CN1309783C - Epoxy resin compositing, its solidification product, new-type epoxy resin, phenol compound, and its preparation method - Google Patents
Epoxy resin compositing, its solidification product, new-type epoxy resin, phenol compound, and its preparation method Download PDFInfo
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- CN1309783C CN1309783C CNB021470073A CN02147007A CN1309783C CN 1309783 C CN1309783 C CN 1309783C CN B021470073 A CNB021470073 A CN B021470073A CN 02147007 A CN02147007 A CN 02147007A CN 1309783 C CN1309783 C CN 1309783C
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Abstract
The present invention relates to an epoxy resin composition a cure article thereof, a novel epoxy resin used therein, a polyhydric phenol compound suited for used as an intermediate thereof, and a process for preparing the same. One of the objects to be achieved by the present invention is to exert the heat resistance, the moisture resistance, the dielectric performances and the flame-resistant effect required of electric or electronic materials such as semiconductor encapsulating materials and varnishes for circuit boards in the epoxy resin composition.
Description
Invention field
The present invention relates to composition epoxy resin, its cured article, use therein neo-epoxy resin is suitable as the polyphenol compound of its intermediate and prepares its method.
Background of invention
The thermoset rubber composition that contains Resins, epoxy and solidifying agent is widely used in electric or electronic material, as semiconductor sealing material and circuit card lacquer.
Recently, at semiconductor applications, although be extensive use of single face closed type packing as ball grillages row N-type semiconductorN, this has also caused big problem, for example the packing bending behind the molding.In order to address this problem, nowadays need a kind of sealing resin that has high glass transition temperature.In the wiring board field, be starved of a kind of material that has high glass transition temperature equally, with it as a kind of means that improve the dimensional stability of multilayer layer pressing plate.
In order to improve the thermotolerance of epoxy resin cure goods, increase the cross-linking density of cured article usually.Therefore, the concentration of epoxy group(ing) is necessary in the increase Resins, epoxy.Yet, method like this, cured article contains the secondary hydroxyl that is derived from epoxy group(ing) in a large number, has therefore damaged the required performance of semiconductor sealing material and circuit card lacquer, for example moistureproof and low stability.
For example, Japanese patent application, publish open No.Hei 8-27250 and Japanese patent application for the first time, publish for the first time and disclose the technology of use dicyclopentadiene-type epoxy resin as Resins, epoxy in the semiconductor sealing material among the open No.Hei 9-48839, the cured article of this material has extraordinary thermotolerance and does not damage its needed performance as moistureproof and low stability.
Although at Japanese patent application, publish open No.Hei 8-27250 and Japanese patent application for the first time, disclosed dicyclopentadiene-type epoxy resin has extraordinary performance as semiconductor sealing material among the open No.Hei 9-48839 of publication for the first time, for example, cured article has extraordinary heat-resisting, waterproof and insulating property, but, additive based flameproofing such as halogen-based flame retardants and phosphine flame retardant have therefore in use unavoidably been used because dicyclopentadiene-type epoxy resin is inflammable.On the other hand, halogen-based flame retardants is the material that can produce dioxin, and also there is the problem that reduces resistance to hydrolysis in phosphine flame retardant except its toxicity.Therefore desired composition epoxy resin is such composition, and Resins, epoxy itself has obtained flame retardant resistance and do not damaged above-mentioned needed performance.
Summary of the invention
The purpose that the present invention will realize is the electric or electronic material of performance in composition epoxy resin, and is needed heat-resisting as semiconductor sealing material and circuit card lacquer, protection against the tide, insulating property and flame retardant effect.
Another purpose that the present invention will realize provide a kind of have very good heat-resisting, protection against the tide, the neo-epoxy resin of insulating property and flame retardant effect.
Another purpose that the present invention will realize provides a kind of phenolic compound that is suitable as the neo-epoxy resin intermediate.
To achieve these goals, inventor of the present invention has made extensive studies, discovers, by introducing epoxy resin structural as the fragrant polynuclear plane of the structure of the repeating unit that constitutes epoxy resin structural, except heat-resisting, outside protection against the tide and the insulating property, flame retardant resistance significantly improves.In fragrant polynuclear plane, two adjacent replacement positions of two kinds of aromatic hydrocarbon aromatic nucleus in aromatic hydrocarbon combine by carbon atom or Sauerstoffatom.Like this, finished the present invention.
The present invention relates to contain the composition epoxy resin of Resins, epoxy and solidifying agent, Resins, epoxy wherein contains fragrant polynuclear plane, in described fragrant polynuclear plane, two kinds of aromatic hydrocarbon combine by carbon atom or Sauerstoffatom two adjacent replacement positions of aromatic nucleus in aromatic hydrocarbon, also contain on fragrant polynuclear plane as substituent glycidyl oxygen base.
Preferably, the present invention relates to a kind of composition epoxy resin that contains Resins, epoxy and solidifying agent, Resins, epoxy wherein has fragrant polynuclear plane, the adjacent replacements of two on aromatic nucleus in aromatic hydrocarbon of two aromatic hydrocarbon in this structure position combines by carbon atom and Sauerstoffatom respectively, and also contains on fragrant polynuclear plane as substituent glycidyl oxygen base.
Another aspect of the present invention relates to the neo-epoxy resin with following general formula (1) expression:
In general formula (1), X represention oxygen atom, methylene radical, with the methylene radical that the alkyl that contains 1-4 carbon atom replaces,, use the methylene radical of naphthyl substituted with the methylene radical that phenyl replaces, methylene radical with the xenyl replacement, with the methylene radical of 9-fluorenyl replacement, or such methylene radical, alkyl is further at phenyl in this methylene radical, naphthyl, or replaced on the aromatic ring on the xenyl, n and m represent integer 0-3, and p represents average number of repeat unit 0-10.
Another aspect of the present invention relates to the neo-epoxy resin by general formula (2) representative:
In the general formula (2), X represention oxygen atom, methylene radical, with the methylene radical that the alkyl that contains 1-4 carbon atom replaces,, use the methylene radical of naphthyl substituted with the methylene radical that phenyl replaces, methylene radical with the xenyl replacement, with the methylene radical of 9-fluorenyl replacement, or a kind of like this methylene radical, alkyl is further at phenyl in this methylene radical, naphthyl, or replaced on the aromatic ring on the xenyl, on behalf of integer 0-5 and p, n and m represent average number of repeat unit 0-10.
Another aspect of the present invention relates to the novel phenolic compound by general formula (3) representative:
In the general formula (3), X represention oxygen atom, methylene radical, methylene radical with the alkyl replacement, with the methylene radical that phenyl replaces, use the methylene radical of naphthyl substituted, with the methylene radical of xenyl replacement, methylene radical with the replacement of 9-fluorenyl, or a kind of like this methylene radical, in this methylene radical alkyl further at phenyl, naphthyl, or replaced on the aromatic ring on the xenyl and n and m represent integer 0-3.
Another aspect of the present invention relates to the novel phenolic compound by general formula (4) representative:
In the general formula (4), X represention oxygen atom, methylene radical, methylene radical with the alkyl replacement, with the methylene radical that phenyl replaces, use the methylene radical of naphthyl substituted, with the methylene radical of xenyl replacement, methylene radical with the replacement of 9-fluorenyl, or a kind of like this methylene radical, in this methylene radical alkyl further at phenyl, naphthyl, or replaced on the aromatic ring on the xenyl and n and m represent integer 0-5.
Another aspect of the present invention relates to a kind of method for preparing polyol, this method is included in acid catalyst when existing, the compound and the compound reaction that contains carbonyl of two hydroxyls will be contained on the phenyl ring, one of described two hydroxyls contain a hydrogen atom at the ortho position, remaining replaces the position all is substituting group upward.
The invention still further relates to by thermofixation and handle the cured article that epoxy composite obtains.
The accompanying drawing summary
Fig. 1 shows resulting polyol among the embodiment 1
13C NMR spectrogram.
Fig. 2 is the IR spectrogram that shows resulting polyol among the embodiment 1.
Fig. 3 is the mass spectrum that shows resulting polyol among the embodiment 1.
Fig. 4 shows resulting Resins, epoxy among the embodiment 2
13C NMR spectrogram.
Fig. 5 is the IR spectrogram that shows resulting Resins, epoxy among the embodiment 2.
Fig. 6 is the mass spectrum that shows resulting Resins, epoxy among the embodiment 2.
Fig. 7 shows resulting polyol among the embodiment 3
13C NMR spectrogram.
Fig. 8 is the IR spectrogram that shows resulting polyol among the embodiment 3.
Fig. 9 is the mass spectrum that shows resulting polyol among the embodiment 3.
Figure 10 shows resulting Resins, epoxy among the embodiment 4
13C NMR spectrogram.
Figure 11 is the IR spectrogram that shows resulting Resins, epoxy among the embodiment 4.
Figure 12 is the mass spectrum that shows resulting Resins, epoxy among the embodiment 4.
Detailed description of the preferred embodiments
The present invention will be described in detail now.
The Resins, epoxy that uses in the composition epoxy resin of the present invention, fragrant polynuclear plane is arranged, in fragrant polynuclear plane, two kinds of aromatic hydrocarbon combine by carbon atom or Sauerstoffatom two adjacent replacement positions of aromatic nucleus in aromatic hydrocarbon, also contain on fragrant polynuclear plane as substituent glycidyl oxygen base.
When by when in epoxy resin structural, introducing such rigidity and symmetrical structure and reduce epoxy group(ing) concentration, because aromaticity content raises, thus not only moistureproof and insulating property are very good, and given play to extraordinary flame retardant effect.Because structure rigidity, thermotolerance also significantly improves.
The specific embodiment of fragrance polycyclic moiety comprises array structure down.In the following structural, the line segment that each bar is drawn from aromatic nucleus is all represented the covalent linkage with other structure division.
Wherein, because flame retardant effect is significantly increased, thus for example contain the compound of structure 14-24 particularly preferably in the compound that contains methyl in the aromatic ring, or wherein aromatic hydrocarbon is the compound of naphthalene, for example contains the compound of structure 5-8.
Although the Resins, epoxy in the composition epoxy resin of the present invention contains above-mentioned fragrant polycyclic moiety as repeating unit, Resins, epoxy can partly comprise the aromatic structure that contains other structure.As selection, can be used in combination the Resins, epoxy that contains another aromatic nucleus.Because effect of the present invention can be brought into play fully, so epoxy resin ingredient preferably contains the fragrant polycyclic moiety of at least one determined number.Specifically, for the situation of front, the carbonatoms of forming fragrant polycyclic moiety account for aromatic carbon atom number in the Resins, epoxy 20% or more.In the situation of back, the carbonatoms of forming fragrant polycyclic moiety accounts in the composition epoxy resin in the whole epoxy resin ingredient 20% of the aromatic carbon atom number.
Resins, epoxy has such feature: when having high relatively epoxy equivalent (weight), the protection against the tide and the insulating property of Resins, epoxy are good.Therefore, consider in protection against the tide, reach well balanced between insulating property and the flame retardant properties, preferably containing epoxy equivalent (weight) is 240-330 gram/equivalent. Resins, epoxy.
The neo-epoxy resin of representing with structural formula 1 or all be suitable as Resins, epoxy with the neo-epoxy resin that structural formula 2 is represented.
To be described in detail these new type resins of the present invention now.
Neo-epoxy resin of the present invention is represented with general formula (1).
In the neo-epoxy resin of general formula (1) expression, particularly preferably in the Resins, epoxy that contains methyl in the fragrant polynuclear plane, promptly contain the Resins, epoxy of general formula (1) structure, wherein n and m represent 1-3.The specific examples of forming the repeating unit of this Resins, epoxy comprises following example.
Wherein, preferably in forming the phenyl ring of fragrant polycyclic moiety, contain the compound of three methyl, for example contain the compound of E2-E9 structure because they be easy to that industry is made and also improve aspect the heat-resisting and fire-retardant effect very good.The compound that preferably contains the E2-E3 structure, because they are very good aspect heat-resisting, and preferably has E1, E2, the compound of E3 and E4 structure is because they mobile satisfactory, preferably have E7, the compound of E8 structure be because they fire-retardant, the insulation and the humidity resistance aspect very good.
The neo-epoxy resin that contains the naphthalene skeleton of the present invention is represented with general formula (2).
The specific examples of the repeating unit of component epoxy comprises following example.
In neo-epoxy resin,, improved the flame retardant effect of cured article owing to the epoxide equivalent height of Resins, epoxy with general formula (1) or (2) expression.When epoxide equivalent was high, along with cross-linking density reduces, thermotolerance reduced usually.Yet, in situation of the present invention,, do not observe thermotolerance and reduce, and in situation of the present invention, given play to very good thermotolerance although epoxy equivalent (weight) has relative increase.Preferred epoxy equivalent (weight) is at 240-330 gram/equivalent, because this makes this feature become more remarkable.
As mentioned above, represent the p value of number of iterations mean value in general formula (1) and (2), between 0-10, but can regulate arbitrarily according to desired performance.For the flowability that improves composition and the thermotolerance of cured article, the preferred 0-1 of mean P value.In order to improve the workability of composition, the preferred 1-5 of mean P value by the softening temperature that improves composition.
In addition, by methyl is introduced aromatic nucleus, the flame retardant effect of neo-epoxy resin of the present invention is significantly increased.Be more significantly: burn easily although contain many alkyl, the flame retardant effect of cured article but is significantly increased.
Can prepare neo-epoxy resin of the present invention as the intermediate and the novel phenolic compound glycidyl etherificate that will obtain by preparing novel phenolic compound of the present invention.
To be described in detail these novel phenolic compound of the present invention now.
Novel phenolic compound of the present invention is represented with general formula (3).
The specific examples of novel phenolic compound comprises those that contain following array structure.
Another novel phenolic compound of the present invention is represented with general formula (4).
The specific examples of novel phenolic compound comprises those that contain following array structure.
As the intermediate of neo-epoxy resin of the present invention, very useful with the novel phenolic compound of general formula (3) or (4) expression, but because its rigidity and symmetrical structure can be used it for multiple purpose, therefore can improve its thermotolerance and flame retardant resistance.Specifically, novel phenolic compound can be used as the starting material of epoxy curing agent and vinyl ester resin, the starting material of photosensitive material such as semi-conductor photoresist and the starting material of polycarbonate, vibrin and polyacrylate resin.
When acid catalyst exists, to contain the dihydroxy-benzene of hydrogen atom in the position of closing on hydroxyl or contain the dihydroxy naphthlene of hydrogen atom in the position of closing on hydroxyl, compound reaction with containing carbonyl can prepare the novel phenolic compound with general formula (3) or (4) expression like this.In this case, when produce as byproduct contain the phenolic compound of other structure the time, can isolate desired compounds by purification process such as recrystallization.
The example that contains the dihydroxy-benzene of hydrogen atom in the position of closing on hydroxyl comprises Resorcinol, the monomethyl Resorcinol, the Trimethyl Hydroquinone, trimethylammonium Resorcinol and trimethylammonium catechol, and the example that contains the dihydroxy naphthlene of hydrogen atom in the position of closing on hydroxyl comprises 1,6-dihydroxy naphthlene, 2,7 dihydroxy naphthlenes and 1,6-dihydroxyl-7-methylnaphthalene.
In the method for preparation phenolic compound of the present invention, the compound that contains two hydroxyls on phenyl ring is used as dihydroxy-benzene, and one of them hydroxyl contains a hydrogen atom at the ortho position, and remaining all replaces on the position substituting group.According to method of the present invention, can high purity ground each novel phenolic compound of system with general formula (3) expression.
The example that contains the compound (one of them hydroxyl contains a hydrogen atom at the ortho position, remaining all replaces on the position substituting group) of two hydroxyls comprises: Trimethyl Hydroquinone, trimethylammonium Resorcinol and trimethylammonium catechol.In addition, can use the Trimethyl Hydroquinone, tri-tert Resorcinol, tribromo Resorcinol and three chlorohydroquinones.
The multiple compound that contains carbonyl can be used for and above-mentioned compound reaction.According to the kind of carbonyl containing compound, can in novel phenolic compound, introduce multiple structure, this makes that giving multiple performance for novel phenolic compound becomes possibility.
Its specific embodiment comprises aldehyde cpd such as formaldehyde, acetaldehyde, phenyl aldehyde, 4-tolyl aldehyde, 3,4-dimethylbenzaldehyde, two benzaldehydes and naphthaldehyde; With ketone compound such as benzophenone, Fluorenone and 2,3-dihydro-1 indone.In these compounds, preferred phenyl aldehyde, the 4-tolyl aldehyde, 3, the 4-dimethylbenzaldehyde, biphenyl aldehyde and naphthaldehyde are to significantly improve the flame retardant resistance of epoxy resin intermediate.
Be used as catalysts with acid catalyst.In order to prepare highly purified novel phenolic compound, as catalyzer, these strong acid are spirit of salt for example, sulfuric acid, tosic acid and methylsulfonic acid with strong acid.
The position of containing the dihydroxy-benzene of hydrogen atom or closing on hydroxyl in the position of closing on hydroxyl is contained the dihydroxy naphthlene of hydrogen atom and is contained reaction between the compound of carbonyl, finish by following phases: the fs, by the condensation reaction between dihydroxyl Three methyl Benzene or dihydroxy naphthlene and the carbonyl containing compound, the dihydroxyl Three methyl Benzene is bonded to each other by methylene radical; Subordinate phase by the dehydrating condensation between the hydroxyl, forms 6-unit cyclic ethers skeleton.For example, synoptic diagram below (1) and (2) have shown first and second elementary reactions of the reaction between Trimethyl Hydroquinone and the formaldehyde.
The condition of reaction can be that this two-stage successive reaction is carried out to form the reaction conditions of required skeleton.Specifically, the compound reaction that contains carbonyl of 1 mole dihydroxy-benzene or dihydroxy naphthlene and 0.1-3.0 mole, preferred 50-200 ℃ especially of temperature of reaction is because can improve the output and the purity of product desired in the reaction product like this.
Because these reaction conditionss have improved product output and purity desired in the reaction product, the compound reaction that contains carbonyl of therefore preferred especially 1 mole dihydroxy-benzene or dihydroxy naphthlene and 0.4-0.7 mole, especially preferably 100-150 ℃ of temperature of reaction.
Preferably pass through at suitable organic solvent such as toluene, benzene, ethylene glycol, or the dissolving starting material react in its mixed solvent.Because the reaction of subordinate phase is a dehydration reaction, so preferably react in the water that in removing reaction process, forms.
Can (this novel phenolic compound be dissolved in epihalohydrins such as Epicholorohydrin by novel phenolic compound that alkali metal hydroxide is obtained as sodium hydroxide or potassium hydroxide join among the present invention, in epibromohydrin or the a-methyl epichlorohydrin) mixture in, make its reaction 1-10 hour or under 20-120 ℃ condition under 20-120 ℃ the condition, when adding alkali metal hydroxide, make its reaction 1-10 hour, to obtain neo-epoxy resin of the present invention.
Based on 1 equivalent hydroxyl in the starting material phenol resins, the amount of epihalohydrins is generally the 0.3-20 equivalent.When the amount of epihalohydrins during, obtain the high-molecular weight compounds that contains secondary hydroxyl that forms by the addition reaction between epoxy group(ing) and the unreacted hydroxyl less than 2.5 equivalents.On the other hand, when the amount of epihalohydrins during greater than 2.5 equivalents, the content of low-molecular weight compound increases.
In the reaction between novel phenolic compound and epihalohydrins, alkali metal hydroxide uses in the mode of the aqueous solution.Under the sort of situation, can make in the following method: the aqueous solution that in reaction system, adds alkalimetal oxide continuously, steaming dewaters and epihalohydrins continuously under decompression or normal pressure, and solution is divided into water and epihalohydrins, removes the epihalohydrins in water and the continuous Returning reacting system.
Also can obtain Resins, epoxy of the present invention: will be as the quaternary ammonium salt such as the tetramethyl ammonium chloride of catalyzer by following method, tetramethyl ammonium chloride, or the tetramethyl-benzyl ammonium chloride joins in the mixture of the novel phenolic compound that is dissolved in epihalohydrins, under 50-150 ℃ condition, make its reaction 1-5 hour, the solid or the liquor that in the epihalohydrins etherificate compound of resultant phenol resins, add alkali metal hydroxide, under 20-120 ℃ condition, make its reaction 1-10 hour once more, thereby cause dehydrohalogenation effect (closed loop).
In these reactions, preferred adding is pure as methyl alcohol, ethanol, Virahol and butanols; Ketone such as acetone and methylethylketone; Ether such as dioxane; To sprotic polar solvent such as dimethyl sulfone and methyl-sulphoxide, so that reacting balance carries out.When using solvent, based on the epihalohydrins of 100 weight parts, the consumption of solvent is usually at the 5-50 weight part, preferred 10-30 weight part.When using sprotic polar solvent, consumption is usually at the 5-100 weight part, and preferred 10-60 weight part is based on 100 weight part epihalohydrins.
After epoxidation reaction is finished, water flushing reaction product or need not, then, be heated to 110-250 ℃ to remove the solvent of epihalohydrins and other interpolation by under 10mmHg or lower reduced pressure, obtain thick Resins, epoxy.
In order to obtain containing the Resins, epoxy of less hydrolyzable halogen, thick Resins, epoxy is dissolved in solvent such as toluene or the methyl iso-butyl ketone (MIBK) again, behind the aqueous solution that has added alkali metal hydroxide such as sodium hydroxide or potassium hydroxide,, thereby guarantee that ring is closed with mixture reaction.In this case, the amount of alkalimetal oxide is usually at the 0.5-10 mole, and preferred 1.2-5.0 mole is based on 1 mole of hydrolyzable chlorine that is retained in the thick Resins, epoxy.The preferred 50-120 of temperature of reaction ℃, and preferred 0.5-3 of reaction times hour.In order to improve speed of reaction, can use phase-transfer catalyst such as quaternary ammonium salt and crown ether.When using phase-transfer catalyst, the preferred 0.1-3.0 weight part of consumption is based on the thick Resins, epoxy of 100 weight parts.
After reaction was finished, with filtering or washing the salt that removes formation, heating was heated up in a steamer and is desolvated as toluene or methyl iso-butyl ketone (MIBK) under reduced pressure, to obtain neo-epoxy resin of the present invention.
Although composition epoxy resin of the present invention comprises the Resins, epoxy that contains fragrant polynuclear plane, preferably can be used in combination neo-epoxy resin in the present invention, solidifying agent, other Resins, epoxy.
The example of the Resins, epoxy that can be used in combination comprises bisphenol A type epoxy resin, bisphenol f type epoxy resin, biphenyl type epoxy resin, tetramethyl biphenyl type Resins, epoxy, phenol novolak type epoxy resin, the cresols phenolic resin varnish type epoxy resin, tritane type Resins, epoxy, three phenylethane type Resins, epoxy, Dicyclopentadiene (DCPD)-phenol addition reaction-type Resins, epoxy, phenol aralkyl-type epoxy resin, naphthol novolac varnish type Resins, epoxy, the naphthols aralkyl-type epoxy resin, naphthols-phenol cocondensation mould assembly Resins, epoxy, naphthols toluene cocondensation mould assembly Resins, epoxy, the resin modified phenolic resin type Resins, epoxy of aromatic hydrocarbon formaldehyde, the phenolic resin varnish type epoxy resin of biphenyl modification, the phenol novolak type epoxy resin that tetrabromo-bisphenol type Resins, epoxy and bromination are handled.In these Resins, epoxy, consider preferred especially bisphenol A type epoxy resin, bisphenol f type epoxy resin, biphenyl type epoxy resin, tetramethyl biphenyl type Resins, epoxy, and Dicyclopentadiene (DCPD)-phenol addition reaction-type Resins, epoxy from the angle of flowability.
The amount of the Resins, epoxy that these can be used in combination, preferred 20% weight or still less is based on the whole epoxy resin ingredient in the composition.
Multiplely be used for the solidifying agent that curing agent for epoxy resin can be used as composition epoxy resin of the present invention, the example comprises the compound of epoxy curing agent such as amido, the compound of anhydride group, the compound of amide group and the compound of phenolic group.
Its specific examples comprises polyphenol compound such as diaminodiphenylmethane, the divinyl triamine, the trivinyl tetramine, diamino diphenylol sulfone, the isophorone diamines, Dyhard RU 100, synthetic from linolenic acid and the dimeric polyamide resin of quadrol, Tetra hydro Phthalic anhydride, trimellitic acid 1,2-anhydride, the pyromellitic acid acid anhydride, maleic anhydride, Tetra Hydro Phthalic Anhydride, methyl tetrahydrophthalic anhydride, methyl Nutting acid anhydrides (methylnadic anhydride), hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, phenol novolac resin, cresols novolac resin, the resin modified phenolic resin type Resins, epoxy of aromatic hydrocarbon formaldehyde, Dicyclopentadiene (DCPD) phenol add-on type resin, phenol aralkyl resin, cresols aralkyl resin, naphthols aralkyl-type resin, the phenol aralkyl resin of biphenyl-modification, phenol Pehanorm resin, four hydroxyphenyl ethane resin, the naphthol novolac varnish resin, naphthols-phenol cocondensation resin, naphthols-cresols cocondensation resin, the phenolic resin of the phenolic resin of biphenyl modification and aminotriazine modification; The compound of its modification; Imidazoles; BF
3-amine complex body; And guanidine derivative.These solidifying agent can use separately, perhaps with its two kinds or two or more being used in combination.
In these solidifying agent, consider preferred especially phenol novolac resin, naphthol novolac varnish resin and phenol Pehanorm resin from the angle of excellent heat resistance.Consider preferred especially phenol aralkyl resin, cresols aralkyl resin, naphthols aralkyl-type resin, the phenol aralkyl resin of biphenyl-modification from the angle of good moistureproofness.Consider preferred especially phenol aralkyl resin, cresols aralkyl resin, naphthols aralkyl-type resin, the phenol aralkyl resin of biphenyl-modification and the phenolic resin of aminotriazine modification from the excellent flame retardancy angle.
Phenol aralkyl resin, naphthols aralkyl-type resin, and the specific examples of the phenol aralkyl resin of biphenyl-modification comprises those resins with following general formula (5) or (6) expression.
In the superincumbent chemical formula, each R
1Represent hydrogen atom independently, methyl or ethyl, and R
2Represent hydrogen atom or methyl.Equally, n is a mean value, represents 0-10.
With respect to the amount of solidifying agent, the preferred 0.7-1.5 equivalent of amount of activation hydrogen base in the solidifying agent, based on the epoxy group(ing) of 1 equivalent Resins, epoxy, this be because this moment curing reaction fully and to solidify physicals satisfactory.
Can suitably use curing catalyst.Can use all conventional known curing catalysts, the example comprises phosphorio compound, tertiary amine, imidazoles, metal salts of organic acids, Lewis acid and amine complexing salt.Preferred tertiary amine is as 1 in semiconductor sealing material, 8-diazabicylo-[5,4,0]-undecylene (DBU), and this is because it has good curing performance, thermotolerance, electrical property and moistureproof security.
Each component except above-mentioned preferably joins inorganic filler in the composition epoxy resin of the present invention.Particularly, these inorganic fillers are the basal components in the semiconductor sealing material.The specific examples of inorganic filling salt comprises fumed silica, crystal aluminum oxide, aluminum oxide, silicon nitride and aluminium nitride.
When the amount of inorganic filling salt significantly increases, preferably use fumed silica.Although can use the silicon-dioxide that forges that grind or spherical, in order to increase the increase of forging silicon-dioxide and inhibition moulding material melt viscosity, the preferred sphere of using is forged silicon-dioxide.In order to increase the amount of preparing spherical SiO 2, preferably make the particle size distribution of preparing spherical SiO 2 wider by regulation and control.
If desired, can add multiple additives such as silane coupling agent, releasing agent and pigment.
In composition epoxy resin of the present invention, because itself has excellent flame retardancy as a kind of Resins, epoxy of main component, so do not need to use flame retardant properties imparting agent such as halogen compounds.In this case, resulting fire-retardant combination is substantially free of halogen compounds.
Yet,, when halogen compounds and other flame retardant properties imparting agent can be used in combination, can randomly use the flame retardant properties imparting agent further to improve flame retardant effect when according to required purpose.As the flame retardant properties imparting agent, listed for example halogen compounds, phosphorous atomic compound, nitrogen atom compound and inorganic fire-retarded compound.Its specific embodiment comprises for example tetrabromo-bisphenol type Resins, epoxy of halogen compounds, the compound that contains phosphorus atom is red phosphorus or phosphate compound for example, and the compound of nitrogen atom is trimeric cyanamide and inorganic fire-retarded compound such as aluminium hydroxide for example, magnesium hydroxide, zinc borate or lime borate.
By mixing above-mentioned each component equably, can obtain composition epoxy resin of the present invention.Composition epoxy resin of the present invention can be used in multiple the needs in flame retardant resistance and the stable on heating purposes, but comparatively useful as the Electrical and Electronic material, in particular as above-mentioned semiconductor sealing material and circuit card lacquer.
Can be by using forcing machine, the mixed fully Resins, epoxy of kneader and cylinder machine, solidifying agent, inorganic filler and, if necessary, other composition prepares semiconductor sealing material up to the mixture that obtains homogeneous.Preferred silicon-dioxide is as weighting agent.The normally such amount of the amount of inorganic filler, it can make a kind of packing factor be set in 30-95% weight.Fire-retardant in order to improve, moistureproof and anti-welding cracking is in order to reduce the coefficient of linear expansion, preferred 70% weight of packing factor or more.In order to have given play to its unusual effect, preferred especially 80% weight of packing factor or more.
Can be by composition epoxy resin of the present invention be dissolved in a kind of solvent such as toluene, dimethylbenzene, acetone, methylethylketone or methyl iso-butyl ketone (MIBK) prepare the circuit board material lacquer.In this case, the amount of solvent is generally the 10-70% weight of circuit board material lacquer weight, preferred 15-65% weight and preferred especially 15-65% weight.The specific examples of circuit board material comprises printed wiring board, printed circuit board (PCB), flexible printed circuit board and integrated routing plate (build-up wiring boards).
Can obtain cured article of the present invention by heat-curable epoxy resin compositions.Cured article can be used as moulded parts, laminated product, and casting article, tackiness agent is filmed and film.For instance, the cured article of semiconductor sealing material is a kind of casting article or moulded parts, and the cured article that is used for these purposes can be by using casting, and die casting or injection moulding machine moulding said composition heat 2-10 down at 80-200 ℃ and obtained in individual hour.The cured article of circuit card lacquer is a laminated product, and can obtain: with circuit card lacquer dipping substrate material such as glass fibre, carbon fiber by following method, trevira, tynex, sapphire whisker and paper, the substrate material of heat drying dipping is to form prepreg (prepreg), this prepreg of hot pressing.
Embodiment
By embodiment and comparative examples, now describe the present invention.
In being equipped with four neck flasks of agitator and well heater, 152 Trimethyl Hydroquinones that restrain (1.0 moles) are dissolved in the mixed solvent of 500 gram toluene and 200 gram ethylene glycol monomethyl ethers.When considering heat production, in solution, add 4.6 gram tosic acid, and in solution, dropwise add the formalin of 44g (0.6mol) 41%, then heating up in a steamer the timesharing that dewaters, stirred 15 hours down at 100-120 ℃.After the cooling, by filtering the collecting precipitation crystallization, water washes repeatedly up to washing lotion and is neutral, and after drying is to obtain 132 gram (GPC purity: the polyol that 98%) shows below.From the NMR spectrum of Fig. 1 (
13C), the mass spectrum of the IR spectrum (KBr) of Fig. 2 and Fig. 3 is identified structure.
Embodiment 2
In being equipped with four neck flasks of thermometer, dropping funnel, cooling tube and agitator, with the air in the nitrogen purge flask time, add and dissolve 149 and restrain the polyol (hydroxyl: 1.0 equivalents) that obtains among the embodiment 1, the Epicholorohydrin of 463 grams (5.0 moles), 53 gram propyl carbinols and 2.3 gram tetraethyl-benzyl ammonium chlorides.After being heated to 65 ℃, pressure is dropped to generation azeotropic pressure, then the aqueous sodium hydroxide solutions with 82 gram (1.0 moles) 49% dropwise added through 5 hours.Under the same conditions, continue to stir 0.5 hour.In the whipping process, separate the distillment that obtains because of azeotropic with the Dean-Stark trap, and heat up in a steamer, then when oil reservoir is turned back to reactive system, react except that water layer.Subsequently, heat up in a steamer under the decompression except that unreacted Epicholorohydrin.
By adding 550 gram methyl iso-butyl ketone (MIBK) and 55 gram propyl carbinols, with resulting thick Resins, epoxy dissolving.In solution, add 15 grams, 10% aqueous sodium hydroxide solution, 80 ℃ of reactions after 2 hours, be neutrality up to washing lotion with 100 gram water cleaning reaction solution 3 times.After making system dehydration by azeotropic, carry out microfiltration, under reduced pressure, heat up in a steamer and desolventize to obtain 188 Resins, epoxy (A) of setting a time limit and hoping, represent with following structural formula.The epoxy equivalent (weight) of resultant Resins, epoxy is 227 gram/equivalents.From the NMR spectrum of Fig. 1 (
13C), the mass spectrum of the IR spectrum (KBr) of Fig. 2 and Fig. 3 is identified structure.By gpc analysis, confirm that average number of repeat unit p is 0.1.
Embodiment 3
Except formalin being replaced by the phenyl aldehyde of 64 grams (0.6 mole), polyol 175 gram (the GPC purity: 99%) of the expectation that shows have below been obtained in similarly to Example 1 mode.From the NMR spectrum of Fig. 4 (
13C), the mass spectrum of the IR spectrum (KBr) of Fig. 5 and Fig. 6 is identified structure.
(hydroxyl equivalent: 1.0 gram/equivalents), the Resins, epoxy (B) 220 that has obtained the expectation represented with following structural formula in similarly to Example 2 mode restrains except the polyphenol compound that will obtain among the embodiment 1 is replaced by the polyphenol compound that 187 grams obtain among the embodiment 3.The epoxy equivalent (weight) of gained Resins, epoxy is 262 gram/equivalents.From the NMR spectrum of Fig. 4 (
13C), the mass spectrum of the IR spectrum (KBr) of Fig. 5 and Fig. 6 is identified structure.By GPC figure, the number of repeat unit p of structural formula is 0.1 below confirming.
Embodiment 5
Except formalin being replaced by the biphenyl aldehyde of 197 grams (1.2 moles), polyphenol compound 448 gram (the GPC purity: 99%) of the expectation represented with following structural formula have been obtained in similarly to Example 1 mode.The hydroxyl equivalent of this compound is 225 gram/equivalents (acetylize methods).Purity with gpc measurement is 99%.
Embodiment 6
(hydroxyl equivalent: 1.0 gram/equivalents), the Resins, epoxy (C) 247 that has obtained the expectation represented with following structural formula in similarly to Example 2 mode restrains except the polyphenol compound that will obtain among the embodiment 1 is replaced by the polyphenol compound that 225 grams obtain among the embodiment 5.Structural formula below the verified resulting used for epoxy resin is represented, because the epoxy equivalent (weight) of gained Resins, epoxy is 303 gram/equivalents, and mass spectral M
+Be 562.By gpc analysis, the number of repeat unit p of structural formula is 0.1 below confirming.
Embodiment 7
Except with 320 the gram (2.0 moles) 2,7-dihydroxy naphthlene and formalin are replaced by the biphenyl aldehyde of 236 grams (1.2 moles), have obtained polyphenol compound 276 gram (the GPC purity: 99%) of the expectation represented with following structural formula in similarly to Example 1 mode.The hydroxyl equivalent of this compound is 157 gram/equivalents (acetylize methods).With gpc measurement purity is 99%.
Except the polyphenol compound that will obtain among the embodiment 1 is replaced by the polyphenol compound that 157 grams obtain among the embodiment 7. (hydroxyl equivalent: 1.0 gram/equivalents), the Resins, epoxy (D) 190 that has obtained the expectation represented with following structural formula in similarly to Example 2 mode restrains.Structural formula below the verified resulting used for epoxy resin is represented, because the epoxy equivalent (weight) of resultant Resins, epoxy is 230 gram/equivalents, and mass spectral M
+Be 426.By gpc analysis, the number of repeat unit p of structural formula is 0.1 below confirming.
Embodiment 9
Except formalin being replaced by the 4-tolyl aldehyde of 162 grams (1.2 moles), polyphenol compound 388 gram (the GPC purity: 99%) of the expectation represented with following structural formula have been obtained in similarly to Example 1 mode.The hydroxyl equivalent of this compound is 194 gram/equivalents (acetylize methods).Purity with gpc measurement is 99%.
(hydroxyl equivalent: 1.0 gram/equivalents), the Resins, epoxy (E) 225 that has obtained the expectation represented with following structural formula in similarly to Example 2 mode restrains except the polyphenol compound that will obtain among the embodiment 1 is replaced by the polyphenol compound that 194 grams obtain among the embodiment 9.Structural formula below the verified resulting used for epoxy resin is represented, because the epoxy equivalent (weight) of resultant Resins, epoxy is 273 gram/equivalents, and mass spectral M
+Be 500.By gpc analysis, the number of repeat unit p of structural formula is 0.1 below confirming.
Embodiment 11
Except formalin being replaced by 3 of 179 grams (1.2 moles), the 4-tolyl aldehyde has obtained polyphenol compound 399 gram (the GPC purity: 99%) of the expectation represented with following structural formula in similarly to Example 1 mode.The hydroxyl equivalent of this compound is 201 gram/equivalents (acetylize methods).Purity with gpc measurement is 99%.
Embodiment 12
(hydroxyl equivalent: 1.0 gram/equivalents), the Resins, epoxy (F) 230 that has obtained the expectation represented with following structural formula in similarly to Example 2 mode restrains except the polyphenol compound that will obtain among the embodiment 1 is replaced by the polyphenol compound that 201 grams obtain among the embodiment 11.Structural formula below the verified resulting used for epoxy resin is represented, because the epoxy equivalent (weight) of gained Resins, epoxy is 277 gram/equivalents, and mass spectral M
+Be 514.By gpc analysis, the number of repeat unit p of structural formula is 0.1 below confirming.
Embodiment 13
Except formalin being replaced by the 2 of 179 grams (1.2 moles), polyphenol compound 398 gram (the GPC purity: 99%) of the expectation represented with following structural formula have been obtained in similarly to Example 1 mode.The hydroxyl equivalent of this compound is 201 gram/equivalents (acetylize methods).Purity with gpc measurement is 99%.
Embodiment 14
(hydroxyl equivalent: 1.0 gram/equivalents), the Resins, epoxy (G) 229 that has obtained the expectation represented with following structural formula in similarly to Example 1 mode restrains except the polyphenol compound that will obtain among the embodiment 1 is replaced by the polyphenol compound that 201 grams obtain among the embodiment 13.Structural formula below the verified resulting used for epoxy resin is represented, because the epoxy equivalent (weight) of gained Resins, epoxy is 276 gram/equivalents, and mass spectral M
+Be 514.By gpc analysis, the number of repeat unit p of structural formula is 0.1 below confirming.
Embodiment 15-17 and comparative examples 1-2
Resins, epoxy (A)-(C), BPA type Resins, epoxy (EPICLON 850S:DAINIPPONINK ﹠amp; CHEMICALS Co., Ltd. makes) and cresols phenolic resin varnish type epoxy resin (EPICLONN665-EXP-S:DAINIPPON INK ﹠amp; CHEMICALS Co., Ltd. make) Resins, epoxy in contrast, phenol aralkyl resin (MILEX XLC-LL:Mitsui Chemicals, Inc. make) as solidifying agent, triphenylphosphine (TPP) and Dicyclopentadiene (DCPD)-phenol addition polymer type Resins, epoxy (epoxy equivalent (weight): 263 gram/equivalents, softening temperature: 65 ℃, 150 ℃ melt viscosity: 0.8 pool, DAINIPPON INK ﹠amp; CHEMICALS Co., Ltd. the EPICLON HP-7200 of Zhi Zaoing) as curing catalyst, preparing spherical SiO 2 is as inorganic filler, above material is mixed with every kind of prescription shown in the table 1, and use twin-roll that every kind of mixture is descended thawing-kneadings 10 minutes at 100 ℃, to obtain compositions desired.Composition shown in the table represents that weight mixes ratio.
Every kind of composition 180 ℃ of down extruding 10 minutes, was solidified 5 hours down at 180 ℃,, produce thickness and be 1.6 millimeters sample then according to the UL-94 testing sequence.Flame retardant resistance test result to the acquisition sample sees Table 1.
[table 1]
| Embodiment | Comparative examples | |||||
| 15 | 16 | 17 | 1 | 2 | 3 | |
| Resins, epoxy (A) | 113 | |||||
| Resins, epoxy (B) | 120 | |||||
| Resins, epoxy (C) | 126 | |||||
| BPA type liquid epoxies | 102 | |||||
| The cresols phenolic resin varnish type epoxy resin | 107 | |||||
| Dicyclopentadiene (DCPD)-phenol addition polymer type Resins, epoxy | 120 | |||||
| Phenol aralkyl resin | 87 | 80 | 74 | 98 | 93 | 80 |
| Triphenylphosphine | 3 | 3 | 3 | 3 | 3 | 3 |
| Fumed | 800 | 800 | 800 | 800 | 800 | 800 |
| Second-order transition temperature (DMA) | 175 | 172 | 170 | 112 | 157 | 139 |
| Rate of moisture absorption | 0.20 | 0.19 | 0.17 | 0.26 | 0.28 | 0.19 |
| The flame retardant resistance test | V-0 | V-0 | V-0 | * | * | * |
| Total combustion time of 5 samples of flame retardant resistance test | 28 | 15 | 7 | * | * | * |
*: burning sample.
According to the present invention, might make composition epoxy resin, when having semiconductor sealing material and circuit card and coat with lacquer needed performance (for example: heat-resisting, protection against the tide and insulating property), can also give play to good flame retardant effect.In addition, can make provides a kind of and has neo-epoxy resin these performances, that be suitable for use as composition epoxy resin and become possibility, and can make provides a kind of oxybenzene compound that is suitable for use as the neo-epoxy resin intermediate to become possibility.
Composition epoxy resin is used for ball lattice arrange type (ball grid array type) semiconductor chip, the buckling problem that can make prevention be considered to a difficult problem up to now becomes possibility, can also make the packing that obtains having good anti-welding cracking character when installing become possibility.Composition epoxy resin is used for printed circuit board, and the multi-ply wood that can make acquisition have high glass transition temperature and good dimensional stability becomes possibility.Owing to can under the situation of halogen contained compound not, give cured article good flame retardant resistance, so this Resins, epoxy be very useful in field of electronic materials such as semiconductor sealing material and printed circuit board (PCB) as epoxide resin material.
Claims (12)
1, a kind of composition epoxy resin that contains Resins, epoxy and solidifying agent, Resins, epoxy wherein has fragrant polynuclear plane, the adjacent replacements of two on aromatic nucleus in aromatic hydrocarbon of two aromatic hydrocarbon in this structure position combines by carbon atom and Sauerstoffatom respectively, and also contains on fragrant polynuclear plane as substituent glycidyl oxygen base.
2, the composition of claim 1, wherein said Resins, epoxy have a methyl in fragrant polynuclear plane, this fragrance polynuclear plane is present in the epoxy resin structural.
3, the composition of claim 1, aromatic hydrocarbon wherein is naphthalene.
4, the composition in the claim 1, the epoxy equivalent (weight) of Resins, epoxy wherein are 240-330 gram/equivalent.
5, the composition in the claim 1, the carbonatoms of wherein forming fragrant polycyclic moiety account for aromatic carbon atom number in the Resins, epoxy 20% or more.
6, the composition in the claim 1 except Resins, epoxy and solidifying agent, also comprises the inorganic filler of 65-95% weight.
7, the Resins, epoxy of representing with general formula (1):
In general formula (1), X represents methylene radical, with the methylene radical of the alkyl replacement that contains 1-4 carbon atom, with the methylene radical that phenyl replaces, use the methylene radical of naphthyl substituted, with the methylene radical of xenyl replacement, methylene radical with the replacement of 9-fluorenyl, or a kind of like this methylene radical, in this methylene radical, alkyl is further at phenyl, naphthyl, or replaced on the aromatic ring on the xenyl, n and m represent integer 0-3, and p represents average number of repeat unit 0-10.
8, the Resins, epoxy of representing with general formula (2):
In the general formula (2), X represents methylene radical, with the methylene radical of the alkyl replacement that contains 1-4 carbon atom, with the methylene radical that phenyl replaces, use the methylene radical of naphthyl substituted, with the methylene radical of xenyl replacement, methylene radical with the replacement of 9-fluorenyl, or a kind of like this methylene radical, in this methylene radical, alkyl is further at phenyl, naphthyl, or replaced on the aromatic ring on the xenyl, n and m represent integer 0-5, and p represents average number of repeat unit 0-10.
9, the phenolic compound of representing with general formula (4):
In the general formula (4), X represents methylene radical, with the methylene radical of alkyl replacement, with the methylene radical of phenyl replacement, methylene radical with naphthyl substituted, with the methylene radical that xenyl replaces, the methylene radical of using the 9-fluorenyl to replace, or a kind of like this methylene radical, alkyl is further at phenyl in this methylene radical, naphthyl, or replaced on the aromatic ring on the xenyl, n and m represent integer 1-5.
10, the method for preparing polyol, this method is included under the situation of acid catalyst existence, the compound and the compound reaction that contains carbonyl of two hydroxyls will be contained on a kind of phenyl ring, in two hydroxyls of this phenyl ring one of them, contain a hydrogen atom at the ortho position, remaining all replaces on the position and contains substituting group.
11, the method in the claim 10, wherein contain the compound of two hydroxyls and the compound that the 0.1-3.0 mole contains carbonyl on 1 mole of phenyl ring, under 50-200 ℃ of temperature condition, react, in two hydroxyls of described phenyl ring one of them, contain a hydrogen atom at the ortho position, remaining all replaces on the position and contains substituting group.
12, the cured article that obtains by the composition of any one among the thermofixation claim 1-6.
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| JP4941804B2 (en) * | 2005-03-02 | 2012-05-30 | Ｄｉｃ株式会社 | Epoxy resin composition, cured product thereof, semiconductor sealing material, novel phenol resin, and novel epoxy resin |
| KR101246187B1 (en) * | 2008-10-22 | 2013-03-22 | 디아이씨 가부시끼가이샤 | Curable resin composition and cured product thereof, printed circuit board, and epoxy resin and method for producing same |
| EP2743770B1 (en) * | 2011-08-12 | 2015-12-30 | Mitsubishi Gas Chemical Company, Inc. | Underlayer film-forming material for lithography, underlayer film for lithography, and pattern formation method |
| EP2743769B1 (en) | 2011-08-12 | 2017-03-22 | Mitsubishi Gas Chemical Company, Inc. | Resist composition, resist pattern formation method, polyphenol compound used therein, and alcohol compound capable of being derived therefrom |
| US10377734B2 (en) | 2013-02-08 | 2019-08-13 | Mitsubishi Gas Chemical Company, Inc. | Resist composition, method for forming resist pattern, polyphenol derivative for use in the composition |
| KR20170099908A (en) | 2014-12-25 | 2017-09-01 | 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 | Compound, resin, underlayer film forming material for lithography, underlayer film for lithography, pattern forming method and purification method |
| WO2016158168A1 (en) | 2015-03-31 | 2016-10-06 | 三菱瓦斯化学株式会社 | Compound, resist composition, and method for forming resist pattern in which same is used |
| US11480877B2 (en) | 2015-03-31 | 2022-10-25 | Mitsubishi Gas Chemical Company, Inc. | Resist composition, method for forming resist pattern, and polyphenol compound used therein |
| WO2017038643A1 (en) | 2015-08-31 | 2017-03-09 | 三菱瓦斯化学株式会社 | Material for forming underlayer films for lithography, composition for forming underlayer films for lithography, underlayer film for lithography and method for producing same, and resist pattern forming method |
| WO2017038645A1 (en) | 2015-08-31 | 2017-03-09 | 三菱瓦斯化学株式会社 | Material for forming underlayer films for lithography, composition for forming underlayer films for lithography, underlayer film for lithography and method for producing same, pattern forming method, resin, and purification method |
| KR20180050665A (en) | 2015-09-10 | 2018-05-15 | 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 | COMPOSITION, RESIN, RESIST COMPOSITION OR RADIATION RADIATIVE COMPOSITION, RESIST PATTERN FORMING METHOD, AMORPHOUS FILM PRODUCTION METHOD, LITHOGRAPHY ROW LAYER FILM FORMING MATERIAL, COMPOSITION FOR FORMING LITHOGRAPHY UNDERLAY FILM |
| CN106010128B (en) * | 2016-07-26 | 2018-08-24 | 江苏中任油漆有限公司 | A kind of flame-resistant insulation epoxy coating and preparation method thereof that wiring board uses |
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| US4266020A (en) * | 1978-10-05 | 1981-05-05 | Fuji Photo Film Co., Ltd. | Color photographic light-sensitive material |
| US5780571A (en) * | 1993-03-22 | 1998-07-14 | Nippon Kayaku Kabushiki Kaisha | Naphthalene ring-containing resins, resin compositions and cured products thereof |
| JP2000038517A (en) * | 1998-05-21 | 2000-02-08 | Yoshitomi Fine Chemical Kk | Organic polymer material containing xanthene-2,7-diol compound |
-
2002
- 2002-10-22 CN CNB021470073A patent/CN1309783C/en not_active Expired - Lifetime
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4266020A (en) * | 1978-10-05 | 1981-05-05 | Fuji Photo Film Co., Ltd. | Color photographic light-sensitive material |
| US5780571A (en) * | 1993-03-22 | 1998-07-14 | Nippon Kayaku Kabushiki Kaisha | Naphthalene ring-containing resins, resin compositions and cured products thereof |
| JP2000038517A (en) * | 1998-05-21 | 2000-02-08 | Yoshitomi Fine Chemical Kk | Organic polymer material containing xanthene-2,7-diol compound |
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