CN104725600A - The optical epoxy resin composition and cured product thereof - Google Patents
The optical epoxy resin composition and cured product thereof Download PDFInfo
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- CN104725600A CN104725600A CN201410804437.0A CN201410804437A CN104725600A CN 104725600 A CN104725600 A CN 104725600A CN 201410804437 A CN201410804437 A CN 201410804437A CN 104725600 A CN104725600 A CN 104725600A
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Abstract
The invention provides an epoxy resin composition, an epoxy resin cured product, and a film adhesive, a color filter protective film, an optical semiconductor sealing material, an optical semiconductor substrate, and an optical semiconductor substrate surface protective film acquired from the epoxy resin composition. The epoxy resin composition may provide a cured product having high transparency and high heat resistance reliability and excellent in optical materials such as an LED encapsulant. The optical epoxy resin composition comprises epoxy resin (a) and curing agent (b), wherein the epoxy resin (a) has an epoxy equivalent of 500 to 2000g/eq, a softening point of 80 to 150 degrees centigrade, a refractive index (nD20) of 1.55 to 1.63, an aromatic ring and an aliphatic ring simultaneously in the molecular structure. An intensity ratio (B/A) of Aliphatic protons (A) and the aromatic protons (B)in the 1H-NMR spectrum 0.3 to 0.7.
Description
Technical field
The present invention relates to the optics epoxy resin cured product being particularly suitable for being exposed to the position of high temperature in optical material, electronic material purposes.
Background technology
Patent Document 1 discloses a kind of to resin interpolation tinting material itself, and make the word of printing become clearly method by the heat applied during Laser Printing, but, the problem of epoxy resin variable color is caused due to the heat also existed because applying during Laser Printing, therefore, expect to prevent variable color with carrying out essence by the improvement of epoxy resin.
In addition, disclose by using specific epoxy resin and introducing the solidifying agent of terpenes skeleton in patent documentation 2,3, thermotolerance, adaptation, xanthochromia etc. when being heated can be improved, but, solidifying agent, epoxy resin are all the materials must with specific skeleton, and curing catalyst is also limit material.
In addition, a kind of composition epoxy resin used for optical part has been shown in patent documentation 4, the adaptation of itself and glass is good, there is high transparent, resistance to thermal reliability (resistance to thermochromism, thermal shrinkage), but, wherein there is following record: this composition epoxy resin suppresses painted by using specific light acid producing agent, if containing the epoxy resin with fluorene skeleton, then by the effect of fluorene skeleton, high refractive index (more than 1.58) can be reached, and sufficient second-order transition temperature can be obtained.The introducing of fluorene skeleton is after the mixing having carried out the epoxy resin with fluorene skeleton, by utilizing the solidification of cationoid polymerisation to carry out, and realizes high refractive index, becomes for the unaccommodated composition of thermopolymerization during the known epoxy curing agents such as use acid anhydrides.
In addition, Patent Document 5 discloses a kind of composition epoxy resin, it makes 2 functional epoxy resins, containing the phenol of fluorenes ring and anhydride reaction and the cured article formed by epoxy resin and acid anhydrides obtained, and there is high transparent and good resistance to thermal reliability, but the resistance to thermochromism of this composition epoxy resin is insufficient.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 6-025513 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2002-12819 publication
Patent documentation 3: Japanese Patent No. 3948980 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2010-265360 publication
Patent documentation 5: Japanese Unexamined Patent Publication 2012-177038 publication
Summary of the invention
Invent problem to be solved
Problem to be solved by this invention is to provide a kind of optics epoxy resin cured product, the sealing material that xanthochromia when it is heated while can being provided in and meeting all the time required performance and visible light permeability is low and protective membrane formation composition.In addition, problem to be solved by this invention is to provide a kind of optics composition epoxy resin, it is when optical waveguides etc. regulates specific refractory power to be important purposes, specific refractory power can be regulated by the composition changing the epoxy resin in core and coating layer, and can bonding force between holding core/coating layer when being heated.
For the means of dealing with problems
The present inventor conducts in-depth research to solve the problem, found that: by the epoxy resin containing aromatic ring and aliphatics ring in the skeleton that is used in epoxy resin, visible light transmissivity can be met, there is the characteristic that xanthochromia when being heated is low simultaneously, thus complete the present invention.
Namely, the present invention is a kind of optics composition epoxy resin, it is characterized in that, it is the optics composition epoxy resin containing epoxy resin (a) and solidifying agent (b), wherein, the epoxy equivalent (weight) of this epoxy resin (a) is 500 ~ 2000g/eq, and softening temperature is 80 ~ 150 DEG C, at 20 DEG C, specific refractory power (n under wavelength 589.3nm
d 20) be 1.55 ~ 1.63, there is in molecular structure aromatic ring and aliphatics ring simultaneously, and the aliphatic protons (A) in 1H-NMR spectrum is 0.3 ~ 0.7 with the strength ratio (B/A) of aromatic protons (B).
As epoxy resin (a), comprise: by the ester cpds (c) of the fatty race ring of terminal carboxyl(group), 2 yuan of phenolic compound (d) or both and 2 officials can aromatic epoxy resin (e1), 2 officials can the epoxy resin (e2) of fatty race ring or the epoxy resin be obtained by reacting of both, described ester cpds (c) is being obtained by reacting by 2 yuan of alcohol and acid anhydrides.More preferably by the ester cpds (c) of the fatty race ring of terminal carboxyl(group) and the epoxy resin be obtained by reacting of 2 officials' energy aromatic epoxy resin (e1), or by the epoxy resin that is obtained by reacting of 2 yuan of phenolic compound (d) with the epoxy resin (e2) of the fatty race ring of 2 officials' energy.
As the ester cpds (c) of the fatty race ring of terminal carboxyl(group), comprising: by the ester cpds of the fatty race ring of the terminal carboxyl(group) be obtained by reacting of 2 yuan of alcohol of fatty race ring and the acid anhydrides of the acid anhydrides of acid anhydrides, 2 yuan of alcohol and fatty race ring or 2 yuan of alcohol of fatty race ring and fatty race ring.
2 yuan of phenolic compound (d) are the phenolic compound containing fluorenes ring.As 2 officials' energy aromatic epoxy resin (e1), 2 officials comprised containing fluorenes ring can aromatic epoxy resins.As the epoxy resin (e2) of the fatty race ring of 2 officials' energy, comprise the alicyclic epoxy resin of 2 officials' energy.
About the usage ratio of epoxy resin (a) with solidifying agent (b), preferably relative to epoxy group(ing) 1 mole, the active hydrogen base of solidifying agent (b) is the scope of 0.4 ~ 1.2 mole.
Above-mentioned optics composition epoxy resin is excellent as film-like adhesive composition epoxy resin, color filter protecting layer composition epoxy resin or photosemiconductor substrate surface protection film composition epoxy resin.
In addition, the present invention is the epoxy resin cured product making above-mentioned optics epoxy resin composition and obtain.In addition, the present invention is the film-like adhesive, color filter protecting layer or the photosemiconductor substrate surface protection film that use above-mentioned film-like adhesive composition epoxy resin, color filter protecting layer composition epoxy resin or photosemiconductor substrate surface protection film composition epoxy resin and obtain.In addition, the present invention uses above-mentioned optics composition epoxy resin and the photosemiconductor sealing material that obtains or photosemiconductor substrate.
The effect of invention
Composition epoxy resin of the present invention can provide the cured article with high transparent, high resistance to thermal reliability (high heat-resisting xanthochromia).Be particularly suitable for the purposes that LED sealing material etc. requires thermotolerance, photostabilization, the transparency, permanent stability.
Accompanying drawing explanation
Fig. 1 is the 1H-NMR spectrum of the epoxy resin 1 obtained in synthesis example 1.
Embodiment
Below, embodiments of the present invention are described in detail.
Optics composition epoxy resin of the present invention, except common CD, lens, light guiding plate or optical fiber etc., is also applicable to resin substrate, LED (Light Emitting Diode) sealing material, film-like adhesive, the colour filter protective membrane of the replacement glass substrate being strongly required the transparency.Optics comprises these purposes with referring to.Optics composition epoxy resin of the present invention is especially suitable for use as the protective membrane of film-like adhesive or colour filter photoreactive semiconductor substrate surface.
Optics composition epoxy resin of the present invention contains epoxy resin (a) and solidifying agent (b).Epoxy resin (a) must meet following condition: epoxy equivalent (weight) is 500 ~ 2000g/eq, and softening temperature is 60 ~ 130 DEG C, at 20 DEG C, specific refractory power (n under wavelength 589.3nm
d 20) be 1.55 ~ 1.63, there is in molecular structure aromatic ring and aliphatics ring simultaneously, and the aliphatic protons (A) in proton NMR spectrum is 0.3 ~ 0.7 with the strength ratio (B/A) of aromatic protons (B).
The scope of the epoxy equivalent (weight) of epoxy resin (a) is 500 ~ 2000g/eq, more preferably 700 ~ 1500g/eq, further preferred 850 ~ 1200g/eq.If epoxy equivalent (weight) is little, then may not obtain the effect of high refractive index and good heat-resisting xanthochromia, on the contrary, if epoxy equivalent (weight) is large, then the softening temperature of the epoxy resin obtained uprises, and shaping and coating may become difficulty.At this, epoxy equivalent (weight) is the grams (g/eq) of the resin of the epoxy group(ing) containing 1 gram equivalent, and the method according to JIS K7236 defined measures.
The scope of the softening temperature of epoxy resin (a) is 80 ~ 150 DEG C, more preferably 100 ~ 145 DEG C, preferably 110 ~ 140 DEG C further.If softening temperature is low, then adhesive uprises, and processibility may worsen, and on the contrary, if softening temperature is high, then shaping and coating may become difficulty, and must at high temperature process, this becomes painted reason.
Epoxy resin (a) is at 20 DEG C, specific refractory power (n under wavelength 589.3nm
d 20) scope be 1.55 ~ 1.63.Because this scope is the scope often used in optical applications, therefore preferably, by skeleton and the aromatic content of adjustment ring epoxy resins (a), this scope can be reached.
There is in the molecular structure of epoxy resin (a) aromatic ring and aliphatics ring simultaneously.If not fatty race ring, even if then have aromatic ring, thermotolerance also may be deteriorated.In addition, if not containing aromatic ring, then fully can meet the transparency and photostabilization, but heat-resisting xanthochromia (thermotolerance) significantly worsens, the use in the optical applications that heating is large is difficult.The ratio of aromatic ring and aliphatics ring is also relevant with the strength ratio (B/A) of the aliphatic protons (A) in 1H-NMR spectrum described later and aromatic protons (B).
The epoxy resin (a) simultaneously in molecular structure with aromatic ring and aliphatics ring such as can be obtained by following method.
1) there is the polycondensation of aromatic ring and the phenolic compound both aliphatics ring and epihalohydrin, 2) there is aromatic ring, aliphatics ring or the epoxy resin of both with there is aromatic ring, the addition polymerization of aliphatics ring or the phenolic compound of both (but, only there is the situation of aromatic ring or aliphatics ring) while of getting rid of epoxy resin and phenolic compound, 3) there is aromatic ring, aliphatics ring or the acid anhydrides of both with there is aromatic ring, the addition polymerization of aliphatics ring or the epoxy resin of both (but, only there is the situation of aromatic ring or aliphatics ring) while of getting rid of epoxy resin and acid anhydrides, 4) there is aromatic ring, the ester cpds of aliphatics ring or the terminal carboxyl(group) of both with there is aromatic ring, the addition polymerization of aliphatics ring or the epoxy resin of both (but, only there is the situation of aromatic ring or aliphatics ring) while of getting rid of epoxy resin and ester cpds.
But, be not limited to these methods.In addition, also these Combination of Methods can be obtained epoxy resin (a).And, under any circumstance, the raw material with aliphatics ring and aromatic ring must be used.Can be that one in raw material has aliphatics ring and aromatic ring, also can be that the one in raw material has aliphatics ring, the one in other raw materials has aromatic ring.
In above-mentioned method for making, the preferred method for making obtaining epoxy resin (a) is: (1) 2 functional epoxy resins, have the polyaddition reaction of the ester cpds of 2 yuan of phenolic compound of fluorene skeleton and the fatty race ring of terminal carboxyl(group), (2) there is the polyaddition reaction of the ester cpds of 2 functional epoxy resins of fluorene skeleton and the fatty race ring of terminal carboxyl(group), (3) 2 officials can alicyclic epoxy resin, the ester cpds of terminal carboxyl(group) and the addition reaction of phenolic compound, (4) 2 officials can alicyclic epoxy resin and the polyaddition reaction of phenolic compound.Preferred method for making is: (1) 2 functional epoxy resins, have the polyaddition reaction of the ester cpds of 2 yuan of phenolic compound of fluorene skeleton and the fatty race ring of terminal carboxyl(group).In addition, be used alone 2 officials can alicyclic epoxy resin when, the adjustment due to aromatic ring introduction volume is difficult, therefore, preferably and with 2 common functional epoxy resins.
In addition, in the present invention, aliphatics ring refers to the circular part of aliphatic hydrocarbon, can containing the heteroatoms such as aerobic, but during the solidification such as oxirane ring or trimethylene oxide ring, open loop the material not showing ring-type when becoming the state of cured article are not included in aliphatics ring.Preferred aliphatics ring does not have the ring of unsaturated link(age) containing the carbon of more than 3 in ring member nitrogen atoms, more preferably the bicyclic alkyl of the cycloalkyl of the monocycle of C4 ~ C8, C8 ~ C16, the condensing or spiral shell type cycloalkyl of C7 ~ C16.Specifically, can enumerate: the polynuclear planes such as bridged ring and the volution such as spiral shell octane, spiral shell bicyclopentane such as the single ring architectures such as tetramethylene ring, pentamethylene ring, cyclohexane ring and bicyclopentane, bicyclooctane, two ring undecanes with heterocycles such as oxane ring, oxepane ring, thiacyclohexane rings, but are not limited to these rings.
In addition, the aliphatic protons (A) of epoxy resin (a) in 1H-NMR (proton N MR) spectrum is 0.3 ~ 0.7 with the scope of the strength ratio (B/A) of aromatic protons (B), more preferably 0.35 ~ 0.65, further preferably 0.4 ~ 0.6.If aromatic protons is many, then there is the effect that thermotolerance improves, specific refractory power improves, but the transparency and photostabilization may be deteriorated, become and cannot be used for optical applications, on the contrary, if aromatic protons is few, then heat-resisting xanthochromia (thermotolerance) may worsen.
Fig. 1 is utilized to be described strength ratio (B/A), Fig. 1 shows the 1H-NMR of the epoxy resin (a) obtained in synthesis example, wherein, peak based on aromatic protons (B) is a, peak based on aliphatic protons (A) is the whole of the proton d of the proton b of alcohol, ether or epoxide, the proton c of ester and methylene radical, and aliphatic protons (A) is [a/ (b+c+d)] with the strength ratio (B/A) of aromatic protons (B).
At this, aromatic protons (B) refers to the H be bonded on the carbon forming aromatic ring, and aliphatic protons (A) refers to the H except aromatic protons (B).
As introducing the phenolic compound with aliphatics ring used in the method for above-mentioned aliphatics ring, specifically, can enumerate: 4,4 '-cyclohexylene biphenol, 4,4 '-cyclohexylene two (2-methylphenol), 4,4 '-isopropylidene two (2-cyclohexylphenol), 4,4 '-(3,3,5-trimethylammonium cyclohexylene) biphenol etc., can be used alone or use as mixture of more than two kinds, but be not limited to these compounds.
As the epoxy resin (e2) of the fatty race ring of 2 officials' energy, specifically, can enumerate: 3-Oxyranyle-7-oxabicyclo [4.1.0] heptane, 3 ', 4 '-epoxy hexane ylmethyl-3,4-epoxy hexane carboxylicesters, the alicyclic epoxy resin of limonene dioxide etc. 2 official energy, and 1,4 cyclohexane dimethanol, 4,4 '-two (methylol) dicyclohexyl, 2,2 '-two (4-hydroxy-cyclohexyl) propane (Hydrogenated Bisphenol A), two (4-hydroxy-cyclohexyl) methane, 3,9-bis-(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetra-oxaspiro [5.5] undecane (spiral shell glycol), 5-ethyl-2-(2-hydroxyl-1,1-dimethyl ethyl)-5-methylol-1,3-diox, Isosorbides etc. have the 2-glycidyl ether resin of 2 yuan of alcohol of aliphatics ring, with 1,2-cyclohexane dicarboxylic acid, methyl bicyclic [2.2.1] heptane-2,3-dicarboxylic acid, two rings [2.2.1] heptane-2,3-dicarboxylic acid etc. has the 2-glycidyl ester resin etc. of the dicarboxylic acid of aliphatics ring, can be used alone or uses as mixture of more than two kinds, but be not limited to these resins.In addition, the resin that in the 2-glycidyl ether resin of 2 yuan of alcohol and the 2-glycidyl ester resin of dicarboxylic acid, total chlorine component is high is many, possibly cannot be used for electronic material purposes, therefore, preferably uses the distillage reducing total chlorine component.In addition, from the view point of thermotolerance, the more preferably alicyclic epoxy resin of 2 officials' energy.
As the acid anhydrides with aliphatics ring, specifically, can enumerate: hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, methyl bicyclic [2.2.1] heptane-2,3-dicarboxylic anhydride, two rings [2.2.1] heptane-2,3-dicarboxylic anhydride etc., can be used alone or use as mixture of more than two kinds, but be not limited to these acid anhydrides.
As the ester cpds (c) with aliphatics ring introducing the terminal carboxyl(group) used in the method for above-mentioned aliphatics ring, can be obtained by following method, but be not limited to these methods.
Have the addition reaction of 2 yuan of alcohol of aliphatics ring and acid anhydrides,
2 yuan of alcohol and have aliphatics ring acid anhydrides addition reaction,
The addition reaction of 2 yuan of alcohol with aliphatics ring and the acid anhydrides with aliphatics ring,
Have the dehydration condensation of 2 yuan of alcohol of aliphatics ring and dicarboxylic acid,
2 yuan of alcohol and have aliphatics ring dicarboxylic acid dehydration condensation,
The dehydration condensation etc. of 2 yuan of alcohol with aliphatics ring and the dicarboxylic acid with aliphatics ring.
In these reactions, relative to 2 yuan of alcohol, the acid anhydrides more than can using etc. mole and/or dicarboxylic acid.In these reactions, the complete open loop of acid anhydrides must be made, not make it remain as unreacted acid anhydrides, in addition, two ends must be made to be that the compound of hydroxyl does not remain separately.In addition, the object lesson of 2 yuan of alcohol, except above-mentioned 2 yuan of alcohol with aliphatics ring, can also be enumerated: the aliphatic diols such as ethylene glycol, propylene glycol, neopentyl glycol, 1,6-hexylene glycol, but be not limited to these 2 yuan of alcohol.In addition, acid anhydrides and dicarboxylic acid can enumerate above-mentioned acid anhydrides and dicarboxylic acid, but are not limited to these compounds.From the simplicity of reaction, preferably there are 2 yuan of alcohol of aliphatics ring and the addition reaction of acid anhydrides, 2 yuan of alcohol and have aliphatics ring acid anhydrides addition reaction or there are 2 yuan of alcohol of aliphatics ring and there is the addition reaction of acid anhydrides of aliphatics ring.
In addition, even the ester cpds obtained by other reaction mechanism, as long as the ester cpds with aliphatics ring of terminal carboxyl(group).Can be used alone these ester cpds, or use as mixture of more than two kinds.
As the method introducing aromatic ring in the skeleton of epoxy resin (a), can enumerate: 2 officials can the polycondensation of phenolic compound and epihalohydrin, 2 officials can phenolic compound and epoxy resin addition polymerization, there is the epoxy resin of aromatic ring and the addition polymerization of phenolic compound or have the addition polymerization of the acid anhydrides of aromatic ring and epoxy resin, terminal carboxyl(group) there is the various method such as the ester cpds of aromatic ring and the addition polymerization of epoxy resin, but be not limited to these methods.In addition, these Combination of Methods can be obtained epoxy resin (a).
As the epoxy resin with aromatic ring, be 2 officials' energy aromatic epoxy resins of the glycidyl ether compound as 2 officials' energy phenolic compound, as 2 officials' energy phenolic compound, can enumerate: dihydroxyphenyl propane (BPA), Bisphenol F, bisphenol S, 4,4 '-bis-phenol, tetramethyl-dihydroxyphenyl propane, dimethyl dihydroxyphenyl propane, tetramethyl-Bisphenol F, dimethyl Bisphenol F, tetramethyl-bisphenol S, dimethyl bisphenol S, tetramethyl--4,4 '-bis-phenol, dimethyl-4,4 '-bis-phenol, 1-(4-hydroxy phenyl)-2-[4-(1,1-bis-(4-hydroxy phenyl) ethyl) phenyl] propane, 2,2 '-methylene radical-two (4-methyl-6-tert butyl phenol), 4,4 '-butylidene-two (3-methyl-6-tert butyl phenol), trihydroxybenzene methylmethane, Resorcinol, Resorcinol, 9,9-bis-(4-hydroxy phenyl)-9H-fluorenes, 9,9-bis-(4-hydroxy-3-methyl phenyl)-9H-fluorenes etc. 2 official energy aromatic series phenol, can be used alone or use as mixture of more than two kinds, but be not limited to these compounds.From the view point of thermotolerance, preferably 9,9-bis-(4-hydroxy phenyl)-9H-fluorenes, 9,9-bis-(4-hydroxy-3-methyl phenyl)-9H-fluorenes.
As the acid anhydrides with aromatic ring, can enumerate: Tetra hydro Phthalic anhydride, 1,2-naphthalene dicarboxylic acids acid anhydride, 2,3-naphthalene dicarboxylic acids acid anhydrides, 1,2,3,4-tetrahydrochysene-1,2-naphthalene dicarboxylic acids acid anhydrides etc., can be used alone or use as mixture of more than two kinds, but be not limited to these compounds.
As the dicarboxylic acid with aromatic ring, can enumerate: phthalic acid, 1,2-naphthalene dicarboxylic acids, 2,3-naphthalene dicarboxylic acids, 1,2,3,4-naphthane-2,3-dicarboxylic acid, 1-phenyl-2,6-naphthalene dicarboxylic acids etc., can be used alone or use as mixture of more than two kinds, but be not limited to these compounds.
In epoxy resin, introduce aliphatics ring thus make epoxy resin (a) than introduce aromatic ring more difficult.In electronic material purposes and optical material purposes, epoxy resin is high purity product is important, but except alicyclic epoxy resin have aliphatics ring epoxy resin major part purity low, need high purity.Therefore, although the fractionation by distillation also existed by repeatedly carrying out epoxy resin and reaction of re-refining carry out high purity and make aromatic ring be converted into the method for aliphatics ring by the hydrogenation of epoxy resin, but no matter which kind of method, all add operation quantity, operation is made to become numerous and diverse, also uneconomical on cost, not commercial preferred method.Therefore, preferably have can introduce with the raw material of the functional group of epoxy reaction from the raw material beyond epoxy resin, specifically, preferably by there is the acid anhydrides of aliphatics ring, dicarboxylic acid or the ester cpds of terminal carboxyl(group) and the reaction of epoxy resin is introduced.
Epoxy resin be phenolic compound 2-glycidyl etherate, namely so-called aromatic epoxy resin when, the reaction preferably by the ester cpds of the fatty race ring with above-mentioned end carboxyl obtains epoxy resin (a).In this case, preferably relative to the epoxy group(ing) 1 mole of epoxy resin, use the carboxyl of the ester cpds of terminal carboxyl(group) with the scope of 0.2 ~ 0.7 mole, within the scope of this, by increasing the content of carboxyl, specific refractory power and heat-resisting xanthochromia uprise.If the ester cpds of terminal carboxyl(group) is very few, then the thermotolerance of epoxy resin (a) is deteriorated, if too much, then the softening temperature of gained epoxy resin (a) uprises, and becomes the resin of poor practicability.
In addition, can be used together 2 yuan of phenolic compound.In this case, preferably relative to the epoxy group(ing) 1 mole of epoxy resin, use with the scope that the total amount of the hydroxyl of the carboxyl of the ester cpds of terminal carboxyl(group) and 2 yuan of phenolic compound is 0.2 ~ 0.7 mole.If aliphatic protons (A) is in the scope of 0.3 ~ 0.7 with the strength ratio (B/A) of aromatic protons (B), then by the content of increase by 2 yuan of phenolic compound, thermotolerance improves.When 2 yuan of phenolic compound containing fluorene skeleton, this Be very effective, more preferably.
About solidifying agent (b), as long as have the material of the function of cured epoxy resin, just be not particularly limited, can preferably use the known solidifying agent such as phenols curing agent, amine curing agent, anhydride curing agent or cationic polymerization initiators, but from the view point of heat-resisting xanthochromia, the solidifying agent more preferably also reacted with alcohol hydroxyl group.As preferred solidifying agent, specifically, can enumerate: the cationic polymerization initiators such as light cationic polymerization initiators, hot cationic polymerization initiators, above-mentioned acid anhydrides and 3,3 ', 4,4 '-phenylbenzene sulfo group tetracarboxylic dianhydride, 1, the carboxylic acid dianhydride etc. such as 2,3,4-butane tetracarboxylic acid dianhydride.These solidifying agent can be used alone or use as mixture of more than two kinds, but are not limited to these solidifying agent.
In composition epoxy resin of the present invention, about the use level of epoxy resin (a) with solidifying agent (b), relative to the epoxy group(ing) 1 mole of epoxy resin (a), the active hydrogen base of solidifying agent (b) the preferably scope of 0.4 ~ 1.2 mole, more preferably 0.5 ~ 1.1 mole, preferably 0.7 ~ 1.0 mole further.Such as, when using phenols, amine curing agent, relative to epoxy group(ing), coordinate almost equimolar active hydrogen base, when using acid anhydride type curing agent, relative to epoxy group(ing) 1 mole, coordinate anhydride group 0.5 ~ 1.2 mole, preferably 0.6 ~ 1.0 mole.When contacting with imidazolium compounds class with cationic polymerization initiators etc. and react, sometimes coordinate with the mass ratio of the regulation relative to epoxy resin.Active hydrogen base described in the present invention is that to have epoxy group(ing) be the functional group of reactive active hydrogen, specifically, can enumerate: anhydride group, carboxyl, amino and phenolic hydroxyl group etc.In addition, about active hydrogen base, if the carboxyl of 1 mole or phenolic hydroxyl group are counted 1 mole, then amino (NH
2) count 2 moles.
In optics composition epoxy resin of the present invention, as required can also not damage the degree of characteristic of the present invention and to use the various epoxy resin except epoxy resin (a).As can and epoxy resin, specifically, can enumerate: Epotohto YDC-1312, ZX-1027 (Nippon Steel & Sumitomo Metal Corporation's system, hydroquinone type epoxy resin), YX-4000 (Mitsubishi chemical Co., Ltd's system), ZX-1251 (Nippon Steel & Sumitomo Metal Corporation's system, bisphenol-type epoxy resin), EpotohtoYD-127, Epotohto YD-128, Epotohto YD-8125, Epotohto YD-825GS, EpotohtoYD-011, Epotohto YD-900, Epotohto YD-901 (Nippon Steel & Sumitomo Metal Corporation's system, BPA type epoxy resin), Epotohto YDF-170, Epotohto YDF-8170, EpotohtoYDF-870GS, Epotohto YDF-2001 (Nippon Steel & Sumitomo Metal Corporation's system, BPF type epoxy resin), Epotohto YDPN-638 (Nippon Steel & Sumitomo Metal Corporation's system, phenolic resin varnish type epoxy resin), Epotohto YDCN-701 (Nippon Steel & Sumitomo Metal Corporation's system, cresol novolak type epoxy resin), ZX-1201 (Nippon Steel & Sumitomo Metal Corporation's system, bisphenol fluorene type epoxy resin), NC-3000 (Nippon Kayaku K. K's system, biphenyl aralkylphenol type epoxy resin), EPPN-501H, EPPN-502H (Nippon Kayaku K. K's system, polyfunctional epoxy resin), ZX-1355 (Nippon Steel & Sumitomo Metal Corporation's system, naphthalene diol type epoxy resin), ESN-155, ESN-185V, ESN-175 (Nippon Steel & Sumitomo Metal Corporation's system, 2-Naphthol aralkyl-type epoxy resin), ESN-355, ESN-375 (Nippon Steel & Sumitomo Metal Corporation's system, bisnaphthol aralkyl-type epoxy resin), ESN-475V, the epoxy resin that ESN-485 (Nippon Steel & Sumitomo Metal Corporation's system, naphthyl alcohol aralkyl-type epoxy resin) etc. are manufactured by the phenolic compound such as polyphenol resin and epihalohydrin, Epotohto YH-434, Epotohto YH-434GS (Nippon Steel & Sumitomo Metal Corporation's system, diamino diphenyl methane tetraglycidyl ether) etc. the epoxy resin that manufactured by amine compound and epihalohydrin, YD-171 (Nippon Steel & Sumitomo Metal Corporation's system, dimer acid type epoxy resin) etc. the epoxy resin etc. that manufactured by carboxylic acid and epihalohydrin, but be not limited to these materials, also two or more kinds may be used.When and use, as the physics value of each epoxy resin composition, must be: epoxy equivalent (weight) is 500 ~ 2000g/eq, softening temperature be 80 ~ 150 DEG C, at 20 DEG C, specific refractory power (n under wavelength 589.3nm
d 20) be 1.55 ~ 1.63, the aliphatic protons (A) in 1H-NMR spectrum is 0.3 ~ 0.7 with the strength ratio (B/A) of aromatic protons (B).Therefore, relative to epoxy resin (a) 100 mass parts, can and other epoxy resin preferably below 20 mass parts, more preferably below 10 mass parts.
In addition, relative to the nonvolatile component 100 quality % in optics composition epoxy resin of the present invention, the total amount of preferred epoxy and solidifying agent is more than 50 quality %.If very few, then can not embody effect of the present invention.
In optics composition epoxy resin of the present invention, curing catalyst can be used as required.If concrete example illustrates spendable curing catalyst, can enumerate: the imidazoles such as glyoxal ethyline, 2-ethyl imidazol(e), 2-ethyl-4-methylimidazole, 2-(dimethylaminomethyl) phenol, 1,8-diazabicylo (5,4,0) tertiary amines such as hendecene-7, the phosphine classes such as triphenylphosphine, tricyclohexyl phosphine, triphenylphosphine triphenylborane, the metallic compounds such as stannous octoate.Curing catalyst may be used alone, two or more kinds can also be used.Relative to epoxy resin (a) 100 mass parts in optics composition epoxy resin of the present invention, curing catalyst can use 0.01 ~ 5.0 mass parts as required.By optionally using these curing catalysts, solidification value can be reduced or shorten set time.
In optics composition epoxy resin of the present invention, as viscosity adjustment purposes, can also be with an organic solvent.As spendable organic solvent, not special stipulation, if particular instantiation, can enumerate: the amidess such as DMF, the ethers such as ethylene glycol monomethyl ether, the ketones such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), the alcohols such as methyl alcohol, ethanol, benzene,toluene,xylenes etc. are aromatic hydrocarbon based, the ester such as methyl acetate, ethyl acetate class, the non-proton class polar solvent such as N-Methyl pyrrolidone.These solvents may be used alone, can also be two or more kinds in combination.
Optics composition epoxy resin of the present invention can coordinate curable resin except epoxy resin and thermoplastic resin in the scope not damaging characteristic.If particular instantiation, can enumerate: resol, acrylic resin, petroleum resin, indene resin, indenes-coumarone indene resin, phenoxy resin, cyanate ester resin, Epocryl, vinyl compound, urethane, polyester, polymeric amide, polyimide, polyamidoimide, polyetherimide, bismaleimide-triazine resin, polyethersulfone, polysulfones, polyether-ether-ketone, polyphenylene sulfide, polyvinyl formal etc., but be not limited to these resins.In optics composition epoxy resin of the present invention, about content during these resins of use, when total usage quantity of epoxy resin (a) and solidifying agent (b) is counted 100 mass parts, preferably 5 ~ 30 mass parts, more preferably 15 ~ 20 mass parts.If content is very few, then can not obtain the effect coordinating these resins fully, if content is too much, then there is the tendency that the wet fastness of cured article etc. reduces.
In optics composition epoxy resin of the present invention, filler can be used as required.Specifically, can enumerate: aluminium hydroxide, magnesium hydroxide, talcum, burn till the mineral fillers such as talcum, clay, kaolin, titanium hydroxide, glass powder, silicon oxide microsphere, also can coordinate the pigment etc. such as the moisture-proof pigment of organic or mineral-type, flakey pigment.As the reason usually using inorganic filler, the raising of shock-resistance can be enumerated.In addition, the organic fillers etc. such as cellulosic weighting agent and particulate rubber, thermoplastic elastomer such as glass fibre, paper pulp fiber, synthon, ceramic fiber can be coordinated.In optics composition epoxy resin of the present invention, about content during use filler, when total usage quantity of epoxy resin (a) and solidifying agent (b) is counted 100 mass parts, preferably 5 ~ 80 mass parts, more preferably 15 ~ 60 mass parts, further preferred 30 ~ 50 mass parts.If content is very few, then fully can not obtain the effect coordinated, if content is too much, then the intensity of the tendency that the viscosity that there is composition rises and cured article reduces thus the tendency become fragile.
In addition, in optics composition epoxy resin of the present invention, fire retardant, thixotropy can be coordinated as required to give the additive such as material, fluidity improving agent.Give material as thixotropy, can enumerate: silicone based, castor-oil plant oils, aliphatic amide wax, oxidized polyethlene wax, organobentonite class etc.Further as required, the lubricants such as the low-stress such as fire retardant, silicone oil agent, calcium stearate such as releasing agent, the carbon black etc. such as carnauba wax, OP wax tinting material, ANTIMONY TRIOXIDE SB 203 99.8 PCT can be coordinated in resin combination of the present invention.
In addition, in optics composition epoxy resin of the present invention, antioxidant and photostabilizer can be coordinated as required.In order to improve the stability in storage of optics composition epoxy resin and improve the weathering resistance of curing composition, preferably add antioxidant and photostabilizer.As antioxidant and photostabilizer, commercially available prod can be used.Such as, can enumerate: Sumilizer BHT, Sumilizer S, Sumilizer BP-76, Sumilizer MDP-S, Sumilizer GM, Sumilizer BBM-S, Sumilizer WX-R, Sumilizer NW, Sumilizer BP-179, Sumilizer BP-101, Sumilizer GA-80, Sumilizer TNP, Sumilizer TPP-R, Sumilizer P-16 (Sumitomo Chemical Co's system), Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-60, Adekastab AO-70, Adekastab AO-80, Adekastab AO-330, Adekastab PEP-4C, Adekastab PEP-8, AdekastabPEP-24G, Adekastab PEP-36, Adekastab HP-10, Adekastab 2112, Adekastab260, Adekastab 522A, Adekastab 329K, Adekastab 1500, Adekastab C, Adekastab 135A, Adekastab 3010 (Asahi Denka Kogyo K. K's system), Tinuvin 770, Tinuvin 765, Tinuvin 144, Tinuvin 622, Tinuvin 111, Tinuvin 123, Tinuvin292 (Ciba Specialty Chemicals Co., Ltd. system), Fancryl FA-711M, FA-712HM (Hitachi Chemical Co., Ltd.'s system), Double Chisorb 292 (ボ Application De ケ ミ カ Le Inc.) etc.The use level of these antioxidants and photostabilizer is not particularly limited, but when total usage quantity of epoxy resin (a) and solidifying agent (b) is counted 100 mass parts, preferably 0.001 ~ 5 mass parts, more preferably 0.01 ~ 3 mass parts.
In order to manufacture film-like adhesive of the present invention and colour filter protective membrane and optics composition epoxy resin be processed into sheet or membranaceous method is not particularly limited, known technology can be used.Such as, can enumerate: (a) extrusion moulding, its be utilize forcing machine optics composition epoxy resin of the present invention is carried out mixing after extrude, and use T-shaped mould or circular die etc. to be shaped to sheet; (b) doctor-blade casting process, it optics composition epoxy resin of the present invention is dissolved or dispersed in after in organic solvent equal solvent, is carrying out curtain coating, thus be shaped to sheet; (c) other sheet forming methods known etc.
In these methods of forming, preferably (b) doctor-blade casting process.Optics composition epoxy resin organic solvent of the present invention is diluted, thus prepare aqueous varnish, this varnish is coated on supporter by flow coat method, rolling method, gravure roll method, coiling rod method, die lip coating method etc., then, by dry solvent, can obtain that there is the sheet of any thickness or membranaceous composition.As the supporter of coating varnish, be not particularly limited, can use plastic film or the generally well-known supporters such as tinsel, metal sheet such as polyester, polyolefins, polyimide, fluorine class, these supporters preferably implement demoulding process or Electrostatic Treatment etc. in advance.When preparing varnish, can dilute with solvent after the cooperation of each composition, or can dilute with solvent in advance before the cooperation of each composition.In addition, drying conditions is not particularly limited, preferably at 50 ~ 100 DEG C dry 3 ~ 15 minutes.
The film formed after dry or the thickness of sheet are not particularly limited, preferably 3 ~ 300 μm, more preferably 5 ~ 200 μm, and 10 ~ 180 μm is further preferred scope.When protective membrane for colour filter photoreactive semiconductor substrate, most preferably 10 ~ 50 μm.If thickness is more than 3 μm, then can obtain insulativity, if be less than 300 μm, then can guarantee the transparency.In addition, the content of the solvent in film or sheet is not particularly limited, but overall relative to resin combination, is preferably 0.01 ~ 5 quality %.If the content of the solvent in film is more than 0.01 quality % relative to resin combination entirety, then, time stacked to substrate etc., adaptation and cementability can be obtained, in addition, if be below 5 quality %, then can obtain the flatness after being heating and curing.
Optics composition epoxy resin of the present invention can come shaping by the method identical with known composition epoxy resin and solidify, thus becomes cured article.Forming method, curing can adopt the method identical with known composition epoxy resin, do not need method specific to resin combination of the present invention.Optics epoxy resin cured product of the present invention can take the forms such as sandwich, forming composition, sticky object, film, film, transparency when using in the position being exposed to high temperature, resistance to thermal reliability (high heat-resisting xanthochromia) are good, are useful as materials such as the sealing material used in the electrical and electronic parts of optical applications, plywood, insulating material, matrix material, insulating adhesives.
Embodiment
Based on embodiment and comparative example, the present invention is specifically described, but scope of the present invention is not limited to these embodiments.In following synthesis example, embodiment and comparative example, " part " represents mass parts, and " % " represents quality %.In addition, following test method is used in the present invention.
(1) epoxy equivalent (weight): measured by JIS K-7236.
(2) softening temperature: measured by JISK-7234.
(3) specific refractory power: use Abbérefractometer (ERMA Inc., ER-7MW), the mode reaching 30% according to solids component is dissolved in pimelinketone, 20 DEG C, measure under wavelength 589.3nm, by calculating the specific refractory power obtaining solids component 100%.
(4) second-order transition temperature (Tg): use means of differential scanning calorimetry determinator (SII Inc., EXTER DSC6200), measured by the heat-up rate of 10 DEG C/min from 20 DEG C.
(5) heat-resisting xanthochromia: use colour examining colour-difference-metre (Tokyo electricity Se Inc., TC-1500MC-88) measure, to the YI value before thermal process be applied as blank value, illustrate with at 250 DEG C, in the baking oven keeping constant temperature, preserve the specified time after the difference of YI value.Numerical value is less, represents that heat-resisting xanthochromia is better.
(6) resistance to ultra violet discoloration: use colour examining colour-difference-metre measure, using the YI value before rayed as blank value, represent and with exposure intensity 400W/m
2(using ATLS Inc. SUNTESTXLS) irradiates the difference of the YI value after 24 hours.Numerical value is less, represents that resistance to ultra violet discoloration is better.
(7) permeability: use spectrophotometer (Japan Spectroscopy Corporation's system, V-650), measures the transmitance (%) at wavelength 450nm place.Using the measured value of test film implemented before thermal process and rayed as initial value, respectively to keeping the test film after 30 minutes and with exposure intensity 400W/m at 250 DEG C in the baking oven keeping constant temperature
2irradiate the test film after 24 hours to measure.
The explanation of the dummy suffix notation used in synthesis example, embodiment, comparative example.
(epoxy resin)
The diglycidylether of Epotohto YD-128:2,2-bis-(4-hydroxy phenyl) propane, epoxy equivalent (weight) 187g/eq, viscosity 13000mPss/25 DEG C, Nippon Steel & Sumitomo Metal Corporation's system
The diglycidylether of ESF-300:9,9-bis-(4-hydroxy phenyl)-9H-fluorenes, epoxy equivalent (weight) 250g/eq, softening temperature 87 DEG C, Nippon Steel & Sumitomo Metal Corporation's system
Celloxide 2021P:3 ', 4 '-epoxycyclohexyl-methyl-3,4-epoxycyclohexane carboxylate, epoxy equivalent (weight) 133g/eq, viscosity 240mPas/25 DEG C, Daicel chemical industry Co., Ltd. system
The diglycidylether of Epotohto ZX-1658GS:1,4-cyclohexanedimethanol, epoxy equivalent (weight) 134g/eq, viscosity 37mPss/25 DEG C, Nippon Steel & Sumitomo Metal Corporation's system
(acid anhydrides)
Rikacid HH: hexahydrophthalic anhydride, New Japan Chem Co., Ltd's system
Rikacid MH:4-methylhexahydrophthalic anhydride, New Japan Chem Co., Ltd's system
(2 yuan of alcohol)
Rikabinol HB: Hydrogenated Bisphenol A, New Japan Chem Co., Ltd's system
SPG: spiral shell glycol, Mitsubishi Gas Chemical Co., Ltd's system
HDL:1,6-hexylene glycol, Ube Industries, Ltd's system
(2 officials' energy phenolic compound)
BPF:9,9-bis-(4-hydroxy phenyl)-9H-fluorenes, hydroxyl equivalent=175g/eq, Osaka gas KCC system
BPA:2,2-bis-(4-hydroxy phenyl) propane, hydroxyl equivalent=114g/eq, Nippon Steel & Sumitomo Metal Corporation's system
(catalyzer)
Hishicolin BTPPBr: normal-butyl three phenyl phosphonium bromide, Nippon Chemical Ind's system
TPP: triphenylphosphine, Bei Xing KCC system
Curezol 2E4MZ:2-ethyl-4-methylimidazole, four countries change into Co., Ltd.'s system
Synthesis example 1
To being equipped with stirrer, thermometer, nitrogen is blown in the reaction unit of pipe and cooling tube and adds the Rikacid HH 121.5 parts as acid anhydrides and the Rikabinol HB 113.6 parts as 2 yuan of alcohol, while this mixture is stirred in nitrogen atmosphere, while make it react 2 hours at 130 DEG C, after obtaining the ester cpds containing terminal carboxyl(group), then the Epotohto YD-128567.5 part as epoxy resin is added, as 2 officials' energy BPF 197.4 parts of phenolic compound and the HishicolinBTPPBr 0.43 part as catalyzer, 4 hours are uniformly mixed at 150 DEG C, obtain epoxy resin 1.
Synthesis example 2
Except use Rikacid HH 112.9 parts as acid anhydrides, Rikabinol HB 105.6 parts as 2 yuan of alcohol, Epotohto YD-128527.5 part as epoxy resin, BPF 254.0 parts as 2 officials can phenolic compound, Hishicolin BTPPBr 0.47 part is as except catalyzer, operate in the same manner as synthesis example 1, obtain epoxy resin 2.
Synthesis example 3
Being equipped with stirrer, thermometer, nitrogen is blown in the reaction unit of pipe and cooling tube, add as epoxy resin Celloxide 2021P 621.8 parts, can the BPF 131.2 parts of phenolic compound and BPA 247.0 parts, TPP 0.38 part as catalyzer as 2 officials, at 150 DEG C, be uniformly mixed 4 hours, obtain epoxy resin 3.
Synthesis example 4
Except use Rikacid MH 229.9 parts as acid anhydrides, Rikabinol HB 195.4 parts as 2 yuan of alcohol, ESF-300574.7 part as epoxy resin, and do not use 2 officials' energy phenolic compound, use Hishicolin BTPPBr 0.42 part as beyond catalyzer, operate in the same manner as synthesis example 1, obtain epoxy resin 4.
Synthesis example 5
Except use Rikacid HH 97.6 parts as acid anhydrides, Rikabinol HB 79.5 parts as 2 yuan of alcohol, Epotohto ZX-1658GS 502.9 parts as epoxy resin, BPF 320.0 parts as 2 officials can phenolic compound, Hishicolin BTPPBr 0.50 part is as except catalyzer, operate in the same manner as synthesis example 1, obtain epoxy resin 5.
Synthesis example 6
Except use Tetra hydro Phthalic anhydride 149.2 parts as acid anhydrides, Rikabinol HB 125.8 parts as 2 yuan of alcohol, Epotohto ZX-1658GS 493.2 parts as epoxy resin, BPF 230.4 parts as 2 officials can phenolic compound, Hishicolin BTPPBr 0.51 part is as except catalyzer, operate in the same manner as synthesis example 1, obtain epoxy resin 6.
Synthesis example 7
Except use Tetra hydro Phthalic anhydride 131.8 parts as acid anhydrides, Rikabinol HB 113.4 parts as 2 yuan of alcohol, Epotohto YD-128493.0 part and Celloxide 2021P 103.7 parts as epoxy resin, BPA 158.1 parts as 2 officials can phenolic compound, Hishicolin BTPPBr 0.40 part is as except catalyzer, operate in the same manner as synthesis example 1, obtain epoxy resin 7.
Synthesis example 8
Except use ESF-300334.5 part and Celloxide 2021P 353.3 parts as epoxy resin, BPA 312.2 parts as 2 officials can phenolic compound, Hishicolin BTPPBr 0.31 part is as except catalyzer, operate in the same manner as synthesis example 3, obtain epoxy resin 8.
Synthesis example 9
Except use Rikacid HH 95.9 parts as acid anhydrides, SPG 106.5 parts as 2 yuan of alcohol, Epotohto YD-128569.3 part as epoxy resin, BPF 228.3 parts as 2 officials can phenolic compound, Hishicolin BTPPBr 0.43 part is as except catalyzer, operate in the same manner as synthesis example 1, obtain epoxy resin 9.
Synthesis example 10
As except catalyzer, operate in the same manner as synthesis example 3, obtain epoxy resin 10 as epoxy resin, BPA 302.0 parts as 2 officials' energy phenolic compound, Curezol 2E4MZ 0.03 part except using Epotohto YD-128698.0 part.
Synthesis example 11
As except catalyzer, operate in the same manner as synthesis example 3, obtain epoxy resin 11 as epoxy resin, BPF 386.0 parts as 2 officials' energy phenolic compound, TPP 0.39 part except using Epotohto YD-128641.0 part.
Synthesis example 12
Except use Tetra hydro Phthalic anhydride 189.6 parts as acid anhydrides, HDL 369.6 parts as 2 yuan of alcohol, Epotohto YD-128440.8 part as epoxy resin, and do not use 2 officials' energy phenolic compound, use Hishicolin BTPPBr 0.56 part as beyond catalyzer, operate in the same manner as synthesis example 1, obtain epoxy resin 12.
Synthesis example 13
Except use Rikacid HH 64.0 parts as acid anhydrides, Rikabinol HB 59.7 parts as 2 yuan of alcohol, Epotohto YD-128594.8 part as epoxy resin, BPF 281.5 parts as 2 officials can phenolic compound, Hishicolin BTPPBr 0.41 part is as except catalyzer, operate in the same manner as synthesis example 1, obtain epoxy resin 13.
Synthesis example 14
As except catalyzer, operate in the same manner as synthesis example 3, obtain epoxy resin 14 as epoxy resin, BPF 491.1 parts as 2 officials' energy phenolic compound, TPP 0.49 part except using Celloxide 2021P 508.9 parts.
Synthesis example 15
Except use Rikacid HH 220.2 parts as acid anhydrides, Rikabinol HB 205.4 parts as 2 yuan of alcohol, Celloxide 2021P 464.4 parts as epoxy resin, BPA 110.0 parts as 2 officials can phenolic compound, Hishicolin BTPPBr 0.54 part is as except catalyzer, operate in the same manner as synthesis example 1, obtain epoxy resin 15.
Synthesis example 16
Except use Rikacid HH 302.7 parts as acid anhydrides, Rikabinol HB 282.4 parts as 2 yuan of alcohol, Celloxide 2021P 414.9 parts as epoxy resin, and do not use 2 officials' energy phenolic compound, use Hishicolin BTPPBr 0.59 part as beyond catalyzer, operate in the same manner as synthesis example 1, obtain epoxy resin 16.
Synthesis example 17
Except use Rikacid HH 275.0 parts as acid anhydrides, Rikabinol HB 256.2 parts as 2 yuan of alcohol, Epotohto ZX-1658GS 468.8 parts as epoxy resin, and do not use 2 officials' energy phenolic compound, use Hishicolin BTPPBr 0.53 part as beyond catalyzer, operate in the same manner as synthesis example 1, obtain epoxy resin 17.
Synthesis example 18
Except use Rikacid HH 248.0 parts as acid anhydrides, Rikabinol HB 229.0 parts as 2 yuan of alcohol, Epotohto YD-128523.0 part as epoxy resin, and do not use 2 officials' energy phenolic compound, use Hishicolin BTPPBr 0.48 part as beyond catalyzer, operate in the same manner as synthesis example 1, obtain epoxy resin 18.
Synthesis example 19
Except use Rikacid HH 140.0 parts as acid anhydrides, Rikabinol HB 120.0 parts as 2 yuan of alcohol, Epotohto YD-128195.0 part and ESF-300545.0 part as epoxy resin, and do not use 2 officials' energy phenolic compound, use Hishicolin BTPPBr 0.30 part as beyond catalyzer, operate in the same manner as synthesis example 1, obtain epoxy resin 19.
Synthesis example 20
Except use Rikacid HH 127.9 parts as acid anhydrides, Rikabinol HB 100.6 parts as 2 yuan of alcohol, Epotohto YD-128527.5 part as epoxy resin, BPF 254.0 parts as 2 officials can phenolic compound, Hishicolin BTPPBr 0.47 part is as except catalyzer, operate in the same manner as synthesis example 1, obtain epoxy resin 20.
The proterties of the epoxy resin 1 ~ 20 obtained is shown in table 1 ~ 2.
Table 1
Table 2
Embodiment 1
Using the epoxy resin 1 obtained in 100 parts of synthesis examples 1 of epoxy resin be dissolved in 75 parts as in the tetrahydrofuran (THF) of solvent as 15 parts of Rikacid HH of solidifying agent, then the Hishicolin PX-4ET (You Ji phosphonium salt compound as curing catalyst is mixed, Nippon Chemical Ind's system) 0.25 part, make liquid composition.
Be that liquid composition is coated on the thick sheet glass of 0.2mm by the mode of 100 μm with dried film, and make its in the Hotaircirculatingoven of 100 DEG C dry 2 hours, then, make it solidify 10 hours in the Hotaircirculatingoven of 140 DEG C, obtain the test film being with sheet glass.The test film of the band sheet glass that direct utilization obtains, measures heat-resisting xanthochromia, resistance to ultra violet discoloration and permeability.
Embodiment 2 ~ 10
Use epoxy resin 2 ~ 9 that 100 parts of synthesis examples 2 ~ 9 obtain as the solidifying agent shown in epoxy resin and table 3, operate similarly to Example 1, make test film, and evaluate.
The kind of epoxy resin, solidifying agent and the usage quantity of solidifying agent are shown in table 3.Evaluation result is shown in table 5.In table 3, HH is Rikacid HH, PA is Tetra hydro Phthalic anhydride.
Table 3
| Embodiment | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 |
| Epoxy resin | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 1 |
| Solidifying agent | HH | HH | HH | HH | HH | HH | HH | HH | HH | PA |
| Usage quantity (part) | 15 | 8 | 28 | 12 | 17 | 17 | 14 | 16 | 14 | 14 |
Comparative example 1 ~ 12
Use the resin 10 ~ 20 obtained in 100 parts of synthesis examples 10 ~ 20 as the solidifying agent shown in epoxy resin and table 4, operate similarly to Example 1, make test film, and evaluate.
The kind of epoxy resin, solidifying agent and the usage quantity of solidifying agent are shown in table 4.Evaluation result is shown in table 6.
Table 4
| Comparative example | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12 |
| Epoxy resin | 10 | 11 | 12 | 13 | 14 | 15 | 16 | 17 | 18 | 19 | 20 | 15 |
| Solidifying agent | HH | HH | HH | HH | HH | HH | HH | HH | HH | HH | HH | PA |
| Usage quantity (part) | 16 | 16 | 15 | 16 | 16 | 16 | 16 | 22 | 16 | 15 | 8 | 14 |
Table 5
Table 6
Claims (16)
1. an optics composition epoxy resin, it is characterized in that, it is the optics composition epoxy resin containing epoxy resin (a) and solidifying agent (b), wherein, the epoxy equivalent (weight) of described epoxy resin (a) is 500 ~ 2000g/eq, softening temperature is 80 ~ 150 DEG C, 20 DEG C, wavelength is refractive index n under 589.3nm
d 20be 1.55 ~ 1.63, there is in molecular structure aromatic ring and aliphatics ring simultaneously, and the strength ratio of aliphatic protons (A) in 1H-NMR spectrum and aromatic protons (B) and B/A are 0.3 ~ 0.7.
2. optics composition epoxy resin according to claim 1, wherein, epoxy resin (a) is by the epoxy resin that is obtained by reacting of the ester cpds (c) of the fatty race ring of terminal carboxyl(group) with 2 officials' energy aromatic epoxy resin (e1), or by the epoxy resin that is obtained by reacting of 2 yuan of phenolic compound (d) with the epoxy resin (e2) of the fatty race ring of 2 officials' energy.
3. optics composition epoxy resin according to claim 2, wherein, the ester cpds (c) of the fatty race ring of terminal carboxyl(group) is by the ester cpds of the fatty race ring of the terminal carboxyl(group) be obtained by reacting of the acid anhydrides of 2 yuan of alcohol of fatty race ring and the acid anhydrides of acid anhydrides, 2 yuan of alcohol and fatty race ring or 2 yuan of alcohol of fatty race ring and fatty race ring.
4. optics composition epoxy resin according to claim 2, wherein, 2 yuan of phenolic compound (d) are the phenolic compound containing fluorenes ring.
5. optics composition epoxy resin according to claim 2, wherein, 2 officials can aromatic epoxy resin (e1) be can aromatic epoxy resin containing 2 officials of fluorenes ring.
6. optics composition epoxy resin according to claim 2, wherein, the epoxy resin (e2) of the fatty race ring of 2 officials' energy is the alicyclic epoxy resin of 2 officials' energy.
7. the optics composition epoxy resin according to any one of claim 1 ~ 6, wherein, relative to the epoxy group(ing) 1 mole of epoxy resin (a), the active hydrogen base of solidifying agent (b) is the scope of 0.4 ~ 1.2 mole.
8. the optics composition epoxy resin according to any one of claim 1 ~ 7, it is film-like adhesive composition epoxy resin.
9. the optics composition epoxy resin according to any one of claim 1 ~ 7, it is color filter protecting layer composition epoxy resin.
10. the optics composition epoxy resin according to any one of claim 1 ~ 7, it is photosemiconductor substrate surface protection film composition epoxy resin.
11. 1 kinds of epoxy resin cured products, it makes the optics epoxy resin composition according to any one of claim 1 ~ 7 obtain.
12. 1 kinds of film-like adhesives, it uses the composition epoxy resin described in claim 8 to obtain.
13. 1 kinds of colour filter protective membranes, it uses the composition epoxy resin described in claim 9 to obtain.
14. 1 kinds of photosemiconductor sealing materials, it uses the optics composition epoxy resin according to any one of claim 1 ~ 7 to obtain.
15. 1 kinds of photosemiconductor substrates, it uses the optics composition epoxy resin according to any one of claim 1 ~ 7 to obtain.
16. 1 kinds of photosemiconductor substrate surface protection films, it uses the composition epoxy resin described in claim 10 to obtain.
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| JP2013262379A JP6364187B2 (en) | 2013-12-19 | 2013-12-19 | Optical epoxy resin composition and cured product thereof |
| JP2013-262379 | 2013-12-19 |
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| CN107922586A (en) * | 2015-08-13 | 2018-04-17 | 株式会社大赛璐 | Solidification compound and its solidfied material |
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| CN112029071A (en) * | 2019-06-03 | 2020-12-04 | 长春人造树脂厂股份有限公司 | Light attenuation resistant epoxy resin and application thereof |
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| KR102283119B1 (en) * | 2018-01-11 | 2021-07-28 | 주식회사 엘지화학 | Coationg composition, manufacturing method of polarizer protecting film using same, polarizer protecting film, polarizing plate comprising same and liquid crystal display device comprising same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105022119A (en) * | 2015-08-07 | 2015-11-04 | 中时讯通信建设有限公司 | Optical fiber fusion splicing method |
| CN105022119B (en) * | 2015-08-07 | 2018-07-31 | 中时讯通信建设有限公司 | A kind of optical fiber splicing method |
| CN107922586A (en) * | 2015-08-13 | 2018-04-17 | 株式会社大赛璐 | Solidification compound and its solidfied material |
| CN107922586B (en) * | 2015-08-13 | 2021-07-23 | 株式会社大赛璐 | Curable composition and cured product thereof |
| CN107057520A (en) * | 2017-02-15 | 2017-08-18 | 盘锦群益管道防腐有限公司 | A kind of preparation method of high-temperaure coating |
| CN108864956A (en) * | 2018-06-14 | 2018-11-23 | 深圳市德彩光电有限公司 | LED encapsulates glue formula and preparation method |
| CN112029071A (en) * | 2019-06-03 | 2020-12-04 | 长春人造树脂厂股份有限公司 | Light attenuation resistant epoxy resin and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| KR102261966B1 (en) | 2021-06-07 |
| JP6364187B2 (en) | 2018-07-25 |
| TW201527407A (en) | 2015-07-16 |
| TWI646143B (en) | 2019-01-01 |
| CN104725600B (en) | 2018-04-24 |
| KR20150072341A (en) | 2015-06-29 |
| JP2015117325A (en) | 2015-06-25 |
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