CN103140523A - Polyhydric hydroxy resin, epoxy resin, production method therefor, epoxy resin composition and cured product thereof - Google Patents
Polyhydric hydroxy resin, epoxy resin, production method therefor, epoxy resin composition and cured product thereof Download PDFInfo
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- CN103140523A CN103140523A CN2011800464068A CN201180046406A CN103140523A CN 103140523 A CN103140523 A CN 103140523A CN 2011800464068 A CN2011800464068 A CN 2011800464068A CN 201180046406 A CN201180046406 A CN 201180046406A CN 103140523 A CN103140523 A CN 103140523A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
- C08G8/30—Chemically modified polycondensates by unsaturated compounds, e.g. terpenes
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
- C07C39/12—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings
- C07C39/15—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings with all hydroxy groups on non-condensed rings, e.g. phenylphenol
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
- C08G59/08—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols from phenol-aldehyde condensates
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
- C08G59/621—Phenols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
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Abstract
Provided are an epoxy resin, a polyhydric hydroxy resin and composition thereof that produce cured products with excellent flame retardancy, moisture resistance, low elasticity, etc. and are suitable for uses such as sealing electronic parts, circuit board material, etc. By reacting 0.3-1.0 moles of a styrene with respect to 1 mole of a phenol novolac as a polyhydric hydroxy compound in the presence of an acid catalyst, a styrene-modified polyhydric hydroxy resin is obtained, wherein the area% of the monohydric hydroxy compound by-product detected by gel permeation chromatography is 3% or less. An epoxy resin is obtained by reacting the styrene-modified polyhydric hydroxy resin with epichlorohydrin. The epoxy resin composition contains the styrene-modified polyhydric hydroxy resin or epoxy resin as an essential component.
Description
Technical field
The present invention relates to the solidified nature excellence, give simultaneously flame retardant resistance, wet fastness, low elasticity also epoxy resin, the polyhydroxy resin that is suitable as its intermediate, their manufacture method, the composition epoxy resin that has used them and the cured article thereof of excellent cured article, be suitable for the insulating material in the electric and electronic such as semiconductor-encapsulating material, printing distributing board field etc.
Background technology
Epoxy resin is using in purposes widely industrial, and it requires performance High Level day by day in recent years.For example, as the field of the representative of the resin combination of host, semiconductor-encapsulating material is being arranged with epoxy resin, follow the raising of the integrated level of semiconductor element, package dimension is to big area, slimming development, simultaneously for the actual load mode, to the transfer development of surperficial actual load, wish the material of exploitation solder heat resistance excellence.Therefore, as sealing material, except low moisture absorption, strong request is in the raising of the cementability adaptation at the foreign material such as lead frame, chip interface.Similarly, wish exploitation except the viewpoint from the solder heat resistance raising in circuit base material, beyond the raising of agent of low hygroscopicity, high heat resistance, high adaptation, the material of the viewpoint low-dielectric excellence that reduces from dielectric loss.In order to tackle these requirements, studied epoxy resin and the solidifying agent of various novel textures.And recently, from alleviating the viewpoint of carrying capacity of environment, require to have more excellent epoxy resin and the solidifying agent of effect, flame retardant resistance of getting rid of the halogen flame retardant.
Therefore, from above-mentioned background, various epoxy resin and epoxy curing agent have been studied.As an example of epoxy curing agent, known naphthalene is resin, shown in patent documentation 1, naphthols aralkyl resin is applied to semiconductor-encapsulating material, has put down in writing the excellences such as flame retardant resistance, agent of low hygroscopicity, low heat expansion property.In addition, proposed to have the solidifying agent of biphenyl structural in patent documentation 2, put down in writing improving flame retardant resistance effective.But all there are the poor shortcoming of solidified nature in naphthols aralkyl resin, biphenyl aralkyl resin, and be in addition, for the effect that improves flame retardant resistance, sometimes also insufficient.
On the other hand, for epoxy resin, not yet know the resin that satisfies these requirements.For example, known bisphenol-type epoxy resin is liquid at normal temperatures, and workability is excellent, and is easy with mixing of solidifying agent, additive etc., therefore uses widely, but has problems aspect thermotolerance, wet fastness.In addition, as the improved epoxy resin of thermotolerance, known ortho-cresol novolac type epoxy resin, about flame retardant resistance, insufficient.
In the situation that do not use the halogen flame retardant to improve the strategy of flame retardant resistance, the method for the fire retardant that adds phosphoric acid ester system is disclosed as being used for.But for the method for the fire retardant that uses phosphoric acid ester to be, wet fastness is insufficient.In addition, under the environment that have high temperature, wets, phosphoric acid ester is hydrolyzed more, makes the problem as the reliability reduction of insulating material.
As in the situation that do not contain the example that phosphorus atom, halogen atom improve flame retardant resistance, the example that the aralkyl-type epoxy resin that will have biphenyl structural is applied to semiconductor-encapsulating material is disclosed in patent documentation 2 and 3.The example that uses the aralkyl-type epoxy resin with naphthalene structure is disclosed in patent documentation 4.But these epoxy resin are in flame retardant resistance, wet fastness or stable on heating either side, and performance is insufficient.
On the other hand, as the example of the raising that is conceived to thermotolerance, wet fastness, resistance to cracking, disclose benzyl polyphenol and epoxy resin thereof in patent documentation 5, these are not to be conceived to flame retardant resistance.In addition, these are by using novolac resin as starting raw material, the resin that then makes the benzyl chloride addition reaction and obtain, but because being utilizes the hydrochloric acid that generates when reacting as the reaction under the strong acidic condition of catalyzer, therefore there is the methylene-crosslinked key part cracking of novolac resin, the problem of by-product phenol.That is, as by product, therefore there is the problem that solidified nature and thermotolerance are reduced due to the phenol body that contains simple function.
In addition, example as the manufacture method of phenylethene modified novolac resin, the method that novolac resin and vinylbenzene are reacted under the existence of acid catalyst is disclosed in patent documentation 6, but owing at high temperature using highly acid sulfuric acid catalyst, so also there is the methylene-crosslinked key part cracking of novolac resin in this method for making and the problem of by-product phenol.
On the other hand, example as the composition epoxy resin of the raising that is conceived to wet fastness, low-stress, disclose the composition epoxy resin that uses SP styrenated phenol Novolac resin and epoxy resin thereof in patent documentation 7 and 8, but these neither be conceived to flame retardant resistance.In addition, these are owing to being to use styrenated phenol as starting raw material, and then the method for making of novolac resin, therefore exist high boiling styrenated phenol remaining in resin, the problem that therefore solidified nature and thermotolerance is reduced.
The prior art document
Patent documentation
Patent documentation 1: JP 2005-344081 communique
Patent documentation 2: Unexamined Patent 11-140166 communique
Patent documentation 3: JP 2000-129092 communique
Patent documentation 4: JP 2004-59792 communique
Patent documentation 5: Unexamined Patent 8-120039 communique
Patent documentation 6: JP 48-52895 communique
Patent documentation 7: Unexamined Patent 5-132544 communique
Patent documentation 8: Unexamined Patent 5-140265 communique
Summary of the invention
The object of the present invention is to provide in stacked, moulding, casting, the purposes such as bonding and have the solidified nature excellence, while flame retardant resistance, wet fastness, low elasticity etc. are the epoxy resin of excellent performance also, provide to have excellent solidified nature, give simultaneously flame retardant resistance, wet fastness, low elasticity etc. also the sealing that can be used for the electrical and electronic parts class, circuit base material etc. of excellent cured article composition epoxy resin and its cured article is provided.
That is, the present invention relates to polyhydroxy resin, it is characterized in that, in by the polyhydroxy resin shown in following general formula (1), used by the monohydroxy compound shown in following general formula (2) and adopt gel permeation chromatography (GPC; Area % when RI) detecting represents, is below 3%.
(R
1The alkyl of expression hydrogen or carbonatoms 1～6, R
2Represent followingly by the substituting group shown in formula (a), n represents 0～20 number.P represents 0.1～2.5 number.In addition, R
3The alkyl of expression hydrogen or carbonatoms 1～6.）
(wherein, p represents 0～3 number, R
1And R
3The alkyl of expression hydrogen or carbonatoms 1～6.）
In addition, the present invention relates to the manufacture method of polyhydroxy resin, it is characterized in that, with respect to by 1 mole of the hydroxyl of the polyol shown in following general formula (3), under the existence of the acid catalyst below 10～400wtppm, make styrenic 0.1～1.0 molar reactive under 40～120 ℃ of temperature of reaction, make above-mentionedly to replace phenyl ring to polyol by the substituting group shown in formula (a).
In addition, the present invention relates to epoxy resin, it is characterized in that, in the epoxy resin shown in following general formula (4), used by the monocycle epoxy resins shown in following general formula (5) and adopt gel permeation chromatography (GPC; Area % when RI) detecting represents, is below 3%.
(wherein, G represents glycidyl, R
1The alkyl of expression hydrogen or carbonatoms 1～6, R
2Represent above-mentioned by the substituting group shown in formula (a), R
3The alkyl of expression hydrogen or carbonatoms 1～6, n represents 1～20 number.In addition, p represents 0.1～2.5 number.）
(wherein, G represents glycidyl, R
1And R
3The alkyl of expression hydrogen or carbonatoms 1～6, p represents 0～3 number.）
In addition, the present invention relates to the manufacture method of epoxy resin, it is characterized in that, make the reaction of above-mentioned polyhydroxy resin and Epicholorohydrin.
In addition, the present invention relates to composition epoxy resin, wherein, coordinate the one or both of above-mentioned polyhydroxy resin and above-mentioned epoxy resin as neccessary composition in the composition epoxy resin that comprises epoxy resin and solidifying agent.In addition, the present invention relates to make above-mentioned composition epoxy resin to solidify the epoxy resin cured product that forms.
Description of drawings
Fig. 1 is the GPC figure of the polyhydroxy resin that obtains in embodiment.
Fig. 2 is the GPC figure of the polyhydroxy resin that obtains in synthesis example.
Fig. 3 is the GPC figure of the epoxy resin that obtains in embodiment.
Fig. 4 is the GPC figure of the epoxy resin that obtains in synthesis example.
Embodiment
At first, polyhydroxy resin of the present invention (being designated hereinafter simply as STPN) is described.StPN of the present invention general formula (1) expression, it can obtain by making by the polyol shown in general formula (3) (also referred to as polyol (3)) and styrenic reaction.
As the method that makes styrenic to the polyol addition, be generally under the existence of the acid catalysts such as hydrochloric acid, react under the high temperature of 120～170 ℃.But, in the situation that at high temperature reaction under acid catalyst exists and follows as the cracking of the methene key of the connection base section of polyol, the problem of by-product monohydric phenol.In order to suppress such side reaction, be reduced to the scope of 40～120 ℃ by making temperature of reaction, and make catalytic amount reduce to the scope of 10～400ppm, can reduce the by-product of monohydric phenol body.That is, in the situation of polyhydroxy resin as the solidifying agent of epoxy resin that obtains, show the physical property of solidified nature, excellent heat resistance.
By side reaction generate by the content in the polyhydroxy resin composition of the monohydroxy compound shown in above-mentioned general formula (2) (also referred to as monohydroxy compound (2)), with adopting gel permeation chromatography (GPC; Area % when RI) detecting represents, is preferably below 3%.In its situation of Duoing, as in the situation of epoxy curing agent, exist the monohydroxy compound that contains as by product to make the tendency of solidified nature reduction polyhydroxy resin.In addition, in epoxy resin cured product, reduce because monohydroxy compound makes cross-linking density, therefore have also poor tendency of thermotolerance.
As by product contained in polyhydroxy resin, as the composition beyond monohydroxy compound, can enumerate styrene oligomer.This is by the by product of the polyreaction generation of vinylbenzene self, especially, as low molecular weight compositions, contains styrene dimer.This styrene dimer composition also with monohydroxy compound similarly, have the tendency that the solidified nature of making and thermotolerance reduce.
In addition, in epoxy resin cured product, the hydroxypropyl that is generated by the reaction of epoxy group(ing) and hydroxyl easily burns, but by making styrenic to the polyol addition, improve hydroxyl equivalent, thereby reduce from the aliphatic carbon rate of the inflammable constituent of epoxy group(ing), can manifest the flame retardant resistance of height.In addition, the addition of the styrenic by being rich in aromatic series, the aromatic series of polyhydroxy resin further improves, and except flame retardant resistance, is also effective for the raising of wet fastness.
Therefore, use these composition epoxy resins that obtains high flame retardant, particularly epoxy resin composition for encapsulating semiconductor.That is, the solidified nature of the excellence in these compositions is manifested, the physical property of high flame retardant, wet fastness, low elasticity excellence is manifested, use this material, can obtain sealing, circuit base material of the high electrical and electronic parts class of reliability etc.
StPN of the present invention obtains by making by polyol (3) and the styrenic addition reaction shown in general formula (3).At this moment, ratio as polyol (3) and styrenic, if the flame retardant resistance of the cured article that consideration obtains and the balance of solidified nature, scope with respect to preferred 0.1～2.5 mole of the usage ratio of the styrenic of 1 mole of polyol, more preferably 0.1～1.0 mole, the scope of 0.3～0.8 mole more preferably.In situation about lacking than this scope, be the not improved state of character of the polyol of raw material, in the situation of Duoing than this scope, exist functional group densities excessively to reduce, the tendency that solidified nature reduces.
In this reaction, styrenic adds the aromatic ring with OH base that is formed in polyol (3), is replaced by the styryl shown in above-mentioned formula (a).In addition, the Adding sites of styrenic is ortho position and/or the contraposition in the room of polyol, is mainly contraposition.
In addition, the scope of the preferred 0.01～10.0Pas of melt viscosity under 150 of StPN of the present invention ℃.From the aspect of workability, melt viscosity is in the preferred low degree of above-mentioned scope.
In addition, softening temperature can be 40～150 ℃, is preferably the scope of 50～100 ℃.Wherein, softening temperature refers to the softening temperature based on the ring and ball method mensuration of JIS-K-2207.If lower than it, when it was coordinated in epoxy resin, the thermotolerance of cured article reduced, if than its height, the mobility during moulding reduces.
R
2Expression is by the styryl shown in above-mentioned formula (a).P represents 0.1～2.5 number, and it means the mean number of 1 cyclosubstituted styryl of phenol (number is average).P is preferred by the order of 0.1～2,0.1～1.0 mole, 0.3～1,0.3～0.8 mole.Have, maximum 4 styryls can replace at the phenol ring of two ends again, and maximum 3 styryls can replace at the phenol ring of centre, so n is that in 1 situation, maximum 8 styryls can replace.
From other viewpoint, the replacement number of the styryl of every 1 molecule of StPN of the present invention (number average) is preferably more than 1, more preferably more than 2, and more preferably 2.6～4.
In formula (a), R
3The alkyl of expression hydrogen or carbonatoms 1～6 is preferably the alkyl of hydrogen or carbonatoms 1～3, more preferably hydrogen.This R
3Determined by the styrenic that uses as reaction raw materials.
In general formula (1), n represents 1～20 number, preferably, and the scope of average out to 1.5～5.0.
Next, the manufacture method of StPN of the present invention described.As the polyol (3) that uses in the method for making StPN of the present invention, use the novolac resin class.
The phenols that uses in order to obtain this polyol (3), alkyl fortified phenol for phenol or carbonatoms 1～6, as the alkyl fortified phenol, can enumerate cresols class, ethylbenzene phenols, isopropyl benzene phenols, tert-butyl phenol, allyl benzene phenols, phenylphenol class etc.Be preferably the alkyl substituted benzene phenols of phenol or carbonatoms 1～3, more preferably phenol.
This phenols can contain the phenol composition of a small amount of other.For example, use as phenols in the situation of phenol, as other phenol composition, can enumerate ortho-, meta-or p-cresols, m-cresol, p-Cresol, ethylbenzene phenols, isopropyl benzene phenols, tert-butyl phenol, allyl benzene phenols, phenylphenol class, 2，6-xylenol, 2,6-diethyl phenol, quinhydrones, Resorcinol, catechol, 1-naphthols, beta naphthal, 1,5-naphthalenediol, 1,6-naphthalenediol, 1,7-naphthalenediol, 2,6-naphthalenediol, 2,7-naphthalenediol etc.These phenol or aphthols can contain more than 2 kinds.
Be used for the styrenic with the reaction of polyol, the vinylbenzene that replaces for the alkyl of vinylbenzene or carbonatoms 1～6.This styrenic can contain the reacted constituent of a small amount of other.As other reacted constituent, contain in the situation of composition that alpha-methyl styrene, Vinylstyrene, indenes, coumarone, thionaphthene, indoles, vinyl naphthalene etc. contain unsaturated link(age), contain group by these generations in the polyhydroxy resin that obtains at the nuclear substituted compound of fragrance.The resol that adopts the manufacture method of polyhydroxy resin of the present invention to obtain can contain and has so substituent polyhydroxy resin.Similarly, adopt epoxy resin that the manufacture method of epoxy resin of the present invention obtains to contain and have so substituent epoxy resin.
This reaction can be carried out under the existence of acid catalyst, uses in the scope that its catalytic amount is 10～400ppm, is preferably the scope of 100～350ppm.If more than it, the methylene-crosslinked key of novolac resin becomes and easily ftractures, and due to the monohydric phenol composition by the cleacvage reaction by-product, solidified nature and thermotolerance is reduced.On the other hand, if lack than it, the reactive reduction makes the unreacted benzene vinyl monomer remaining in a large number.In addition, said catalytic amount here means the amount with respect to the catalyzer of the total weight of the polyol that is used for reaction and styrenic.
This reaction can be carried out under the existence of acid catalyst.As this acid catalyst, can suitably be selected by known mineral acid, organic acid.Can enumerate mineral acids such as hydrochloric acid, sulfuric acid, phosphoric acid, the organic acids such as formic acid, oxalic acid, trifluoroacetic acid, tosic acid, dimethyl sulfate, diethyl sulfuric acid, solid acid such as the Lewis acid such as zinc chloride, aluminum chloride, iron(ic) chloride, boron trifluoride or ion exchange resin, atlapulgite, silica-alumina, zeolite etc.
In addition, the temperature of reaction in this reaction is to carry out under the scope of 40～120 ℃.If lower than it, the reactive reduction, the reaction times becomes for a long time.In addition, if than its height, the part of the methylene-crosslinked key of novolac resin becomes and easily ftractures, and due to the monohydric phenol composition by the cleacvage reaction by-product, solidified nature and thermotolerance is descended.
In addition, this reaction was carried out 1～20 hour usually.In addition, during reaction, can use the alcohols such as methyl alcohol, ethanol, propyl alcohol, butanols, ethylene glycol, methylcyclohexane, ethyl cellosolve, the aromatics such as the ethers such as the ketones such as acetone, methylethylketone, methyl iso-butyl ketone (MIBK), dme, diethyl ether, diisopropyl ether, tetrahydrofuran (THF), dioxan, benzene, toluene, chlorobenzene, dichlorobenzene etc. are as solvent.
As the concrete method of implementing this reaction, pack into whole raw materials are disposable, make its reaction like this at the temperature of regulation, perhaps polyol and catalyzer are packed into, remain on the temperature of regulation, simultaneously the limit splashes into the styrenic limit to make the method for its reaction is general method.At this moment, the time that splashes into is preferred below 5 hours, is generally 1～10 hour.After reaction, used in the situation of solvent, after as required catalyst component being removed, solvent has been heated up in a steamer, can access resin of the present invention, do not used in the situation of solvent, discharged during by direct heat, can access object.
Next, epoxy resin of the present invention is described.
Epoxy resin of the present invention (referred to as StPNE) is represented by general formula (4).In addition, polyhydroxy resin (StPN) is represented by general formula (1).StPNE can be by obtaining the StPN epoxidation.
In general formula (4), the symbol common with general formula (1) has identical implication.G represents glycidyl, and the hydroxyl reaction of general formula (1) generates.R
1Be styryl.
To be made by the reaction of the StPN shown in above-mentioned general formula (1) and Epicholorohydrin be favourable to StPNE of the present invention by making, but be not limited to this reaction.But StPN does not contain the above-mentioned monohydroxy compound greater than 3%.Thus, can make by the monocycle epoxy resins shown in above-mentioned general formula (5) (also referred to as monocycle epoxy resins (5)) is below 3%.
Except the reaction that makes the reaction of StPN and Epicholorohydrin, also can take to make the reaction of StPN and allyl halide, after becoming allyl ether compound, with the method for peroxide reactions.The reaction of above-mentioned StPN and Epicholorohydrin reaction can similarly be carried out with common epoxidation reaction.
For example, can enumerate be dissolved in above-mentioned StPN in excessive Epicholorohydrin after, reacting the method for 1～10 hour under the existence of the alkali metal hydroxides such as sodium hydroxide, potassium hydroxide under the scope of 20～150 ℃, preferred 30～80 ℃.The usage quantity of alkali metal hydroxide of this moment with respect to 1 mole of the hydroxyl of StPN, is the scope of 0.8～1.5 mole, preferred 0.9～1.2 mole.In addition, Epicholorohydrin excessively uses with respect to 1 mole of hydroxyl in StPN, usually, with respect to 1 mole of the hydroxyl in StPN, is 1.5～30 moles, is preferably the scope of 2～15 moles.After reaction finishes, the Epicholorohydrin of surplus is heated up in a steamer, residue is dissolved in toluene, methyl iso-butyl ketone (MIBK) equal solvent, filter, inorganic salt are removed in washing, next solvent are heated up in a steamer, thereby can access the epoxy resin of target.
Composition epoxy resin of the present invention comprises epoxy resin and solidifying agent at least, has following 3 kinds.
1) coordinated the composition of above-mentioned StPNE as part or all of epoxy resin.
2) coordinated the composition of above-mentioned StPN as part or all of solidifying agent.
3) coordinated the composition of above-mentioned SPE and StPN as part or all of epoxy resin and solidifying agent.
Above-mentioned 2) and 3) the situation of composition under, contain StPN as neccessary composition.The use level of StPN usually, with respect to epoxy resin 100 weight parts, is 2～200 weight parts, is preferably the scope of 5～80 weight parts.If lack than it, the effect that flame retardant resistance and wet fastness improve is little, if more than it, has the problem of the strength decreased of formability and cured article.
Use in the situation of StPN as the whole amounts of solidifying agent, usually, the use level of StPN is considered the equivalent balanced of the OH base of StPN and the epoxy group(ing) in epoxy resin and is coordinated.The equivalence ratio of epoxy resin and solidifying agent is generally 0.2～5.0 scope, is preferably 0.5～2.0 scope.If larger or less than it than it, the solidified nature of composition epoxy resin reduces, simultaneously the reductions such as the thermotolerance of cured article, mechanical strength.
As solidifying agent, can and use the solidifying agent beyond StPN.The use level of other solidifying agent determines the use level of StPN keeps the scope of scope of 2～200 weight parts, preferred 5～80 weight parts usually with respect to epoxy resin 100 weight parts within.If the use level of StPN is lacked than it, the effect that agent of low hygroscopicity, adaptation and flame retardant resistance improve is little, if more than it, has the problem of the strength decreased of formability and cured article.In this case, the equivalence ratio of epoxy resin and solidifying agent (total) is above-mentioned scope.
Solidifying agent as beyond StPN generally all can use as the known solidifying agent of the solidifying agent of epoxy resin, and Dyhard RU 100, anhydrides, polyatomic phenol, aromatic series and aliphatics amine etc. are arranged.In these, in semiconductor-encapsulating material etc. requires the field of high electric insulation, preferably use polyatomic phenol as solidifying agent.The concrete example of solidifying agent below is shown.
As anhydride curing agent, such as Tetra hydro Phthalic anhydride, Tetra Hydro Phthalic Anhydride, methyl tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl humic acids acid anhydride (methyl himic anhydride), dodecyl succinic anhydride, carbic anhydride, trimellitic acid 1,2-anhydride etc. arranged.
As polyatomic phenol, can enumerate for example dihydroxyphenyl propane, Bisphenol F, bisphenol S, fluorenes bis-phenol, 4,4 '-xenol, 2,2 yuan of phenols such as 2 '-xenol, quinhydrones, Resorcinol, naphthalenediol, perhaps three-(4-hydroxy phenyl) methane, 1,1,2,2-four (4-hydroxy phenyl) ethane, phenol novolac resin, ortho-cresol novolac resin, naphthol novolac varnish resin, polyvinylphenol etc. are the phenols more than 3 yuan of representative.In addition, also have by phenol, aphthols, dihydroxyphenyl propane, Bisphenol F, bisphenol S, fluorenes bis-phenol, 4,4 '-xenol, 2, the polynary phenoloid that the condensing agents such as 2 yuan of phenols such as 2 '-xenol, quinhydrones, Resorcinol, naphthalenediol and formaldehyde, acetaldehyde, phenyl aldehyde, p-Hydroxybenzaldehyde, p-xylylene dichloro, two (chloromethyl) biphenyl, two (chloromethyl) naphthalene are synthetic etc.
As amine, have 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino-diphenyl propane, 4, the aliphatics amines such as the aromatic amines such as 4 '-diamino diphenyl sulfone, mphenylenediamine, p dimethylamine, quadrol, hexamethylene-diamine, diethylenetriamine, Triethylenetetramine (TETA).
In above-mentioned composition, the one kind or two or more mixing of these solidifying agent can be used.
As the epoxy resin that uses in above-mentioned composition, have from 1 molecule in the epoxy resin of 2 above epoxy group(ing) and select.can enumerate for example dihydroxyphenyl propane, Bisphenol F, 3, 3', 5, 5 '-tetramethyl--Bisphenol F, bisphenol S, the fluorenes bis-phenol, 2, the 2'-xenol, 3, 3', 5, 5 '-tetramethyl--4, 4 '-dihydroxybiphenyl phenol, Resorcinol, the epoxide of the dihydric phenols such as naphthalenediol class, three-(4-hydroxy phenyl) methane, 1, 1, 2, 2-four (4-hydroxy phenyl) ethane, the phenol novolac resin, the epoxide of the phenols more than 3 yuan such as ortho-cresol novolac resin, the epoxide of the cocondensation resin of dicyclopentadiene and phenols, epoxide by the synthetic phenol aralkyl resene such as phenol and terephthaldehyde's base dichloro, epoxide by the synthetic biphenyl aralkyl-type phenol resins such as phenol and two (chloromethyl) biphenyl, by the epoxide of the synthetic naphthols aralkyl resene such as aphthols and terephthaldehyde base dichloro etc.These epoxy resin can use one kind or two or more mixing.
Above-mentioned 1) and 3) the situation of composition under, comprise StPNE as the composition of necessity.In this composition epoxy resin, as the epoxy resin composition, can coordinate the epoxy resin of other kinds beyond StPNE.As the epoxy resin of this situation, the common epoxy resin that has 2 above epoxy group(ing) in molecule all can use.If for example, dihydroxyphenyl propane, bisphenol S, fluorenes bis-phenol, 4 are arranged, 4 '-xenol, 2,2 yuan of phenols such as 2 '-xenol, quinhydrones, Resorcinol, perhaps three-(4-hydroxy phenyl) methane, 1,1, phenols, the phenol more than 3 yuan such as 2,2-four (4-hydroxy phenyl) ethane, phenol novolac resin, ortho-cresol novolac resin are that aralkyl resene, biphenyl aralkyl resene, naphthols are aralkyl resene or by the derivative glycidyl ether compound of the halogenated bisphenol classes such as tetrabromo-bisphenol etc.These epoxy resin can use one kind or two or more mixing.And under the situation of StPNE of the present invention as the composition of neccessary composition, the use level of StPNE can be 5～100% in epoxy resin is all, be preferably 60～100% scope.
In composition epoxy resin of the present invention, can suitably coordinate the oligopolymer such as polyester, polymeric amide, polyimide, polyethers, urethane, petroleum resin, indene resin, indenes coumarone resin, phenoxy resin or macromolecular compound as other properties-correcting agent etc.Addition usually with respect to epoxy resin 100 weight parts, is the scope of 2～30 weight parts.
In addition, in composition epoxy resin of the present invention, can coordinate the additives such as inorganic filler, pigment, fire retardant, thixotropy imparting agent, coupling agent, fluidity improving agent.As inorganic filler, can enumerate SiO 2 powder, alumina powder, glass powder or mica, talcum, calcium carbonate, aluminum oxide, the hydrated aluminum oxides etc. such as fused silica such as spherical or broken shape, crystalline silica, the preferred use level that is used for the situation of semiconductor-encapsulating material is more than 70 % by weight, more preferably more than 80 % by weight.
As pigment, filler pigment, flakey pigment of organic system or inorganic system etc. are arranged.As the thixotropy imparting agent, can enumerate silicon system, Castor oil system, aliphatic amide wax, oxidized polyethlene wax, organobentonite system etc.
In addition, in composition epoxy resin of the present invention, can use as required curing catalyst.If for example, amine, imidazoles, organic phosphine class, Lewis acid etc. are arranged, particularly, have 1,8-diazabicyclo (5,4,0) organic phosphine class, the tetraphenyls such as the imidazoles such as tertiary amine, glyoxal ethyline, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecyl imidazoles, tributylphosphine, methyldiphenyl base phosphine, triphenylphosphine, diphenylphosphine, Phenylphosphine such as undecylene-7, triethylenediamine, benzyl dimethyl amine, trolamine, dimethylaminoethanol, three (dimethylaminomethyl) phenol
Tetraphenyl borate salts, tetraphenyl
Ethyl triphenyl borate, the tetrabutyl
Tetrabutyl borates etc. four replace
The tetraphenyl boron salt such as four substituted boracic acid salt, 2-ethyl-4-methylimidazole tetraphenyl borate salts, N-methylmorpholine tetraphenyl borate salts etc.As addition, usually with respect to epoxy resin 100 weight parts, be the scope of 0.2-5 weight part.
In addition, as required, can use the lubricants such as low-stress agent, calcium stearate such as the fire retardants such as the tinting materials such as the coupling agents such as releasing agent, γ-glycidoxypropyltrimewasxysilane, carbon black, ANTIMONY TRIOXIDE SB 203 99.8 PCT, the silicone oil such as carnauba wax, OP wax etc. in resin combination of the present invention.
Composition epoxy resin of the present invention becomes with after the varnish state of organic solvent dissolution, after being impregnated in the fibrous materials such as polyester non-woven fabric such as woven fiber glass, aramid nonwoven fabric, liquid crystalline polymers, carries out solvent to remove, and makes the preimpregnation blank.In addition, sometimes, by being coated with, can make sandwich on the flaps such as Copper Foil, stainless steel foil, polyimide film, polyester film.
If composition epoxy resin of the present invention is heating and curing, can make epoxy resin cured product, this cured article becomes the cured article in aspect excellences such as solidified nature, flame retardant resistance, agent of low hygroscopicity, low elasticities.This cured article can obtain by composition epoxy resin being adopted the methods such as casting, compressed moulding, transfer molding carry out forming process.The temperature of this moment is generally the scope of 120～220 ℃.
Embodiment
By the following examples the present invention is described more specifically.
(synthesizing of polyhydroxy resin)
Embodiment 1
Pack in 4 mouthfuls of flasks of 1L as novolac resin (the clear and polymer system of polyol composition; Melt viscosity 0.08Pas under 67 ℃, 150 ℃ of BRG-555, hydroxyl equivalent 105g/eq., softening temperatures) 105g, toluene 5.3g, as the tosic acid 0.078g(300ppm of acid catalyst), be warmed up to 100 ℃.Next, stir under 100 ℃ on the limit, the limit with 3 hours with vinylbenzene 156g(1.5 mole) splash into and make its reaction.And then, after 2 hours, add 30%Na in reaction under 100 ℃
2CO
30.071g, neutralize.Next, be dissolved in MIBK485g, carried out 5 washings under 80 ℃.Then, after the MIBK decompression is heated up in a steamer, obtained polyhydroxy resin 250g.Its hydroxyl equivalent is 261g/eq., and softening temperature is that the melt viscosity of 82 ℃, 150 ℃ is 0.21Pas.This resin is called StPN-A.At gel permeation chromatography (GPC; RI) in mensuration, the area % of monohydroxy compound (2) is 1.2%.The GPC of StPN-A is illustrated in Fig. 1.
Synthesis example 1
Pack in 4 mouthfuls of flasks of 1L as novolac resin (the clear and polymer system of polyol composition; BRG-555) 105g, toluene 5.3g, as the tosic acid 0.131g(500ppm of acid catalyst), be warmed up to 150 ℃.Next, stir under 150 ℃ on the limit, and the limit splashed into vinylbenzene 156g(1.5 mole with 3 hours), make its reaction.And then, after 2 hours, add 30%Na in reaction under 150 ℃
2CO
30.118g, neutralize.Next, be dissolved in MIBK485g, carried out 5 washings under 80 ℃.Then, after the MIBK decompression is heated up in a steamer, obtained polyhydroxy resin 247g.Its softening temperature is 80 ℃, and the melt viscosity under 150 ℃ is 0.19Pas, and hydroxyl equivalent is 261g/eq..This resin is called StPN-B.Gel permeation chromatography (GPC; RI) in mensuration, the area % of monohydroxy compound (2) is 5.2%.In addition, the area % of styrene dimer is 0.8%.The GPC of StPN-B is illustrated in Fig. 2.In Fig. 1～2, A represents the peak of monohydroxy compound (2), and B represents the peak of styrene dimer.
(synthesizing of epoxy resin)
Embodiment 2
StPN-A150g, the Epicholorohydrin 319g, the diglyme 48g that pack in the removable flask of four-hole and obtain in embodiment 1, stirring and dissolving.After the dissolving, remain on 65 ℃ under the decompression of 130mmHg equably, with splashing into 48% aqueous sodium hydroxide solution 47.9g in 4 hours, splash at this and middlely with separator tank, the water that backflow distillates is separated with Epicholorohydrin, Epicholorohydrin is turned back in reaction vessel, water is removed outside system, react.After reaction finishes, by filtering, the salt that generates is removed, and then after washing, Epicholorohydrin is heated up in a steamer, obtained epoxy resin 172g(StPNE-A).The epoxy equivalent (weight) of the resin that obtains is 325g/eq., and softening temperature is 60 ℃, and the melt viscosity under 150 ℃ is 0.19Pas.At gel permeation chromatography (GPC; RI) in mensuration, the area % of mono-epoxy compounds (5) is 1.1%.The GPC of StPNE-A is illustrated in Fig. 3.
Synthesis example 2
The StPN-B150g that obtains in the synthesis example 1 of packing in the removable flask of four-hole, Epicholorohydrin 319g, diglyme 48g, stirring and dissolving.After uniform dissolution, remain on 65 ℃ under the decompression of 130mmHg, with splashing into 48% aqueous sodium hydroxide solution 47.9g in 4 hours, drip at this and middlely with separator tank, the water that backflow distillates is separated with Epicholorohydrin, Epicholorohydrin is turned back in reaction vessel, water is removed outside system, react.After reaction finishes, by filtering, the salt that generates is removed, and then after washing, Epicholorohydrin is heated up in a steamer, obtained epoxy resin 170g(StPNE-B).The epoxy equivalent (weight) of the resin that obtains is 330g/eq., and softening temperature is 57 ℃, and the melt viscosity under 150 ℃ is 0.18Pas.Gel permeation chromatography (GPC; RI) in mensuration, the area % of mono-epoxy compounds (5) is 5.0%.In addition, the area % of styrene dimer is 0.6%.The GPC of StPNE-B is illustrated in Fig. 4.In Fig. 3～4, A represents the peak of mono-epoxy compounds (5), and B represents the peak of styrene dimer.
Embodiment 3 and comparative example 1,2
As the epoxy resin composition, use ortho-cresol novolac type epoxy resin (OCNE; 65 ℃ of epoxy equivalent (weight) 200, softening temperatures), as solidifying agent, the STPN-B that obtains in the STPN-A that obtains, synthesis example 1, used novolac resin (PN in embodiment 1; PSM-4261(group's honorization length of schooling); 82 ℃ of OH equivalent 103, softening temperatures).Will be as the silicon-dioxide (median size 18 μ m) of weighting agent, undertaken mixingly by the cooperation shown in table 1 as the triphenylphosphine of curing catalyst and other additives, obtained composition epoxy resin.Use this composition epoxy resin, at 175 ℃ of compacted unders, carry out 12 hours after fixing under 175 ℃, after having obtained the cured article test film, supply in various physical property measurements.The details of physical property measurement below is shown, shows the result in table 2.
1) molecular weight distribution of polyhydroxy resin, epoxy resin
Use GPC determinator (Japanese ウ ォ ー タ ー ズ system, 515A type GPC), for post, use TSKgel SuperHZ2000(Dong ソ ー system) 3 pieces, TSKgel SuperHZ4000(Dong ソ ー system) 1 piece, making detector is RI, making solvent is tetrahydrofuran (THF), measures under 40 ℃ of flow 0.6ml/ minutes, column temperature.
2) softening temperature
Use automatic softening temperature device (bright peak society system, ASP-M4SP), according to JIS-K-2207, adopt ring and ball method to measure.
3) melt viscosity
Use BROOKFIELD system, CAP2000H type rotational viscosimeter, measure under 150 ℃.
4) mensuration of hydroxyl equivalent
Use the potential difference titration apparatus, Isosorbide-5-Nitrae-dioxan is used for solvent, carry out acetylize with the 1.5mol/L Acetyl Chloride 98Min., water decomposes superfluous Acetyl Chloride 98Min., uses the titration of 0.5mol/L-potassium hydroxide.
5) mensuration of epoxy equivalent (weight)
Use the potential difference titration apparatus, use methylethylketone as solvent, add the tetraethylammonium bromide acetum, adopt the potential difference titration apparatus to use 0.1mol/L perchloric acid-acetum to measure.
6) gel time
Add composition epoxy resin being heated on the plate of gelation trier (day new science (strain) system) of 175 ℃, use the fluoro-resin rod, stir with the speed that turns a second 2, investigate until composition epoxy resin solidifies needed gelation time.
7) linear expansivity (CTE, second-order transition temperature (Tg))
Adopt セ イ コ ー イ Application ス Star Le TMA120C type processed heat engine tool determinator, obtain Tg under the condition of 10 ℃/minute of heat-up rates, the CTE that α 1(Tg is following) obtained by the mean value of the scopes of 30～50 ℃, and the above CTE of α 2(Tg) obtained by the mean value of the scope of 20 ℃～40 ℃ of Tg プ ラ ス.
8) flexural strength and the elasticity of flexure
According to JISK6911, adopt 3 bend test methods to measure at normal temperatures.
9) bonding strength
By adopting compacting shape machine in the forming composition of 175 ℃ of compacted under 25mm * 12.5mm * 0.5mm between 2 copper coins, after having carried out 12 hours after fixing under 180 ℃, obtain tensile shear strength and estimate.
10) water-intake rate
25 ℃, the condition of relative humidity 50% as standard state, are the weight rate of moisture absorption after 100 hours under 85 ℃, the condition of relative humidity 85%.
11) flame retardant resistance
The test film that moulding is thick 1/16 inch is estimated according to the UL94V-0 standard, with representing combustion time of the total of 5 test films.
[table 1]
[table 2]
Embodiment 4,5 and comparative example 3～5
As the epoxy resin composition, the StPNE-B that obtains in the StPNE-A that obtains, synthesis example 2, use ortho-cresol novolac type epoxy resin (OCNE in embodiment 2; 65 ℃ of epoxy equivalent (weight) 200, softening temperatures), as curing agent component, used phenol aralkyl resin (PA; MEH-7800SS(is bright and change into system), 67 ℃ of OH equivalents 175, softening temperature) or novolac resin (PN; PSM-4261(group's honorization length of schooling), OH equivalent 103, softening temperature are 82 ℃).In addition, as weighting agent, use spherical silicon dioxide (median size 18 μ m), as curing catalyst, used triphenylphosphine.Obtained composition epoxy resin with the cooperation shown in table 3.Weight part during numeric representation in table coordinates.
Use this composition epoxy resin at 175 ℃ of compacted unders, and then carry out 12 hours after fixing under 175 ℃, after having obtained the cured article test film, supply in various physical property measurements.Show the result in table 4.
[table 3]
[table 4]
The possibility of the utilization on industry
Epoxy resin of the present invention and polyhydroxy resin, be applied in the situation of composition epoxy resin, solidified nature is excellent, gives simultaneously also excellent cured article of flame retardant resistance, wet fastness and low elasticity, can be adapted at using in the purposes such as sealing, circuit base material of electrical and electronic parts class.Especially, solidified nature and excellent in flame retardance are guaranteed excellent formability, do not need to use the fire retardant with carrying capacity of environment or make its minimizing simultaneously.
Claims (9)
1. polyhydroxy resin, is characterized in that, in by the polyhydroxy resin shown in following general formula (1), used by gel permeation chromatography (GPC by the monohydroxy compound shown in following general formula (2); Area % when RI) detecting represents, is below 3%,
Wherein, R
1The alkyl of expression hydrogen or carbonatoms 1～6, R
2Expression is by the substituting group shown in formula (a), and n represents 0～20 number; In addition, p represents 0.1～2.5 number, R
3The alkyl of expression hydrogen or carbonatoms 1～6;
Wherein, p represents 0～3 number, R
1And R
3The alkyl of expression hydrogen or carbonatoms 1～6.
2. the manufacture method of polyhydroxy resin, it is characterized in that, under the existence of the acid catalyst of 10～400wtppm, make by the polyol shown in following general formula (3) and styrenic reaction under 40～120 ℃ of temperature of reaction, make by the substituting group shown in formula (a) and replace phenyl ring to polyol
Wherein, R
1And R
3The alkyl of expression hydrogen atom or carbonatoms 1～6, n represents 1～20 number.
3. the manufacture method of polyhydroxy resin claimed in claim 2, is characterized in that, with respect to by 1 mole of the hydroxyl of the polyol shown in general formula (3), makes the styrenic reaction of 0.1～1.0 mole.
4. composition epoxy resin, is characterized in that, in the composition epoxy resin that comprises epoxy resin and solidifying agent, as part or all of solidifying agent, take polyhydroxy resin claimed in claim 1 as neccessary composition.
5. epoxy resin cured product, is characterized in that, composition epoxy resin claimed in claim 4 solidified form.
6. epoxy resin, is characterized in that, in by the epoxy resin shown in following general formula (4), the area % when being detected with gel permeation chromatography by the monocycle epoxy resins shown in following general formula (5) represents, is below 3%,
Wherein, G represents glycidyl, R
1The alkyl of expression hydrogen or carbonatoms 1～6, R
2Expression is by the substituting group shown in formula (a), and n represents 0～20 number; In addition, p represents 0.1～2.5 number, R
3The alkyl of expression hydrogen or carbonatoms 1～6;
Wherein, G represents glycidyl, and p represents 0～3 number, R
1And R
3The alkyl of expression hydrogen or carbonatoms 1～6.
7. the manufacture method of epoxy resin, is characterized in that, makes the reaction of polyhydroxy resin claimed in claim 1 and Epicholorohydrin, makes the hydroxyl of polyhydroxy resin become glycidyl ether.
8. composition epoxy resin, it is by coordinating epoxy resin claimed in claim 6 to form as neccessary composition in the composition epoxy resin that comprises epoxy resin and solidifying agent.
9. epoxy resin cured product, it forms by composition epoxy resin claimed in claim 8 is solidified.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
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| JP2010-214971 | 2010-09-27 | ||
| JP2010214971 | 2010-09-27 | ||
| PCT/JP2011/070804 WO2012043213A1 (en) | 2010-09-27 | 2011-09-13 | Polyhydric hydroxy resin, epoxy resin, production method therefor, epoxy resin composition and cured product thereof |
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| CN103140523A true CN103140523A (en) | 2013-06-05 |
| CN103140523B CN103140523B (en) | 2014-07-23 |
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| JP (3) | JP5324712B2 (en) |
| KR (1) | KR101410919B1 (en) |
| CN (1) | CN103140523B (en) |
| MY (1) | MY157418A (en) |
| SG (1) | SG188247A1 (en) |
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| CN108474991A (en) * | 2016-01-17 | 2018-08-31 | 伊英克加利福尼亚有限责任公司 | Polyhydroxy composition for encapsulated electrophoretic display |
| TWI779446B (en) * | 2020-12-30 | 2022-10-01 | 聯茂電子股份有限公司 | LOW EXPANSION COEFFICIENT, LOW Df, HIGH RIGIDITY, HALOGEN-FREE RESIN COMPOSITION, LAMINATES AND PRINTED CIRCUIT BOARDS |
| CN115141331A (en) * | 2021-03-29 | 2022-10-04 | 长春人造树脂厂股份有限公司 | Polyhydric phenol resin, glycidyl ether of polyhydric phenol resin and application thereof |
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| JP6183918B2 (en) * | 2012-06-12 | 2017-08-23 | 新日鉄住金化学株式会社 | Polyhydroxy polyether resin, method for producing polyhydroxy polyether resin, resin composition containing polyhydroxy polyether resin, and cured product obtained therefrom |
| TWI631173B (en) * | 2012-10-11 | 2018-08-01 | 新日鐵住金化學股份有限公司 | Epoxy resin composition and hardened material |
| JP6073720B2 (en) * | 2013-03-21 | 2017-02-01 | 新日鉄住金化学株式会社 | Alkali development type photosensitive resin composition and cured product thereof |
| CN104870514B (en) | 2013-11-25 | 2019-10-01 | 锦湖石油化学株式会社 | Suitable for the curing agent of epoxy resin or the styrenated phenol of plasticizer |
| JP6406847B2 (en) | 2014-03-26 | 2018-10-17 | 新日鉄住金化学株式会社 | Modified polyvalent hydroxy resin, epoxy resin, epoxy resin composition and cured product thereof |
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| CN108474991A (en) * | 2016-01-17 | 2018-08-31 | 伊英克加利福尼亚有限责任公司 | Polyhydroxy composition for encapsulated electrophoretic display |
| CN108474991B (en) * | 2016-01-17 | 2021-04-20 | 伊英克加利福尼亚有限责任公司 | Polyhydroxy compositions for sealing electrophoretic displays |
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| JP2015083704A (en) | 2015-04-30 |
| JP5931234B2 (en) | 2016-06-08 |
| JPWO2012043213A1 (en) | 2014-02-06 |
| TWI522397B (en) | 2016-02-21 |
| KR20130099116A (en) | 2013-09-05 |
| MY157418A (en) | 2016-06-15 |
| CN103140523B (en) | 2014-07-23 |
| WO2012043213A1 (en) | 2012-04-05 |
| KR101410919B1 (en) | 2014-06-24 |
| JP2013237859A (en) | 2013-11-28 |
| TW201229097A (en) | 2012-07-16 |
| JP6073754B2 (en) | 2017-02-01 |
| SG188247A1 (en) | 2013-04-30 |
| JP5324712B2 (en) | 2013-10-23 |
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Effective date of registration: 20191211 Address after: No.13-1, No.1, No.1, No Patentee after: Nippon Iron Chemical Materials Co., Ltd. Address before: Tokyo, Japan Patentee before: Nippon Steel Chemical Co. |