyst 〉
Method as reducing catalyst, can enumerate following method: for example, use reductive agents such as formalin, formic acid, hydrazine or methyl alcohol to carry out the method for liquid-phase reduction, similarly, with slurry state contact with hydrogen in liquid phase the reductive method or, catalyzer is contacted with methanol gas or hydrogen carries out reductive method etc.For example, for the method for carrying out liquid-phase reduction with formalin etc., can use the spy to open disclosed method etc. in the flat 11-217379 communique.
After clean the removing of impurity such as reductive agent that the reductive hydrogenation catalyst will use usually, optionally carry out drying like this in the time will reducing, offer the nuclear hydrogenation reaction again.The catalyzer that has supported platinum group metal compounds is suspended in the appropriate solvent, when in liquid phase, reducing with hydrogen, reduce handle after, can separating catalyst and directly dissolve aromatic epoxy resin and carry out the nuclear hydrogenation reaction.
＜particularly preferred hydrogenation catalyst 〉
Compound method as particularly preferred hydrogenation catalyst among the present invention, can enumerate following method: carbon class carrier is contained in the aqueous solution that is immersed in rhodium compound, add alkali cpd again, rhodium compound is supported on the carbon class carrier, with the catalyst-loaded solid-liquid separation of carrying out, wash with water and remove impurity, optionally carry out the exsiccant method.
When this catalyzer directly is used in the nuclear hydrogenation reaction not reducing, in the nuclear hydrogenation reaction system (in the presence of the hydrogen in liquid phase), rhodium compound is reduced to active state, shows high reactivity, just can carry out the nuclear hydrogenation reaction effectively with catalyzer usage quantity still less.
(nuclear hydrogenation reaction)
Nuclear hydrogenation reaction can come aromatic epoxy resin is carried out by hydrogen in the presence of reaction solvent and above-mentioned nuclear hydrogenation catalyzer.
The usage quantity of nuclear hydrogenation catalyzer is suitably selected in the scope that can obtain practical speed of response corresponding to various conditions such as temperature of reaction or reaction pressures.The catalyzer usage quantity can be reacted under low temperature, low pressure, short period of time for a long time, but catalyst costs increases, and is not economical therefore.In addition, when the catalyzer usage quantity was very few, speed of response was slack-off, was difficult to react in the common time.As the catalyzer usage quantity that is more preferably, with respect to aromatic epoxy resin 100 weight parts, convert with reactive metal (platinum family element), be 0.001～0.5 weight part, preferred 0.002～0.2 weight part, more preferred 0.003～0.1 weight part.Therefore, that uses the reactive metal for example supported 5 weight % is catalyst-loaded during as catalyzer, as the catalyzer usage quantity that comprises carrier, is 0.02～10 weight part with respect to aromatic epoxy resin 100 weight parts, preferred 0.04～4 weight part, more preferred 0.06～2 weight part.
As the reaction solvent of nuclear hydrogenation reaction, can enumerate for stabilized hydrogenation and can not make the ether solvent, esters solvent, alcoholic solvent, paraffinic solvent etc. of catalyst deactivation.Particularly, can preferably use ether-ether classes such as ester class, ethylene glycol monomethyl ether acetate such as chains such as ether, isopropyl ether, methyl tertiary butyl ether, glycol dimethyl ether, tetrahydrofuran (THF), diox, two oxa-s, penta ring or cyclic ethers, ethyl acetate, butylacetate etc.These solvents can also use more than 2 kinds or 2 kinds except that can using separately simultaneously.Wherein, preferred ether solvent or esters solvent, preferred especially esters solvent.
As esters solvent, from the operability aspect, the boiling point under the preferred normal pressure is the fatty acid ester of 50～180 ℃ of scopes, preferred especially acetic ester and propionic ester.Particularly, ethyl acetate, propyl acetate, butylacetate, methyl propionate, special ethyl acetate.
The usage quantity of reaction soln is generally 0.1～20, preferred 0.5～10 in the weight ratio with respect to the aromatic epoxy resin of raw material.When the amount of reaction solvent is very few, since the viscosity height of common raw material aromatic epoxy resin, the diffusion variation of hydrogen, speed of response reduces, and the selectivity of nuclear hydrogenation reaction reduces.When reaction solvent was too much, reaction vessel maximized, and also is disadvantageous in the recovery of resultant.Particularly, the aromatic epoxy resin that the big melt viscosity of molecular weight is high is during as raw material, and the quantity of solvent that needs is many, but the amount of reaction solvent is when too much, and productivity reduces, and is disadvantageous economically.
Temperature of reaction is generally 30～150 ℃, preferred 50～130 ℃.Reaction temperature is spent when hanging down, and speed of response reduces, and for finishing reaction, needs a large amount of hydrogenation catalyst and long-time.When temperature of reaction was too high, side reactions such as the hydrogenation decomposition of epoxy group(ing) increased, and the quality of goods descends.Reaction pressure is generally 1～30MPa, preferred 2～15MPa.Reaction pressure is crossed when hanging down, and speed of response reduces, and for finishing reaction, needs a large amount of hydrogenation catalyst and long-time.When reaction pressure was too high, therefore necessary equipment enlarging was disadvantageous economically.
As reactive mode, can be liquid phase suspension reaction or fixed bed reaction, but special preferred liquid phase suspension reaction.Hydrogen can import in the mode of circulation, also can only import the part that consumes.In addition, hydrogen can import and be dispersed in the liquid, also can be involved in from gas phase and is absorbed in the liquid with modes such as stirrings.
The terminal point of nuclear hydrogenation reaction can absorb monitor or sampling analysis is judged with hydrogen.
(post-treating method)
After reaction finishes, from the reaction mixture separating catalyst, then, heat up in a steamer the dereaction solvent, obtain the purpose resultant by distillation with operations such as filtration centrifugations.
But, after the nuclear hydrogenation reaction finishes, if only catalyzer is separated from reaction mixture simply, because reactive metal stripping etc. from catalyzer makes the hydrogenated epoxy resin that obtains painted, light penetration reduces, therefore, heat up in a steamer desolvate before, preferably handle by sorbent material.At this moment, after the nuclear hydrogenation reaction, can after separating hydrogenation catalyst, carry out adsorption treatment, not separate hydrogenation catalyst, sorbent material be joined in the reaction solution mix, catalyzer and sorbent material be carried out simultaneously the method for solid-liquid separation but also can adopt.If this method then is more easy, in addition, can also obtain to accelerate the effect of filtration velocity, be favourable therefore.
As above-mentioned sorbent material, can enumerate, solid alkaline compounds such as gac, atlapulgite, ion exchange resin, synthetic adsorbent, magnesium oxide etc. wherein, preferably contain magnesian compound and gac, preferred especially magnesium oxide.
Above-mentioned adsorption treatment also can be carried out with the any-mode that the contact in batches of adopting powder sorbent is handled, handled to the circulation of sorbent material packing layer.As powder sorbent, preferably using median size is the sorbent material of 1～1000 μ m, and as granulated sorbent, preferably using median size is the sorbent material of 1～10mm.
The usage quantity of sorbent material is according to the kind of reaction conditions or sorbent material and different, but with respect to the Resins, epoxy that is included in the process object liquid, is generally 0.01～100 weight %, preferred 0.1～20 weight %, more preferred 0.2～10 weight %.During the usage quantity less than 0.01 weight % of sorbent material, can not give full play to the result of use of sorbent material, when surpassing 100 weight %, the loss of goods increases.
The temperature of adsorption treatment is generally 0～100 ℃, preferred 10～80 ℃.In addition, the state of adsorption treatment preferably contains the state of solvent from aspects such as operability, the rate of recovery, adsorption efficiencies.Solvent types has no particular limits so long as the solvent of dissolved epoxy gets final product, but adopts the refining step of absorption to carry out before concentration of reaction solution usually, the therefore preferred reaction solvent that directly uses.The content of solvent is generally 5～80 weight % with the densitometer in the process object liquid, is more preferably 10～50 weight %.When the amount of solvent was very few, the viscosity of process object liquid uprised, and adsorption efficiency reduces.
After having carried out such aftertreatment, usually with 50～220 ℃, preferred 70～180 ℃ condition is heated up in a steamer from the epoxy resin solution that has separated catalyzer or sorbent material and is desolvated, and cooling curing obtains water white solid-state hydrogenated epoxy resin then.
Below, to alicyclic epoxy resin of the present invention, that is, solid-state alicyclic epoxy resin (hydrogenated epoxy resin) describes.The feature of alicyclic epoxy resin of the present invention is to satisfy the regulation of following (a)～(d).
(a) epoxy equivalent (weight) is 500～10000;
(b) the nuclear hydrogenation rate is more than 96% or 96%;
(c) softening temperature in the JIS-K-7234 ring and ball method is 40～500 ℃;
(d) more than the light penetration of measuring under the wavelength 400nm 90% or 90%.
The epoxy equivalent (weight) of alicyclic epoxy resin of the present invention preferred 550～10000, more preferred 600～6000, preferred especially 600～3000.In addition, when the nuclear hydrogenationization by above-mentioned aromatic epoxy resin obtains alicyclic epoxy resin of the present invention, the rate of decomposition decision of the epoxy group(ing) that the epoxy equivalent (weight) of alicyclic epoxy resin takes place as side reaction during by the epoxy equivalent (weight) of raw material aromatic epoxy resin and nuclear hydrogenation.The scope of epoxy equivalent (weight) preferred 600～10000.The rate of decomposition of epoxy group(ing) is the ratio that epoxy group(ing) is decomposed into other functional groups such as hydroxyl, and the theoretical epoxy equivalent (weight) that can be when only aromatic nucleus is by hydrogenation and the actual epoxy equivalent (weight) of goods are obtained by calculating.Below the rate of decomposition of the epoxy group(ing) of the alicyclic epoxy resin that obtains preferred 50% or 50%, below more preferred 30% or 30%, below preferred especially 20% or 20%.When the rate of decomposition of epoxy group(ing) is big, use the thermotolerance of the cured article of this alicyclic epoxy resin that the tendency of decline is arranged.
The nuclear hydrogenation rate of alicyclic epoxy resin of the present invention is especially need be to light stable the time, more than preferred 98% or 98%.Be limited to 100% on the nuclear hydrogenation rate.During this nuclear hydrogenation rate less than 96%, when composition epoxy resin of the present invention is used in the LED sealing of nitride-based semiconductor, can absorb short wavelength's light, pass in time, cause the deterioration of resin, because it is not xanthochromia causes luminosity significantly to reduce, therefore preferred.
In addition, preferred 50～150 ℃ of softening temperature, more preferred 60～140 ℃.The alicyclic epoxy resin of higher softening temperature can be that raw material is made with the big high-molecular weight aromatic epoxy resin of epoxy equivalent (weight).Softening temperature is crossed when low, become be clamminess easily, melt bonded easily, operability reduces sometimes, on the contrary, if need high temperature during melting mixing such as too high and solidifying agent, operability reduces sometimes.
In addition, the form and aspect of alicyclic epoxy resin of the present invention are represented with light penetration, hydrogenated epoxy resin 100 mass parts are dissolved with organic solvents such as ethyl acetate 200 mass parts, using the quartz cell of the long 1cm in pond, is more than 90% or 90% at the light penetration (being designated hereinafter simply as " light penetration ") of the solution that obtains by spectrophotometric determination under the wavelength 400nm.
As operable organic solvent in the above-mentioned light penetration mensuration, so long as the light of absorption measurement wavelength not in fact, and the solvent of dissolving hydrogenated epoxy resin gets final product, also can use ethyl acetate material in addition, for example, can use ether solvents such as esters solvent, tetrahydrofuran (THF), diox such as butylacetate.
During the light penetration less than 90% of alicyclic epoxy resin, because the form and aspect variation of Resins, epoxy, so its cured article can not obtain water white material, can not use with material as optics, and is therefore not preferred.As alicyclic epoxy resin of the present invention, preferably use the high person of light penetration of the light of near ultraviolet region.Particularly, the light penetration of wavelength 340nm is more than 80% or 80%, more than preferred 85% or 85%, is more preferably more than 90% or 90%.
In addition, the preferred 10ppm of total content of the alkali metal in the alicyclic epoxy resin of the present invention and periodictable the 15th family's element or below the 10ppm, such alicyclic epoxy resin is the alkali-free material in fact is as electric and electronic material for example the time, because impurity is few, be favourable therefore.
In addition, alicyclic epoxy resin of the present invention is served as reasons for example above-mentioned nuclear hydrogenationization when obtaining, and compares with the aromatic epoxy resin of raw material, and melt viscosity reduces, the mobile raising.In addition, so that for example the melt viscosity under 150 ℃ compared, the viscosity of alicyclic epoxy resin was generally below 70% or 70% with respect to the melt viscosity of raw material aromatic epoxy resin.
Alicyclic epoxy resin of the present invention is solid at normal temperatures, and the transparency is excellent, is useful as various optics with the raw material of material or coating material etc.Alicyclic epoxy resin of the present invention can be by for example above-mentioned method manufacturing of the present invention.Wherein, preferably be 500～10000 with epoxy equivalent (weight), the total content of alkali metal and periodictable the 15th family's element is the alicyclic epoxy resin that 10ppm or the aromatic epoxy resin nuclear hydrogenationization below the 10ppm obtain, in addition, the above-mentioned preferred epoxy equivalent (weight) of aromatic epoxy resin is 600～6000 bisphenol A type epoxy resin and/or bisphenol f type epoxy resin.
[purposes of alicyclic epoxy resin compositions, epoxy resin cured product and alicyclic epoxy resin compositions]
Alicyclic epoxy resin compositions of the present invention is characterised in that, contains above-mentioned alicyclic epoxy resin and epoxy curing agent.
(hardener for epoxy resin),
Hardener for epoxy resin as (B) of the present invention composition can use common hardener for epoxy resin, for example, can enumerate following material.
(i) amine: two (4-aminocyclohexyl) methane, two (amino methyl) hexanaphthene, ortho-toluene diamine, 3, two (the 3-aminopropyls)-2 of 9-, 4,8, aliphatics and alicyclic amines such as 10-four spiral shells [5,5] hendecane, aromatic amines such as mphenylenediamine, diaminodiphenyl-methane, diamino diphenyl sulfone, benzyl dimethyl amine, 2,4,6-three (dimethylaminomethyl) phenol, 1,8-diazabicylo (5,4,0)-and undecylene-7,1,5-azabicyclic (4,3,0)-nonene-7 tertiary amine such as grade and its esters.
(ii) anhydrides: aromatic anhydride classes such as Tetra hydro Phthalic anhydride, trimellitic acid 1,2-anhydride, pyromellitic acid acid anhydride, annular aliphatic anhydrides such as Tetra Hydro Phthalic Anhydride, methyl tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl carbic anhydride, dodecenyl succinic anhydride, trialkyl Tetra Hydro Phthalic Anhydride.
(iii) polyatomic phenol: catechol, Resorcinol, Resorcinol, Bisphenol F, dihydroxyphenyl propane, bisphenol S, bis-phenol, phenol phenolic varnish class, the phenolic varnish thing class of 2 yuan of phenol such as cresols phenolic varnish class, dihydroxyphenyl propane, three hydroxyphenyl methane classes, aralkyl polyphenyl phenols, Dicyclopentadiene (DCPD) polyphenyl phenols etc.
(iv) other: the BF of amine
3Coordination compound, aliphatics sulfonium salt, aromatic series sulfonium salt, salt compounded of iodine with and organic acid hydrazides class, resole, hexanodioic acid, sebacic acid, terephthalic acid, trimellitic acid such as Bronsted Barbiturates, dicyano diamide, adipic dihydrazide and O-phthalic acid dihydrazide such as phosphonium salt and the polycarboxylic acids such as polyester etc. that contain carboxyl.
These hardener for epoxy resin can use separately, also can use simultaneously more than 2 kinds or 2 kinds.
The use level of hardener for epoxy resin is according to the kind of the hardener for epoxy resin that uses and different, but is generally 0.01～200 mass parts with respect to hydrogenated epoxy resin 100 mass parts, in the scope of preferred 0.1～100 mass parts.
(anhydride compound or cationic polymerization initiators)
Especially, when composition epoxy resin of the present invention is used as the sealing material of luminous element, on the photostabilization this point of the composition epoxy resin that obtains, as hardener for epoxy resin, preferred anhydride compound or the cationic polymerization initiators of using, as anhydride compound, can enumerate, for example, Tetra hydro Phthalic anhydride, trimellitic acid 1,2-anhydride, aromatic anhydride classes such as pyromellitic acid acid anhydride, Tetra Hydro Phthalic Anhydride, methyl tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, the methyl carbic anhydride, annular aliphatic acid anhydrides such as trialkyl Tetra Hydro Phthalic Anhydride.Wherein, on the photostabilization this point that improves composition of the present invention, especially preferably use hexahydrophthalic anhydride, methylhexahydrophthalic anhydride.
In addition, when using acid anhydrides, be cured as purpose, can cooperate curing catalyst to promote it.As the example of this curing catalyst, can enumerate metallic soap classes such as tertiary amines, imidazoles, organic phosphine compound class or their salt, zinc octoate, stannous octoate.
Usage ratio as the anhydride compound of hardener for epoxy resin, hydrogenated epoxy resin 100 mass parts with respect to (A) composition are 5～200 mass parts, in the scope particularly preferably in 10～100 mass parts, when cooperating above-mentioned curing catalyst, its usage ratio is with respect to preferred 0.01～10 mass parts of hydrogenated epoxy resin 100 mass parts.
In addition, as cationic polymerization initiators, can use by active energy beam and produce positively charged ion kind or lewis acidic active energy beam cationic polymerization initiators or because thermogenesis positively charged ion kind or lewis acidic hot cationic polymerization initiators.
As the active energy beam cationic polymerization initiators, can enumerate the metal fluorine boron coordination salt and the boron trifluoride coordination compound of record in No. the 3379653rd, the United States Patent (USP); Two (perfluoroalkyl sulphonyl) methane metal-salts of record in No. the 3586616th, the United States Patent (USP); The aryl diazo compound of record in No. the 3708296th, the United States Patent (USP); The aromatic series salt of the VIa family element of record in No. the 4058400th, the United States Patent (USP); The aromatic series salt of the Va elements of record in No. the 4069055th, the United States Patent (USP); The dicarbapentaborane inner complex of the IIIa～Va elements of record in No. the 4068091st, the United States Patent (USP); The sulfydryl pyranium salt of No. 4139655 record of United States Patent (USP); The VIb element of the form of the MF6-negatively charged ion (wherein, M selects from phosphorus, antimony and arsenic) of record in No. the 4161478th, the United States Patent (USP); The aryl sulfonium coordination salt of No. 4231951 record of United States Patent (USP); The aromatic series iodine coordination salt and the aromatic matte coordination salt of No. 4256828 record of United States Patent (USP); Be documented in " polymer science magazine (Journal ofPolymer Science), polymer chemistry (Polymer Chemistry) version " that people such as W.R.Watt writes, two [4-(hexichol sulfonium) phenyl] more than 1 kinds or 2 kinds or 2 kinds of thioether-two hexafluoro metal-salts (for example, phosphoric acid salt, arsenate, stibnate etc.) in the 22nd volume, 1789 pages (1984).In addition, also can use the mixed ligand Base Metal salt and the silanol-aluminium coordination compound of iron cpd.
Preferred active energy beam cationic polymerization initiators comprises the aromatic series salt of aryl sulfonium coordination salt, the aromatic matte that contains the halogen coordination ion or salt compounded of iodine and II family, V family and VI family element.In these salt some are made " FX-512 " (3M company), " UVR-6690 " and " UVR-6974 " { ユ ニ オ Application カ-バ イ De (Union Carbide) company }, " UVE-1014 " and " UVE-1016 " { ジ エ ネ ラ Le エ レ Network ト リ Star Network (General Electric) company } " KI-85 " { デ グ Star サ (Degussa) company }, " SP-150 " and " SP-170 " (rising sun electrification company) and " サ Application エ イ De SI-60L ", " サ Application エ イ De SI-80L " and " サ Application エ イ De SI-100L " (three new chemical industrial companies) obtains as commodity.
As hot cationic polymerization initiators, can enumerate, trifluoromethanesulfonic acid (Triflic acid) salt, boron trifluoride ether coordination compound, cationic or bronsted acid catalysts such as boron trifluoride, as preferred hot cationic polymerization initiators is fluoroform sulphonate, as its example, the trifluoromethanesulfonic acid diethyl ammonium that can obtain from " FC-520 " of 3M company is arranged, the trifluoromethanesulfonic acid triethyl ammonium, trifluoromethanesulfonic acid di-isopropyl ammonium, trifluoromethanesulfonic acid ethyl di-isopropyl ammonium etc. (in these multiple all on the books in (ModernCoating)) at " the modern coating " of distribution in October, 1980 that R.RAlm writes.In addition, in the aromatic series salt that can be used as the use of active energy beam cationic polymerization initiators, the material by thermogenesis positively charged ion kind is arranged, they also can be used as hot cationic polymerization initiators and use.As its example, " サ Application エ イ De SI-60L ", " サ Application エ イ De SI-80L " and " サ Application エ イ De SI-100L " (three new chemical industrial companies) are arranged.
In these active energy beams and hot cationic polymerization initiators, see on this some in that the balance of operability and potentiality and solidified nature is excellent, preferably salt, wherein, on excellent this aspect of balance of operability and potentiality, see that preferred especially diazonium salt, salt compounded of iodine, sulfonium salt Yi are Ji phosphonium salt.
The usage quantity of cationic polymerization initiators is with respect to hydrogenated epoxy resin 100 mass parts of (A) composition, preferred 0.01～15 weight part, preferred especially 0.05～5 weight part.
When using any hardener for epoxy resin, if its usage quantity breaks away from its suitable scope, the balance variation of the thermotolerance of epoxy resin cured product and wet fastness, therefore not preferred.
(oxidation inhibitor)
Cooperate oxidation inhibitor to composition epoxy resin of the present invention, particularly encapsulating luminescent element material in composition epoxy resin, the oxidative degradation in the time of can preventing to heat is preferred obtaining on this aspect of painted few cured article.
At this moment,, can enumerate as operable oxidation inhibitor, phenols, sulphur class, Phosphorus oxidation inhibitor, with respect to hydrogenated epoxy resin 100 mass parts of (A) composition, usually with 0.005～5 mass parts, preferred 0.01～1 mass parts cooperates.As the object lesson of operable oxidation inhibitor, can enumerate following material.
[phenolic antioxidant]
Single phenols: 2,6 ditertiary butyl p cresol, butylated hydroxy anisole (BHA), 2,6-di-t-butyl p-ethyl phenol, stearyl-β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester etc.;
Bisphenols: 2,2 '-methylene-bis (4-methyl-6-tert butyl phenol), 2,2 '-methylene-bis(4-ethyl-6-t-butyl phenol), 4,4 '-thiobis (3 methy 6 tert butyl phenol), 4,4 '-butylidene-bis(3-methyl-6-t-butyl phenol), 3,9-two [1,1-dimethyl-2-{ β-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyl oxygen } ethyl]-2,4,8,10-four oxygen spiral shell [5,5] hendecanes etc.;
The polymer phenols: 1,1,3-three (2-methyl-4 hydroxyls-5-tert-butyl-phenyl) butane, 1,3,5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene, four [methylene radical-3-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic ester] methane, two [3,3 '-two (4 '-hydroxyl-3 '-tert-butyl-phenyl) butyric acid] glycol ester, 1,3,5-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl)-and S-triazine-2,4,6-(1H, 3H, 5H) triketone, tocopherol etc.
[sulfur type antioxidant]
Dilauryl-3,3 '-thiodipropionate, myristyl-3,3 '-thiodipropionate, distearyl-3,3 '-thiodipropionate etc.
[Phosphorus oxidation inhibitor]
Phosphoric acid ester: triphenylphosphate, phenylbenzene isodecyl phosphoric acid ester, phenyl diiso decyl phosphoric acid ester, three (nonyl phenyl) phosphoric acid ester, the diiso decyl pentaerythritol phosphate, three (2, the 4-di-tert-butyl-phenyl) phosphoric acid ester, ring-type neopentane four bases (cyclic neopentanetetrailbis (octadecyl) phosphite) two (octadecyl) phosphoric acid ester, ring-type neopentane four bases two (2, the 4-di-tert-butyl-phenyl) phosphoric acid ester, two (2, the 4-di-t-butyl-4-aminomethyl phenyl) phosphoric acid ester of ring-type neopentane four bases, two [the 2-tertiary butyl-6-methyl-4-{2-(octadecane oxygen carbonyl) ethyl } phenyl] the hydrogenation phosphoric acid ester etc.
Luxuriant and rich with fragrance oxide compound (Oxaphosphaphenanthrene oxides) class of oxa-phosphorus: 9, the 10-dihydro-9-oxy is assorted-10-phosphorus phenanthrene-10-oxide compound, 10-(3, the 5-di-tert-butyl-4-hydroxyl benzyl)-9, the 10-dihydro-9-oxy is assorted-10-phosphorus phenanthrene-10-oxide compound, 10-oxygen in last of the ten Heavenly stems base-9, and the 10-dihydro-9-oxy is assorted-10-phosphorus phenanthrene-10-oxide compound etc.
These oxidation inhibitor can be distinguished use separately, but preferred especially phenols/sulphur class or phenols/Phosphorus such combination are used more than 2 kinds or 2 kinds.
(composition arbitrarily)
Optionally, can in composition epoxy resin of the present invention, add the following composition of cooperation.
(1) other Resins, epoxy: for example, 3,4-epoxycyclohexyl methyl-3 ', alicyclic epoxy resins such as 4 '-epoxycyclohexane carboxylate, " EHPE3150 " multifunctional heterocyclic ring epoxy resins such as solid-state alicyclic epoxy resin, triglycidyl group isocyanuric acid ester such as (ダ イ セ Le chemical company trade(brand)names);
(2) pulverous toughener or weighting agent: for example, metal hydroxides such as transparent fillers such as silicon compound, granulated glass sphere, aluminium hydroxides such as metal oxides such as aluminum oxide, magnesium oxide, micropowder silicon-dioxide, fused silica, crystalline silica and, kaolin, mica, quartz powder, graphite, molybdenumdisulphide etc.
Above-mentioned (1), (2) composition can be in the range fit of the transparency of not damaging composition epoxy resin of the present invention, hydrogenated epoxy resin 100 mass parts with respect to (A) composition, respectively preferred 100 mass parts or below 100 mass parts, for example 10～100 mass parts.
(3) tinting material or pigment: for example, titanium dioxide, chrome vermillion, Prussian blue, ultramarine, cadmium yellow, cadmium red and organic pigment etc.
(4) fire retardant: for example, ANTIMONY TRIOXIDE SB 203 99.8 PCT, bromine compounds and phosphorus compound etc.
(5) additives such as UV light absorber, ionic adsorption body, coupler, releasing agent.
When cooperating above-mentioned (3)～(5) composition, with respect to hydrogenated epoxy resin 100 mass parts of (A) composition, can cooperate 30 mass parts respectively or below 30 mass parts, for example 0.01～30 mass parts.
In addition, be purpose with the character of improving the curable epoxide thing, composition epoxy resin of the present invention can cooperate the synthetic resins beyond various solidified nature monomers, oligopolymer and the epoxy.Can enumerate, for example, the combination more than a kind or 2 kinds or 2 kinds of glycol or three alcohols, vinyl ethers, oxetane compound, fluoro-resin, acrylic resin, polyorganosiloxane resin etc.The cooperation ratio of these compounds and resene is the amount of scope of the original character of not damaging composition epoxy resin of the present invention, for example, with respect to hydrogenated epoxy resin 100 mass parts of (A) composition, preferred 50 mass parts or below 50 mass parts.
(epoxy resin cured product)
Composition epoxy resin solidified method of the present invention is had no particular limits, after other compositions of blending epoxy and hardener for epoxy resin and cooperation optionally, be cured reaction by light and heat etc., can obtain epoxy resin cured product.Epoxy resin cured product of the present invention has tough performance, and the content of impurities such as water-disintegrable chlorine and basic cpd is few, therefore be particularly suitable as the electrical and electronic parts material, for example use such as insulating material, especially, owing to the epoxy resin cured product transparency of the present invention, photostabilization excellence, be suitable for the sealing of following luminous element.
(luminous element and semiconductor light-emitting apparatus)
Composition epoxy resin of the present invention is because photostabilization is excellent especially, is that the sealing of luminous element of light of the shorter wavelength of 350～550nm is effectively for sending spike length therefore, and excellent semiconductor light-emitting apparatus can be provided.
As such luminous element, can enumerate, use the semi-conductive luminous element of III group-III nitride compounds that crystallizes into regular way (MBE method), halogenide gas-like phase flop-in method (HVPE method) formation by Metal Organic Vapor Phase Epitaxy (mocvd method), molecular ray, as general formula, can use Al
XGa
YIn
1-X-YN (0≤X≤1,0≤Y≤1,0≤X+Y≤1) expression comprises Al
X, GaN and InN 2 yuan of systems of what is called, Al
XGa
1-XN, Al
XIn
1-XN and Ga
XIn
1-X3 yuan of systems of what is called of N (above 0≤X≤1).As semiconductor structure, can enumerate, have equal structure, assorted structure or two assorted structures such as MIS joint, PIN joint or pn engage.Can select various emission wavelengths by material or its mixed crystal degree of semiconductor layer.In addition, can be formed in single quantum well (well) structure or the multiple quantum well structure that forms the semiconductor active layer on the film that produces the quantum effect.
(manufacture method of solid-state sealing material)
Used the luminous element sealing material of composition epoxy resin of the present invention, preferred normal temperature is solid down, as its manufacture method, can enumerate following method: use stirrer, mixing machine, rollers etc. are with above-mentioned solid-state hydrogenated epoxy resin, hardener for epoxy resin and any heating and melting limit, composition limit uniform mixing, perhaps the pre-reaction of hydrogenated epoxy resin and hardener for epoxy resin is carried out on the limit, the limit is adjusted into 40～150 ℃ with softening temperature, preferred 50～130 ℃ scope is pulverized the method for Powdered luminous element with sealing material that obtain behind the cooling curing.In addition, also can optionally more Powdered thing be beaten sheet and become strip.
During 40 ℃ of the softening temperature deficiencies of sealing material, the sealing material can not can not carry out the transfer mould moulding as solids treatment.Therefore, optionally, preferably carry out the pre-reaction of hydrogenated epoxy resin and hardener for epoxy resin, the softening temperature of sealing material is brought up to more than 40 ℃ or 40 ℃.In addition, when softening temperature surpassed 150 ℃, it is too high that melt temperature becomes, and so the transfer mould difficult forming is not preferred.
(sealing method of luminous element)
For with luminous element of the present invention with sealing material sealed light emitting element, preferably use the method for known low pressure transfer mould shaper, preferably at 100～200 ℃, 0.1～20 minute condition of molding lower seal luminous element.In addition, after the moulding,, preferably carry out after fixing in 70～170 ℃ temperature, 0.1～10 hour scope for seeking the further raising of seal member material properties.
Embodiment
Below, enumerate embodiment and comparative example the present invention more specifically is described, but the present invention is only otherwise exceed its purport, then is not limited to following examples.In addition, analytical procedure of using in each example below and physical property measurement method are as follows.
(1) hydrogenation rate of the aromatic nucleus of alicyclic epoxy resin:
Use is dissolved in the test materials in the ethyl acetate, is determined at the absorbancy at wavelength 275nm place, with the absorbancy comparison of the aromatic epoxy resin of raw material and calculate.Adopt the multiplying power of the dilution of ethyl acetate to be set at 10～1000 times corresponding to the nuclear hydrogenation rate.
(2) epoxy equivalent (weight):
According to JIS-K7236-1995, in the presence of acetate and cetrimonium bromide, use perchloric acid titration, the hydrogen bromide addition that produces on epoxy group(ing), is judged terminal point with potential difference.
(3) rate of decomposition of epoxy group(ing)
Calculate by the following method.
(i) in the occasion of bisphenol A type epoxy resin, molecular formula is shown in following formula, and molecular-weight average is 340+284n.
[Chemical formula 1]
(ii) the epoxy equivalent (weight) WR by raw material epoxy resin obtains n by following formula.
[mathematical expression 1]
WR＝(340+284n)/2
Can get thus, n=(2 * WR-340)/284
(iii) epoxy group(ing) is not decomposed but molecular formula during by hydrogenation ideally is as follows, calculates ideal epoxy equivalent (weight) WC by n.
[mathematical expression 2]
WC＝(352+296n)/2
[Chemical formula 2]
(iv) epoxy equivalent (weight) WP and the ideal value WC by the actual Resins, epoxy that obtains calculates rate of decomposition according to following formula.
[mathematical expression 3]
Rate of decomposition (%)=(1-WC/WP) * 100
(4) light penetration
Resins, epoxy is dissolved in the ethyl acetate of 2 times of weight, to the light penetration of solution, the spectrophotometer " UV-2400PC " with Shimadzu Seisakusho Ltd. makes uses the 1cm pond, with ethyl acetate is blank sample, the light penetration of the light of the wavelength of mensuration 400nm and 340nm.
(5) softening temperature
Measure according to ring and ball method (JIS-K-7234-1986).
(6) melt viscosity
Use ICI viscometer (cone-and-plate type rotational viscosimeter), the melt viscosity under measuring 150 ℃.
(7) glass transition temperature Tg (℃):
According to TMA method (heat-up rate is 5 ℃/minute).
(8) resistance to sudden heating (cracking resistance)
To 3 epoxy resin cured products of imbedding オ リ Off ア Application ト (oliphant) packing ring, thermal shock test is carried out in circulation with 170 ℃ shown in the following table 1～-75 ℃, stop when on cured article, cracking occurring, represent with the mean value that produces rimose round-robin " cracking resistance ".
[table 1]
| Recirculation | Testing condition | Experimental period (branch) | Cracking resistance |
| 1 | The former state state | - | 0 |
| 2 | Be cooled to 5 ℃ from 25 ℃ | 10 | 1 |
| 3 | Be heated to 25 ℃ from 5 ℃ | 30 | 2 |
| 4 | Be cooled to-15 ℃ from 25 ℃ | 10 | 3 |
| 5 | Be heated to 25 ℃ from-15 ℃ | 30 | 4 |
| 6 | Be cooled to-35 ℃ from 25 ℃ | 10 | 5 |
| 7 | Be heated to 25 ℃ from-35 ℃ | 30 | 6 |
| 8 | Be cooled to-55 ℃ from 25 ℃ | 10 | 7 |
| 9 | Be heated to 25 ℃ from-55 ℃ | 30 | 8 |
| 10 | Be heated to 130 ℃ from 25 ℃ | 30 | 9 |
| 11 | Be cooled to-55 ℃ from 130 ℃ | 10 | 10 |
| 12 | Be heated to 150 ℃ from-55 ℃ | 30 | 11 |
| 13 | Be cooled to-75 ℃ from 150 ℃ | 10 | 12 |
| 14 | Be heated to 170 ℃ from-75 ℃ | 30 | 13 |
| 15 | Be cooled to-75 ℃ from 170 ℃ | 10 | 14 |
| 16 | Be heated to 25 ℃ from-75 ℃ | 30 | 15 |
| 17 | By whole circulations | 16 |
(9) ultraviolet resistance
Use metering burn-in test instrument (metaling weather meter) (manufacturing of ス ガ trier company), be determined at exposure intensity 0.4kW/m
2, under 63 ℃ of the blackboard temperatures, the YI value of the cured article of irradiation ultraviolet radiation after 72 hours (Yellowness Index).
(10) resistance to thermal deterioration
Be determined at 150 ℃ of YI values (YellownessIndex) of the epoxy resin cured product of heating after 72 hours down.
(11) rate of moisture absorption (%)
Measure the rate of moisture absorption of discoid epoxy resin cured product after placing 24 hours under 121 ℃ of thick 3mm, diameter 50mm.
Production Example 1 (manufacturing of hydrogenation catalyst)
Rhodium chloride (the NE ケ system キ ヤ Star ト manufacturing) 625mg of 40 weight % is dissolved in the 20g water, and (" HSAG100 ", specific surface area that TIMCAL makes are 130m to add commercially available graphite in the rhodium chloride aqueous solution that obtains
2/ g) 4.75g contains the rhodium chloride aqueous solution and is immersed in the graphite.Interpolation is dissolved in the aqueous solution in the 6ml water with the ammoniacal liquor 0.78g of 28 weight %, at room temperature carries out immobilization and handles.Behind the solid resultant that filtering separation obtains, fully clean with ion exchanged water, 50 ℃ of following dryings, obtained supporting the not reduced form rhodium/graphite catalyst of 5 weight % rhodiums thus.
[embodiment 1～5 and comparative example 1～4: alicyclic epoxy resin relation]
Embodiment 1:
In 1L volumetrical induction stirred autoclave, bisphenol A-type solid epoxy resin (" the エ ピ コ-ト 1002 " that japan epoxy resin company (ジ ヤ パ Application エ Port キ シ レ ジ Application society) makes packs into, epoxy equivalent (weight): 642, Li, Na, K, N, each constituent content of P is 1ppm or below the 1ppm, total content is 5ppm or below the 5ppm, the light penetration of 400nm is 96%, 340 light penetration is 69%, melt viscosity: 1400mPas, the product that 1 terrace work is made) 200g, ethyl acetate 200g, (with respect to Resins, epoxy is 0.2 weight % to the not reduced form 5 weight % rhodium/graphite catalyst 0.4g that obtain as the Production Example 1 of hydrogenation catalyst, as rhodium, with respect to Resins, epoxy is 0.01 weight %), after carrying out the nitrogen displacement in the autoclave, carry out the hydrogen displacement.Then, under 110 ℃, carry out 6 hours hydrogenation reaction (by the absorption of pressure accumulator monitor hydrogen, absorb to finish reaction when stopping substantially at hydrogen) with the hydrogen pressure of 8MPa.
After reaction finishes, in reaction solution, add ethyl acetate and dilute, add magnesium oxide (consonance chemical company makes " キ ヨ-ワ マ グ 150 ") 4g, at room temperature carry out mixing in 30 minutes after-filtration.After filter finishing, the ethyl acetate in the reaction solution is reclaimed in distillation, removes under 160 ℃, pressure 100MPa and desolvates, and extracts the liquid postcooling out, obtains water white hydrogenated epoxy resin (alicyclic epoxy resin).
The hydrogenated epoxy resin that obtains is water white solid, and the nuclear hydrogenation rate is 99.4%, and epoxy equivalent (weight) is 719, the rate of decomposition of epoxy group(ing) is 7%, and the light penetration of 400nm is 99%, and the light penetration of 340nm is 96%, softening temperature is 71 ℃, and melt viscosity is 860mPas.
Embodiment 2
Add bisphenol A-type solid epoxy resin (" the エ ピ コ-ト 1003 " that japan epoxy resin company (ジ ヤ パ Application エ Port キ シ レ ジ Application society) makes, epoxy equivalent (weight): 741, Li, Na, K, N, each constituent content of P is 1ppm or below the 1ppm, total content is 5ppm or below the 5ppm, the light penetration of 400nm is 96%, 340 light penetration is 65%, melt viscosity: 2700mPas, the product that 1 terrace work is made) 200g, ethyl acetate 200g, (with respect to Resins, epoxy is 0.5 weight % to the not reduced form 5 weight % rhodium/graphite catalyst 1g that obtain as the Production Example 1 of hydrogenation catalyst, as rhodium, with respect to Resins, epoxy is 0.025 weight %), after carrying out the nitrogen displacement in the autoclave, carry out the hydrogen displacement.Then, under 110 ℃, carry out 1.8 hours hydrogenation reaction with the hydrogen pressure of 8MPa after, implement post-processing operation similarly to Example 1, obtain hydrogenated epoxy resin (alicyclic epoxy resin).
The hydrogenated epoxy resin that obtains is water white solid, and the nuclear hydrogenation rate is 99.8%, and epoxy equivalent (weight) is 909, the rate of decomposition of epoxy group(ing) is 15%, and the light penetration of 400nm is 99%, and the light penetration of 340nm is 96%, softening temperature is 72 ℃, and melt viscosity is 1540mPas.
Embodiment 3
Add bisphenol A-type solid epoxy resin (" the エ ピ コ-ト 1004AF " that japan epoxy resin company (ジ ヤ パ Application エ Port キ シ レ ジ Application society) makes, epoxy equivalent (weight): 919, Li, Na, K, N, each constituent content of P is 1ppm or below the 1ppm, total content is 5ppm or below the 5ppm, the light penetration of 400nm is 95%, 340 light penetration is 66%, melt viscosity: 6900mPas, the product that 1 terrace work is made) 200g, ethyl acetate 200g, (with respect to Resins, epoxy is 0.5 weight % to the not reduced form 5 weight % rhodium/graphite catalyst 1g that obtain as the Production Example 1 of hydrogenation catalyst, as rhodium, with respect to Resins, epoxy is 0.025 weight %), after carrying out the nitrogen displacement in the autoclave, carry out the hydrogen displacement.Then, under 110 ℃, carry out 2 hours hydrogenation reaction with the hydrogen pressure of 8MPa after, implement post-processing operation similarly to Example 1, obtain hydrogenated epoxy resin (alicyclic epoxy resin).
The hydrogenated epoxy resin that obtains is water white solid, and the nuclear hydrogenation rate is 99.9%, and epoxy equivalent (weight) is 1184, the rate of decomposition of epoxy group(ing) is 19%, and the light penetration of 400nm is 99%, and the light penetration of 340nm is 96%, softening temperature is 85 ℃, and melt viscosity is 3200mPas.
Embodiment 4
Add bisphenol A-type solid epoxy resin (" the エ ピ コ-ト 1007 " that japan epoxy resin company (ジ ヤ パ Application エ Port キ シ レ ジ Application society) makes, epoxy equivalent (weight): 2015, Li, Na, K, N, each constituent content of P is 1ppm or below the 1ppm, total content is 5ppm or below the 5ppm, the light penetration of 400nm is 90%, 340 light penetration is 65%, melt viscosity: 40000mPas, the product that 1 terrace work is made) 100g, ethyl acetate 300g, (with respect to Resins, epoxy is 2 weight % to the not reduced form 5 weight % rhodium/graphite catalyst 2g that make as the Production Example 1 of hydrogenation catalyst, as rhodium, with respect to Resins, epoxy is 0.1 weight %), after carrying out the nitrogen displacement in the autoclave, carry out the hydrogen displacement.Then, under 110 ℃, carry out 1 hour hydrogenation reaction with the hydrogen pressure of 8MPa.Then, use MgO as sorbent material (" AD100P " that rich field drugmaker makes), in addition, implement post-processing operation similarly to Example 1, obtain hydrogenated epoxy resin (alicyclic epoxy resin).
The hydrogenated epoxy resin that obtains is water white solid, and the nuclear hydrogenation rate is 99.2%, and epoxy equivalent (weight) is 2199, the rate of decomposition of epoxy group(ing) is 5%, and the light penetration of 400nm is 92%, and the light penetration of 340nm is 85%, softening temperature is 101 ℃, and melt viscosity is 14700mPas.
Embodiment 5
After being dissolved in Bisphenol F type solid epoxy resin (" エ ピ コ-ト 4004P " that japan epoxy resin company (ジ ヤ パ Application エ Port キ シ レ ジ Application society) makes) 300g in the 1200g hexone, under 70～80 ℃ temperature, carrying out 3 times and clean with the 500g pure water.Then, Resins, epoxy 200g (the epoxy equivalent (weight): 878 that interpolation obtains by heating up in a steamer the demethyl isobutyl ketone, Li, Na, K, N, each constituent content of P are 1ppm or below the 1ppm, total content is that 5ppm or 5ppm are following), (with respect to Resins, epoxy is 2 weight % for ethyl acetate 200g, not reduced form 5 weight % rhodium/graphite catalyst 1g of making as the Production Example 1 of hydrogenation catalyst, as rhodium, with respect to Resins, epoxy is 0.1 weight %), after carrying out the nitrogen displacement in the autoclave, carry out the hydrogen displacement.Then, under 110 ℃, carry out 2 hours hydrogenation reaction with the hydrogen pressure of 8MPa after, implement post-processing operation similarly to Example 1, obtain hydrogenated epoxy resin (alicyclic epoxy resin).
The hydrogenated epoxy resin that obtains is water white solid, and the nuclear hydrogenation rate is 99.8%, and epoxy equivalent (weight) is 1022, and softening temperature is 74 ℃.
Comparative example 1
Remove " エ ピ コ-ト the 1004F " (epoxy equivalent (weight): 933 that uses japan epoxy resin company (ジ ヤ パ Application エ Port キ シ レ ジ Application society) to make, nitrogen element: contain 18ppm, the product that 2 terrace works are made) as beyond the bisphenol A-type solid epoxy resin, carry out operation similarly to Example 3, reacted 1 hour, do not consume hydrogen fully, so stopped reaction.
Comparative example 2
Remove " エ ピ コ-ト the 1006F " (epoxy equivalent (weight): 1103 that uses japan epoxy resin company (ジ ヤ パ Application エ Port キ シ レ ジ Application society) to make, nitrogen element: contain 17ppm, the product that 2 terrace works are made) as beyond the Resins, epoxy, carry out operation similarly to Example 4, reacted 1 hour, do not consume hydrogen fully, so stopped reaction.
Comparative example 3
Remove " エ ピ コ-ト the 1006FS " (epoxy equivalent (weight): 965 that uses japan epoxy resin company (ジ ヤ パ Application エ Port キ シ レ ジ Application society) to make, sodium element: contain 20ppm, the product that 2 terrace works are made) as beyond the Resins, epoxy, carry out operation similarly to Example 4, reacted 1 hour, do not consume hydrogen fully, so stopped reaction.
Comparative example 4
Remove " エ ピ コ-ト 1001 " (epoxy equivalent (weight): 465 that uses japan epoxy resin company (ジ ヤ パ Application エ Port キ シ レ ジ Application society) to make, Li, Na, K, N, each constituent content of P are 1ppm or below the 1ppm, total content is that 5ppm or 5ppm are following) as beyond the bisphenol A-type solid epoxy resin, similarly carry out hydrogenation reaction and post-processing operation with Production Example 1, obtain hydrogenated epoxy resin.
The hydrogenated epoxy resin that obtains is water white thick liquid, and the nuclear hydrogenation rate is 99.8%, and epoxy equivalent (weight) is 534, and light penetration is 99%.
From above result as can be known, according to the present invention, can obtain being under the normal temperature the excellent alicyclic epoxy resin of the solid transparency with high hydrogenation rate with the aromatic epoxy resin nuclear hydrogenationization.
[embodiment 6～11 and comparative example 5,6: the relation of composition epoxy resin]
Embodiment 6:
For cooperating 100 parts of the solid-state hydrogenated epoxy resins that embodiment 1 obtains, as " the リ カ シ Star De MH-700 " of solidifying agent (new Japanese physics and chemistry company trade(brand)name, methylhexahydrophthalic anhydride) 23 part, " ヒ シ コ-リ Application PX-4ET " (Japanese chemical industrial company trade(brand)name as curing catalyst, Si Zheng Ding Ji Phosphonium-o, 1 part of o-diethyl idol phosphorus two thionuric acid ester (チ オ ネ-ト)), as 2 of oxidation inhibitor, 0.2 part of 6-ditertbutylparacresol and phenylbenzene isodecyl phosphoesterase 30 .2 part, use mixing roll, under 80～90 ℃ temperature, carry out 20 minutes melting mixing, carry out pre-reaction simultaneously, make the composition epoxy resin of semi-cured state (B level).Softening temperature of this composition epoxy resin (according to the ring and ball method of JIS-K-7234) and gelation time (measuring down at 150 ℃ by the iron plate method) are as shown in table 2.The fusion composition epoxy resin that obtains takes out to sheet, obtains formed material after the pulverizing.In addition, in the table 2, Resins, epoxy I represents the hydrogenated epoxy resin that the present invention relates to, and Resins, epoxy II represents other Resins, epoxy.
Use low pressure transfer mould shaper at 150 ℃ of die temperatures, 180 seconds compacted unders of molding time by the above-mentioned formed material that obtains, obtain each test film, carry out 3 hours after fixing again under 140 ℃, obtain water white cured article, the evaluation result of this cured article is shown in table 2.
Embodiment 7～11, comparative example 5～6
Except that change Resins, epoxy and hardener for epoxy resin according to table 2, carry out operation similarly to Example 6, obtain the composition epoxy resin of softening temperature shown in the table 2 (according to the ring and ball method of JIS-K-7234) and gelation time (measuring down at 150 ℃) by the iron plate method, similarly obtain cured article (wherein by this composition epoxy resin, because the composition epoxy resin of comparative example 1 is a liquid, therefore can not moulding, curing).The evaluation result of these cured articles is shown in table 2.
[table 2]
*1: the cooperation beyond the oxygenant
*2: the solid-state alicyclic epoxy resin of Resins, epoxy A=(" EHPE3150 " that ダ イ セ Le industrial makes)
Resins, epoxy B=3,4-epoxycyclohexyl methyl-3 ', 4 '-epoxycyclohexane carboxylate (manufacturing of ジ ヤ パ Application エ Port キ シ レ ジ Application company)
Resins, epoxy C=bisphenol A-type solid epoxy resin (" E1004AF " that ジ ヤ パ Application エ Port キ シ レ ジ Application company makes)
*3: aromatic series sulfonium salt type cationic polymerization initiators (Japanese Cao Da company make)
As shown in Table 2, according to the present invention, can obtain the epoxy resin cured product of water white and resistance to sudden heating, photostabilization, excellent heat resistance.
Claims (15)
1. one kind is the solid alicyclic epoxy resin at normal temperatures, this alicyclic epoxy resin be with epoxy equivalent (weight) be 500～10000, the total content of basic metal and the 15th family's element is that 10ppm or the aromatic epoxy resin below the 10ppm carry out nuclear hydrogenationization and obtain, and satisfies the regulation of following (a)～(d):
(a) epoxy equivalent (weight) is 500～10000;
(b) the nuclear hydrogenation rate is more than 96% or 96%;
(c) softening temperature in the ring and ball method of JIS-K-7234 is 40～200 ℃;
(d) be more than 90% or 90% at the light penetration of measuring under the wavelength 400nm.
2. according to the alicyclic epoxy resin of claim 1 record, wherein, aromatic epoxy resin is that epoxy equivalent (weight) is 600～6000, bisphenol A type epoxy resin and/or bisphenol f type epoxy resin.
3. one kind is the manufacture method of solid alicyclic epoxy resin at normal temperatures, it is characterized in that, with epoxy equivalent (weight) be 500～10000, the total content of basic metal and the 15th family's element is 10ppm or the aromatic epoxy resin nuclear hydrogenationization below the 10ppm, described alicyclic epoxy resin satisfies the regulation of following (a)～(d):
(a) epoxy equivalent (weight) is 500～10000;
(b) the nuclear hydrogenation rate is more than 96% or 96%;
(c) softening temperature in the ring and ball method of JIS-K-7234 is 40～200 ℃;
(d) be more than 90% or 90% at the light penetration of measuring under the wavelength 400nm.
4. according to the manufacture method of claim 3 record, wherein, nuclear hydrogenationization in the presence of the catalyzer that contains platinum family element.
5. according to the manufacture method of claim 4 record, wherein, the catalyzer that contains platinum family element obtains the catalyst precursor reduction that has supported platinum family compound on carrier.
6. according to the manufacture method of claim 5 record, wherein, when the reducing catalyst precursor, make the aromatic epoxy resin coexistence, in same reaction system, carry out the reduction of catalyst precursor and the nuclear hydrogenation reaction of aromatic epoxy resin simultaneously.
7. an alicyclic epoxy resin compositions is characterized in that, contains the alicyclic epoxy resin and the epoxy curing agent of claim 1 or 2 records.
8. according to the composition epoxy resin of claim 7 record, wherein, epoxy curing agent is anhydride compound and/or cationic polymerization initiators.
9. according to the composition epoxy resins of claim 7 or 8 records, wherein,, contain at least a kind the oxidation inhibitor in phenolic antioxidant, sulfur type antioxidant and the Phosphorus oxidation inhibitor of being selected from of 0.005～5 mass parts with respect to alicyclic epoxy resin 100 mass parts.
10. an epoxy resin cured product is characterized in that, this cured article is that the composition epoxy resin of each record in the claim 7～9 is solidified to form.
11. an electric and electronic material sealing material is characterized in that, contains the alicyclic epoxy resin compositions of each record in claim 1 or 2 Resins, epoxy of putting down in writing or the claim 7～9.
12. according to the sealing material of claim 11 record, the sealing material is the luminous element sealing material.
13. according to the sealing material of claim 12 record, wherein, the main glow peak of luminous element is 350～550nm.
14. according to the sealing material of claim 11 record, the sealing material is used in the sealing of photodiode, sealing uses low pressure transfer mould shaper to carry out.
15. a semiconductor light-emitting apparatus is characterized in that this device has used the sealing material of each record in the claim 11～14.
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