CN104334597A - Polyvalent hydroxy resin, epoxy resin, method for producing same, epoxy resin composition and cured product thereof - Google Patents
Polyvalent hydroxy resin, epoxy resin, method for producing same, epoxy resin composition and cured product thereof Download PDFInfo
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- CN104334597A CN104334597A CN201380010483.7A CN201380010483A CN104334597A CN 104334597 A CN104334597 A CN 104334597A CN 201380010483 A CN201380010483 A CN 201380010483A CN 104334597 A CN104334597 A CN 104334597A
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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
- C08G59/02—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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Abstract
Provided are an epoxy resin, a polyvalent hydroxy resin and a composition thereof which have excellent curability, which provide cured products with excellent mechanical strength, flame resistance, humidity resistance, low elasticity, etc., and which are suitable for applications such as encapsulation of electronic components, circuit board material, etc. This polyvalent hydroxy resin is an aralkyl denatured polyvalent hydroxy resin which is obtained by reacting a narrow disperse polyvalent hydroxy compound with an aralkylating agent of styrenes, etc., the narrow disperse polyvalent hydroxy compound comprising 15% or less of n=1 component, and 50% or more of a total of n=2 and n=3 components, and having Mw/Mn of 1.2 or less. In addition, the present invention is an epoxy resin obtained by reacting the aralkyl denatured polyvalent hydroxy resin with epichlorohydrin. Furthermore, the present invention is an epoxy resin composition which contains, as an essential component, the aralkyl denatured polyvalent hydroxy resin or the epoxy resin.
Description
Technical field
The present invention relates to a kind of solidified nature excellence and give the epoxy resin of the also excellent cured article of physical strength, flame retardant resistance, wet fastness, low elasticity, the multi-hydroxy resin being suitable as its intermediate, their manufacture method, the composition epoxy resin using them and its cured article, being suitable for the insulating material etc. in the electric and electronic such as semiconductor-encapsulating material, printed circuit board (PCB) field.
Background technology
Epoxy resin is industrially used in purposes widely, and it requires performance High Level all the more in recent years.Such as, semiconductor-encapsulating material is had in the representative field of resin combination taking epoxy resin as host, along with the raising of the integrated level of semiconductor element, package dimension is towards big area, slimming, mounting means also shifts towards surface mounting simultaneously, wishes the material developing scolding tin excellent heat resistance.Therefore, as sealing material, except low moisture absorption, be also strongly required the raising of the cementability in the foreign material such as lead frame, chip interface, adaptation.For circuit base material too, improve from the view point of scolding tin thermotolerance, except the raising of agent of low hygroscopicity, high heat resistance, high adhesion, reduce from the view point of dissipation loss, also wish the material of exploitation low-dielectric excellence.In order to correspond to these requirements, have studied epoxy resin and the solidifying agent of various innovative construction.In addition, recently, reduce from the view point of carrying capacity of environment, have the trend getting rid of halogenated flame retardant, the epoxy resin requiring flame retardant resistance more excellent and solidifying agent.
Therefore, based on above-mentioned background, have studied various epoxy resin and epoxy curing agent.As an example of epoxy curing agent, there will be a known naphthalene system resin, illustrated in patent documentation 1 and naphthols aralkyl resin is applied to semiconductor-encapsulating material, described the excellences such as flame retardant resistance, agent of low hygroscopicity, low heat expansion property.In addition, propose there is the solidifying agent with biphenyl structure in patent documentation 2, and describe to flame retardant resistance raising effectively.But naphthols aralkyl resin, biphenyl aralkyl resin all have the shortcoming of solidified nature difference, in addition, the effect for flame retardant resistance raising is sometimes also insufficient.
On the other hand, about epoxy resin, also not yet know the epoxy resin meeting these and require.Such as, well-known bisphenol-type epoxy resin, owing to being liquid at normal temperatures, operability is excellent, with mixing easily of solidifying agent, additive etc., is therefore widely used, but has problems in thermotolerance, wet fastness this point.In addition, as the epoxy resin improving thermotolerance, there will be a known o-cresol phenolic epoxy varnish, but about flame retardant resistance, for insufficient.
As the countermeasure making flame retardant resistance improve for not using halogenated flame retardant, disclose the method for the fire retardant adding phosphoric acid ester system.But in the method for fire retardant using phosphoric acid ester system, wet fastness is insufficient.In addition, under high temperature, many wet environment, there is the problem that phosphoric acid ester is hydrolyzed, the reliability as insulating material is reduced.
As not containing phosphorus atom, halogen atom and the epoxy resin that makes flame retardant resistance improve, disclose in patent documentation 2 and 3 and will have aralkyl-type epoxy resin that biphenyl constructs and be applied to the example of semiconductor-encapsulating material.The example using the aralkyl-type epoxy resin with naphthalene structure is disclosed in patent documentation 4.But these epoxy resin are all insufficient in the arbitrary middle performance of flame retardant resistance, wet fastness or thermotolerance.
As the example of raising being conceived to thermotolerance, wet fastness, crack resistance, disclose Benzylation polyphenol and epoxy resin thereof in patent documentation 5, but these materials are not conceived to flame retardant resistance.In addition, disclose the manufacture method of phenylethene modified phenolic varnish (ノ ボ ラ ッ Network) in patent documentation 6, but be not the manufacture method obtaining as composition epoxy resin gazing at.
And then, as the example of composition epoxy resin of raising being conceived to wet fastness, low-stress, disclose phenylethene modified phenol resol resins in patent documentation 7 and 8 and use the composition epoxy resin of this epoxy resin, but they are not also to the example that the molecular weight distribution of styrenated phenol phenolic varnish and epoxy resin studies in great detail.Be explained, molecular weight distribution (dispersion) represents with Mw/Mn.
On the other hand, as the example of raising being conceived to flame retardant resistance, disclose phenylethene modified phenol resol resins in patent documentation 9 and use the composition epoxy resin of this epoxy resin.At this, being conceived to phenylethene modified amount, using the resin adjusting hydroxyl equivalent or epoxy equivalent (weight) by increasing modification amount higher.Thinking in the cured article using such resin, by making the containing ratio of the aliphatic character being derived from epoxy group(ing) relatively reduce, the flame retardant resistance of height can be manifested.But, at this also not to the example that the molecular weight distribution of multi-hydroxy resin and epoxy resin studies in great detail.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2005-344081 publication
Patent documentation 2: Japanese Unexamined Patent Publication 11-140166 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2000-129092 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2004-59792 publication
Patent documentation 5: Japanese Unexamined Patent Publication 8-120039 publication
Patent documentation 6: Japanese Laid-Open Patent Publication 48-52895 publication
Patent documentation 7: Japanese Unexamined Patent Publication 5-132544 publication
Patent documentation 8: Japanese Unexamined Patent Publication 5-140265 publication
Patent documentation 9: Japanese Unexamined Patent Publication 2010-235819 publication
Summary of the invention
The object of the invention is to, there is provided a kind of stacked, be shaped, casting, in the purposes such as bonding solidified nature and mechanical properties excellent and there is the epoxy resin of the also excellent performance such as flame retardant resistance, wet fastness, low elasticity, there is provided a kind of there is excellent solidified nature and mechanical characteristics and give the sealing to electrical/electronic part class, circuit base material etc. of the also excellent cured article such as flame retardant resistance, wet fastness, low elasticity useful composition epoxy resin, and its cured article is provided.
Namely, the present invention relates to a kind of aralkyl modified multi-hydroxy resin, it is characterized in that, it reacts for making the multi-hydroxy compound shown in following general formula (1) and aralkyl agent, on the phenyl ring making the substituting group being derived from aralkyl agent shown in formula (a) be replaced in multi-hydroxy compound and the aralkyl modified multi-hydroxy resin obtained, as the multi-hydroxy compound of general formula (1), use in the area % n=1 composition measured with gel permeation chromatography (GPC) as less than 15%, n=2 and n=3 composition add up to more than 50%, Mw/Mn be less than 1.2 narrow dispersion multi-hydroxy compound obtain.
(at this, R
1and R
2represent the alkyl of hydrogen atom or carbon number 1 ~ 6, R
3and R4 represents the alkyl of hydrogen atom or carbon number 1 ~ 6, n represents the number of 1 ~ 5)
Another way of the present invention is a kind of phenylethene modified multi-hydroxy resin, it is characterized in that, it reacts for making the multi-hydroxy compound shown in above-mentioned general formula (1) and styrenic, make to be derived from phenyl ring that cinnamic substituting group is replaced in multi-hydroxy compound and the phenylethene modified multi-hydroxy resin obtained shown in formula (a2), as the multi-hydroxy compound of general formula (1), use in the area % n=l composition of GPC mensuration as less than 15%, n=2 and n=3 composition add up to more than 50%, Mw/Mn be less than 1.2 narrow dispersion multi-hydroxy compound obtain.
(at this, R
2with formula (a) synonym).
Another way of the present invention is a kind of manufacture method of aralkyl modified multi-hydroxy resin, it is characterized in that, in manufacture, the aralkyl agent shown in the multi-hydroxy compound shown in above-mentioned general formula (1) and following formula (b1) or (b2) is reacted, on the phenyl ring making the substituting group being derived from aralkyl agent shown in above-mentioned formula (a) be replaced in multi-hydroxy compound and the aralkyl modified multi-hydroxy resin obtained time, as the multi-hydroxy compound of general formula (1), use in the area % n=l composition of GPC mensuration as less than 15%, n=2 and n=3 composition add up to more than 50%, Mw/Mn is the narrow dispersion multi-hydroxy compound of less than 1.2, and make above-mentioned reaction under the existence of the acid catalyst of 10 ~ 1000ppm, react temperature of reaction 40 ~ 120 DEG C.
(at this, R
2represent the alkyl of hydrogen atom or carbon number 1 ~ 6, R
3and R
4represent the alkyl of hydrogen atom or carbon number 1 ~ 6, X represents halogen, OH or OR
5, R
5represent the alkyl of carbon number 1 ~ 6).
In the manufacture method of above-mentioned aralkyl modified multi-hydroxy resin, be preferably the hydroxyl 1 mole relative to multi-hydroxy compound, make aralkyl agent 0.1 ~ 1.5 molar reactive, or aralkyl agent be vinylbenzene.
Another way of the present invention is a kind of composition epoxy resin and cured article thereof, the feature of described composition epoxy resin is, comprise epoxy resin and solidifying agent, as part or all of solidifying agent, form as neccessary composition using above-mentioned aralkyl modified multi-hydroxy resin.
Another way of the present invention is a kind of epoxy resin, it is characterized in that, makes above-mentioned aralkyl modified multi-hydroxy resin and epichlorohydrin reaction and obtains.In addition, another way is a kind of manufacture method of epoxy resin, it is characterized in that, makes above-mentioned aralkyl modified multi-hydroxy resin and epichlorohydrin reaction, and the hydroxyl of aralkyl modified multi-hydroxy resin is formed glycidyl ether.
Another way of the present invention is a kind of composition epoxy resin and epoxy resin cured product thereof, and described composition epoxy resin contains epoxy resin and solidifying agent, wherein, carries out cooperation form using above-mentioned epoxy resin as neccessary composition.
Accompanying drawing explanation
Fig. 1 is the GPC figure of multi-hydroxy compd A.
Fig. 2 is the GPC figure of multi-hydroxy compd B.
Fig. 3 is the GPC figure of multi-hydroxy Compound C.
Fig. 4 is the GPC figure of modified multicomponent hydroxy resin A.
Fig. 5 is the GPC figure of modified multicomponent hydroxy resin B.
Fig. 6 is the GPC figure of modified multicomponent hydroxy resin C.
Fig. 7 is the GPC figure of modified multicomponent hydroxy resin D.
Fig. 8 is the GPC figure of epoxy resin A.
Fig. 9 is the GPC figure of epoxy resin B.
Figure 10 is the GPC figure of epoxy resin C.
Figure 11 is the GPC figure of epoxy resin D.
Embodiment
In epoxy resin cured product, to think due to the reaction of epoxy group(ing) and hydroxyl and the hydroxypropyl generated easily burns, but by improving hydroxyl equivalent to multi-hydroxy compound addition aralkyl, being derived from the aliphatic carbon rate step-down of the inflammable constituent of epoxy group(ing), the flame retardant resistance of height can be manifested.In addition, by being imbued with the addition of the aralkyl of aromatic series, the aromatic series of multi-hydroxy resin improves further, except flame retardant resistance, also effective to the raising of wet fastness.
But, on the other hand, the tendency that the method bringing physical property to improve by the modification ratio of increase aralkyl has the solidified nature caused because of the increase of steric hindrance to reduce, the physical strength of cured article is reduced.Therefore, by controlling the molecular weight distribution of the multi-hydroxy compound of substrate, in the aralkyl modified ratio not damaging solidified nature, physical strength, and then the aralkyl modified multi-hydroxy resin that solidified nature, mechanical strength and flame retardant resistance, wet fastness and low elasticity are also excellent and epoxy resin are found.
The multi-hydroxy compound used in the present invention is the narrow dispersion multi-hydroxy compound shown in general formula (1), therefore, also referred to as multi-hydroxy compound (1) or narrow dispersion multi-hydroxy compound.In addition, owing to being also a kind of novolac resin, so also referred to as phenol novolacs.
When employing aralkyl modified multi-hydroxy resin using narrow dispersion multi-hydroxy compound as substrate and epoxy resin, the composition epoxy resin that solidified nature, physical strength and flame retardant resistance etc. are excellent can be obtained.That is, when the ratio of the aralkyl modified thing of n=1 (the 2 officials' energy) composition for multi-hydroxy compound increases, due to the increase of steric hindrance, thus the tendency that solidified nature reduces, the physical strength of cured article also reduces is had.On the other hand, when being used as the much higher first oxy-compound of the ratio of the n=2 of more multifunctional composition (3 officials can) and n=3 (4 officials can) composition, even if due to when carrying out aralkyl modified, the impact of steric hindrance also relatively reduces, thus can obtain the cured article of solidified nature, mechanical strength.In addition, when multifunctional composition increases, because the cross-linking density of cured article increases, thus become the more excellent cured article of thermostability, the tendency that display flame retardant resistance is also excellent.But when n=4 (5 officials' energy) above composition increases, molecular weight uprises, and therefore, there is the tendency of mobility, shaping processability difference.
Therefore, these materials are used can to obtain the excellent composition epoxy resin such as solidified nature, physical strength and flame retardant resistance, especially epoxy resin composition for encapsulating semiconductor.That is, manifest the excellent solidified nature of these compositions, manifest the physical property of physical strength, high flame retardant, wet fastness, low elasticity excellence simultaneously, use this material can obtain the sealing, circuit base material etc. of high electric, the electronic component class of reliability.
First, aralkyl modified multi-hydroxy resin (StPN) of the present invention is described.Aralkyl modified multi-hydroxy resin of the present invention can by making in the multi-hydroxy compound shown in general formula (1), with gel permeation chromatography (GPC; Area % when RI) detecting counts that n=1 composition is less than 15%, n=2 and n=3 composition add up to more than 50%, Mw/Mn be less than 1.2 narrow dispersion multi-hydroxy compound and aralkyl agent react and obtain.
Aralkyl modified multi-hydroxy resin of the present invention being called StPN, being called multi-hydroxy compound or narrow dispersion multi-hydroxy compound by order to obtain the multi-hydroxy compound shown in general formula (1) that StPN uses.The aralkyl of this aralkyl modified multi-hydroxy resin refers to the group shown in formula (a).The aralkyl agent used to obtain StPN refers to the compound shown in formula (c1) or (c2).In addition, sometimes represent aralkyl agent with vinylbenzene, and sometimes aralkyl modified multi-hydroxy resin is called phenylethene modified multi-hydroxy resin.
As the scope of the molecular weight distribution of the narrow dispersion multi-hydroxy compound used in the present invention, the containing ratio of n=l composition is less than 15%, is preferably the scope of less than 10%.In addition, the scope of the containing ratio of n=2 and n=3 composition is more than 50%, is more preferably more than 60%, more preferably the scope of more than 70%.By reducing the containing ratio of n=l composition, the physical property such as solidified nature, physical strength, flame retardant resistance can be improved.And then, dispersity (Mw/Mn) range preferably from less than 1.2, be more preferably the scope of less than 1.1.When it is more than 1.2, there is the tendency of the poor properties such as solidified nature, physical strength.Be explained, because GPC area % and wt% is roughly proportional, therefore GPC area % can be considered wt%.
Remove low molecular weight compositions to obtain in the thick multi-hydroxy compound that the narrow dispersion multi-hydroxy compound used in the present invention can be obtained by the mol ratio from adjustment phenols and aldehydes.
The mol ratio of phenols and aldehydes represents by the mol ratio of aldehydes relative to phenols 1 mole, and the scope with 0.1 ~ 0.9 manufactures, in mol ratio hour, more generate n=l ~ 3 composition, when mol ratio is large, more generate the high molecular weight components of more than n=4, n=l ~ 3 composition tails off.
The method that the narrow dispersion multi-hydroxy compound used in the present invention can be obtained by the operation making phenols and aldehydes under the existence of phosphorus acid catalyst, utilize nonuniformity system to make it react, utilize remove the high molecular weight components of more than n=l composition and/or n=4 composition the poorly soluble thick multi-hydroxy compound from obtaining of all kinds of SOLVENTS method, in alkali aqueous solution, dissolve two nucleomes (two nucleomes) and the method etc. of carrying out removing obtains, but also can be obtained by other well-known separation method.
StPN of the present invention carries out addition reaction by making the narrow dispersion multi-hydroxy compound shown in general formula (1) and aralkyl agent and obtains.Now, as the ratio of multi-hydroxy compound and aralkyl agent, the flame retardant resistance of cured article obtained if consider and the balance of solidified nature, then aralkyl agent is preferably the scope of 0.1 ~ 1.5 mole relative to the usage ratio of multi-hydroxy compound 1 mole, be more preferably 0.1 ~ 1.0 mole, more preferably the scope of 0.3 ~ 0.8 mole.When being less than this scope, the state that the character for the multi-hydroxy compound of raw material does not improve, when more than this scope, functional group densities too step-down and the tendency having solidified nature to reduce.
In the reaction, addition on the aromatic ring with OH base of aralkyl agent in multi-hydroxy compound, the aralkyl shown in above-mentioned formula (a) replaces.In formula (a), R
3and R
4represent the alkyl of hydrogen atom or C1 ~ 6.Alkyl is preferably methyl.More preferably R
3and R
4in a side or two sides be hydrogen atom or methyl, preferably a side or two sides are hydrogen atom further.When two sides are hydrogen atom, being benzyl, when a side is hydrogen atom, is alpha-alkyl substituted benzyl.Also substituent R can be had at the benzene substitution in ring of this benzyl or alpha-alkyl substituted benzyl
2.The Adding sites of aralkyl in the ortho position in the room of multi-hydroxy compound and/or contraposition, but is mainly contraposition.
In addition, the melt viscosity at 150 DEG C of StPN of the present invention is preferably the scope of 0.01 ~ 10.0Pas.From the viewpoint of operability, melt viscosity is more low better in above-mentioned scope.
And then softening temperature can be 40 ~ 150 DEG C, be preferably the scope of 50 ~ 100 DEG C.At this, softening temperature refers to the softening temperature that the ring and ball method based on JIS-K-2207 measures.If lower than this softening temperature, then when coordinating StPN in the epoxy, the thermotolerance of cured article reduces, if higher than this softening temperature, then mobility when being shaped reduces.
The addition amount of aralkyl can be adjusted, usually for the phenyl ring addition 0.1 ~ 2.5 of multi-hydroxy compound according to the usage quantity of aralkyl agent.This refers to the mean number (quantity is average) of the aralkyl being replaced in 1 phenol ring.As addition amount, relative to the phenyl ring 1 mole of multi-hydroxy compound, preferred with the order of 0.1 ~ 1.5 mole, 0.1 ~ 1.0 mole, 0.3 ~ 0.8 mole.Be explained, due to 4 aralkyl can be replaced at most on the phenol ring of two ends, the phenol ring of centre can replace at most 3 aralkyl, therefore, when n is 1,8 aralkyl can be replaced at most.
In formula (a), R
2represent the alkyl of hydrogen or carbon number 1 ~ 6, be preferably the alkyl of hydrogen or carbon number 1 ~ 3, be more preferably hydrogen.This R
2can be determined by the aralkyl agent used as reaction raw materials.
In general formula (1), n represents the number of 1 ~ 5, and preferably average (quantity is average) is the scope of 1.9 ~ 3.4, the more preferably scope of 2.0 ~ 3.0, but must meet above-mentioned dispersion.From another viewpoint, n be 1 ~ 5 composition can be principal constituent.Principal constituent refers to more than 80wt%, is preferably more than 90wt%, is more preferably essentially all.In general formula (1), R
1represent the alkyl of hydrogen atom or carbon number 1 ~ 6, preferably represent the alkyl of hydrogen atom or carbon number 1 ~ 4.
Then, the manufacture method of StPN of the present invention is described.The multi-hydroxy compound that the general formula (1) used in method as manufacture StPN of the present invention represents, phenol novolacs class is suitable.Phenol novolacs can be obtained by phenols and aldehydes.
As the phenols for obtaining this multi-hydroxy compound, be mainly phenol.This phenols also can containing other a small amount of phenol composition.Such as can enumerate ortho-cresol, meta-cresol, p-cresol, ethyl phenols, sec.-propyl phenols, tertiary butyl phenols, allyl group phenols, phenyl phenols etc.These phenols can be used alone, and also two or more kinds may be used.Be explained, if on a small quantity, then can coordinate 2，6-xylenol, 2,6-diethyl phenol, Resorcinol, Resorcinol, pyrocatechol, 1-naphthols, beta naphthal, 1,5-naphthalenediol, 1,6-naphthalenediol, 1, other phenols or the aphthols such as 7-naphthalenediol, 2,6-naphthalenediols, 2,7-naphthalenediols.When coordinating these materials, below 30wt%, preferably below 20wt% can be limited to.
Aralkyl agent for reacting with multi-hydroxy compound uses the compound shown in above-mentioned formula (c1) or (c2).Compound shown in formula (c1) is called styrenic.Styrenic is the vinylbenzene that the alkyl of vinylbenzene or carbon number 1 ~ 6 replaces.In formula (c1), R
3for the alkyl of hydrogen or carbon number 1 ~ 6, be preferably hydrogen.This styrenic also containing other a small amount of reacted constituent, as other reacted constituent, can enumerate the composition containing unsaturated link(age) such as Vinylstyrene, indenes, coumarone, thionaphthene, indoles, vinyl naphthalene.When coordinating these materials, less than 30% can be limited to, preferred below 20wt%.
In above-mentioned formula (c2), R
2, R
3and R
4with the R of formula (a)
2, R
3and R
4synonym.X is halogen atom, the alkoxyl group of carbon number 1 ~ 6 or hydroxyl.In formula (c1), R
2, R
3with the R of formula (a)
2, R
3synonym.
As the aralkyl agent shown in above-mentioned formula (c2), when X is halogen atom, can enumerate: benzyl chloride, bromotoluene, benzyl iodide, adjacent methyl-benzyl chlorine, between methyl-benzyl chlorine, to methyl-benzyl chlorine, to ethylbenzyl chloride, p-isopropyl benzyl chloride, to t-butylbenzyl chlorine, to cyclohexyl benzyl chlorine, to phenylbenzyl chlorine, α-methylbenzyl chlorine, alpha, alpha-dimethylbenzyl chlorine etc., when X is alkoxyl group, is preferably the alkoxyl group of carbon number 1 ~ 4, can enumerates: benzyl methyl ether, adjacent methyl-benzyl methyl ether, between methyl-benzyl methyl ether, to methyl-benzyl methyl ether, to Ethylbenzyl methyl ether, benzyl ethyl ether, benzyl isopropyl ether, benzyl n-propyl ether, benzyl isobutyl ether, benzyl n-butyl ether, to methyl-benzyl methyl ether etc., when X is hydroxyl, can enumerate: phenylcarbinol, o-methyl-benzene methyl alcohol, between methylbenzyl alcohol, to methylbenzyl alcohol, to ethylbenzene methyl alcohol, isopropylbenzyl alcohol, to butyl-benzyl alcohol, to phenylcyclohexane methyl alcohol, to phenyl benzil alcohol, α-methylbenzylalcohol, α, alpha-alpha-dimethyl phenylcarbinol etc.As the aralkyl agent shown in formula (c1), can enumerate: vinylbenzene, have the ring-alkylated styrenes, alpha-alkyl phenylethylene class etc. of the alkyl of C1 ~ 6 at cinnamic benzene substitution in ring, be preferably that alkylbenzene second is rare or benzene second is rare, be more preferably benzene second rare.
Adopt the aralkyl glycosylation reaction of aralkyl agent to carry out in the presence of acid catalyst, this catalytic amount uses with the scope of 10 ~ 1000ppm (wt), is preferably the scope of 100 ~ 500ppm.If higher than this scope, then the methylene-crosslinked key of multi-hydroxy compound becomes easy fracture, due to cleavage reaction the secondary monohydric phenol composition generated, and solidified nature and thermotolerance are reduced.On the other hand, if lower than scope, then reactive reduction, makes unreacted aralkyl agent remaining in a large number.In addition, the amount of total weight of the multi-hydroxy compound that catalyzer uses relative to reaction and aralkyl agent is referred at this said catalytic amount.
As acid catalyst, can be suitable for selecting from well-known mineral acid, organic acid.Such as can enumerate: the mineral acids such as hydrochloric acid, sulfuric acid, phosphoric acid, the organic acids such as formic acid, oxalic acid, trifluoracetic acid, tosic acid, dimethyl sulfate, diethyl sulfuric acid, the solid acids etc. such as the Lewis acids such as zinc chloride, aluminum chloride, iron(ic) chloride, boron trifluoride or ion exchange resin, atlapulgite, silica-alumina, zeolite.
In addition, the temperature of reaction in this reaction is carried out in the scope of 40 ~ 120 DEG C.If lower than this scope, then reactive reduction, the reaction times becomes long-time.In addition, if higher than this scope, then the methylene-crosslinked key of multi-hydroxy compound becomes easy fracture, due to cleavage reaction the secondary monohydric phenol composition that generates and solidified nature and thermotolerance are reduced.
In addition, this reaction carries out 1 ~ 20 hour usually.And then, when reacting, the alcohols such as methyl alcohol, ethanol, propyl alcohol, butanols, ethylene glycol, methylcyclohexane, ethyl cellosolve can be used, the ketones such as acetone, methyl ethyl ketone, mibk, the ethers such as dimethyl ether, Anaesthetie Ether, Di Iso Propyl Ether, tetrahydrofuran (THF), diox, the aromatics such as benzene, toluene, chlorobenzene, dichlorobenzene etc. are as solvent.
As the concrete grammar implementing this reaction, whole raw material is loaded in the lump, directly reacts at specified temperatures, or multi-hydroxy compound and catalyzer are loaded, while remain on the temperature of regulation, drip aralkyl agent, make its method of reacting be general simultaneously.Now, time for adding is preferably less than 5 hours, is generally 1 ~ 10 hour.After reaction, when using solvent, as required after eliminating catalyst component, desolventizing can being heated up in a steamer and obtain resin of the present invention, when not using solvent, by directly discharging when heat, can object be obtained.
Then, epoxy resin of the present invention (StPNE) is described.
Epoxy resin of the present invention (StPNE) can by obtaining StPN epoxidation.
For StPNE of the present invention, be favourable by making above-mentioned StPN and epichlorohydrin reaction and manufacturing.StPN can be carried out with the reaction of epichlorohydrin reaction in the same manner as common epoxidation reaction.
Such as can enumerate after making above-mentioned StPN be dissolved in excessive epoxy chloropropane, the reaction method of 1 ~ 10 hour under the existence of the alkali metal hydroxide such as sodium hydroxide, potassium hydroxide, in the scope of 20 ~ 150 DEG C, preferably 30 ~ 80 DEG C.The usage quantity of alkali metal hydroxide is now 0.8 ~ 1.5 mole relative to the hydroxyl 1 mole of StPN, is preferably the scope of 0.9 ~ 1.2 mole.In addition, epoxy chloropropane uses relative to hydroxyl 1 molar excess in StPN, is 1.5 ~ 30 moles usually relative to the hydroxyl in StPN 1 mole, is preferably the scope of 2 ~ 15 moles.After reaction terminates, heat up in a steamer excessive epoxy chloropropane, be dissolved in by residue in toluene, methyl iso-butyl ketone (MIBK) equal solvent, and filter, wash, removing inorganic salt, then heat up in a steamer desolventizing, can obtain the epoxy resin of object thus.
Composition epoxy resin of the present invention at least containing epoxy resin and solidifying agent, has following 3 kinds.
1) part or all the composition of above-mentioned StPNE as epoxy resin is combined with.
2) part or all the composition of above-mentioned StPN as solidifying agent is combined with.
3) part or all the composition of above-mentioned StPNE and StPN as epoxy resin and solidifying agent is combined with.
When above-mentioned 2) and 3) composition, containing StPN as neccessary composition.The use level of StPN is 2 ~ 200 weight parts relative to epoxy resin 100 weight part usually, is preferably the scope of 5 ~ 80 weight parts.If lower than this scope, then the effect of flame retardant resistance and wet fastness raising is little, if higher than this scope, then and the problem that the intensity that there is plasticity and cured article reduces.
When the total amount using StPN as solidifying agent, the use level of usual StPN considers that the OH base of StPN coordinates with the equivalent balanced of the epoxy group(ing) in epoxy resin.The equivalence ratio of epoxy resin and solidifying agent is generally the scope of 0.2 ~ 5.0, is preferably the scope of 0.5 ~ 2.0.If larger than this scope or little, then the solidified nature of composition epoxy resin reduces, simultaneously the reduction such as thermotolerance, mechanical strength of cured article.
As solidifying agent, can be used together the solidifying agent beyond StPN.The use level of other solidifying agent the use level of StPN is remained on usually relative to epoxy resin 100 weight part be 2 ~ 200 weight parts, the scope being preferably 5 ~ 80 weight parts scope in decide.If the use level of StPN is lower than this scope, then the effect of agent of low hygroscopicity, adaptation and flame retardant resistance raising is little, if higher than this scope, then and the problem that the intensity that there is plasticity and cured article reduces.In this case, the equivalence ratio of epoxy resin and solidifying agent (total) is set to above-mentioned scope.
As the solidifying agent beyond StPN, generally all can use as the material that the solidifying agent of epoxy resin is known, have: dicyanodiamide, anhydrides, polyatomic phenol, aromatic series and aliphatics amine etc.Wherein, require the field of high electrical insulating properties at semiconductor-encapsulating material etc., preferably use polyatomic phenol as solidifying agent.When using StPN of the present invention as the composition of neccessary composition, the use level of StPN can be 50 ~ 100%, be preferably the scope of 60 ~ 100% in solidifying agent entirety.Below, the concrete example of the solidifying agent beyond StPN is represented.
As anhydride curing agent, such as have: Tetra hydro Phthalic anhydride, Tetra Hydro Phthalic Anhydride, methyl tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl-5-norbornylene-2,3-dicarboxylic anhydride (acid of メ チ Le No water Ha イ ミ ッ Network), dodecenyl succinic (De デ シ ニ Le) succinyl oxide, Na Dike (Na ジ ッ Network) acid anhydrides, trimellitic acid 1,2-anhydride etc.
As polyatomic phenol, such as have: dihydroxyphenyl propane, Bisphenol F, bisphenol S, fluorenes bis-phenol, 4,4 '-xenol, 2,2 yuan of phenols such as 2 '-xenol, Resorcinol, Resorcinol, naphthalenediol, or with three-(4-hydroxy phenyl) methane, 1, the phenols of more than 3 yuan that 1,2,2-tetra-(4-hydroxy phenyl) ethane, phenol novolacs, o-cresol novolak, naphthol novolac varnish, polyvinylphenol etc. are representative.And then have: by phenols, aphthols, dihydroxyphenyl propane, Bisphenol F, bisphenol S, fluorenes bis-phenol, 4,4 '-xenol, 2, the polynary phenoloid etc. of the condensing agent synthesis such as 2 yuan of phenols such as 2 '-xenol, Resorcinol, Resorcinol, naphthalenediol and formaldehyde, acetaldehyde, phenyl aldehyde, p-Hydroxybenzaldehyde, terephthaldehyde's base dichloro, dichloride methyl biphenyl, dichloride methyl naphthalene.
As amine, have: 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino-diphenyl propane, 4, the aliphatics amine such as aromatic amine, quadrol, hexamethylene-diamine, Diethylenetriamine, three second tetramines of 4 '-diamino diphenyl sulfone, mphenylenediamine, terephthaldehyde's base diamines etc.
In above-mentioned composition, 1 of these solidifying agent kind or mix two or more and use can be used.
As the epoxy resin used in above-mentioned composition, have from 1 molecule in the epoxy resin of the epoxy group(ing) of more than 2 and select.Such as can enumerate: dihydroxyphenyl propane, Bisphenol F, 3, 3 ', 5, 5 '-tetramethyl--Bisphenol F, bisphenol S, fluorenes bis-phenol, 2, 2 '-xenol, 3, 3 ', 5, 5 '-tetramethyl--4, 4 '-dihydroxybiphenyl phenol, Resorcinol, the epoxide of 2 yuan of phenols such as naphthalenediol class, three (4-hydroxy phenyl) methane, 1, 1, 2, 2-tetra-(4-hydroxy phenyl) ethane, phenol novolacs, the epoxide of the phenols that o-cresol novolak etc. are more than 3 yuan, the epoxide of the cocondensation resin of Dicyclopentadiene (DCPD) and phenols, the epoxide of the phenol aralkyl resin class synthesized by phenols and terephthaldehyde's base dichloro etc., the epoxide of the biphenyl aralkyl-type phenol resin synthesized by phenols and dichloride methyl biphenyl etc., the epoxide etc. of the naphthols aralkyl resin class synthesized by aphthols and terephthaldehyde's base dichloro etc.These epoxy resin can use a kind or mix two or more and use.
When above-mentioned 1) and 3) composition, containing StPNE as neccessary composition.In this composition epoxy resin, as epoxy resin ingredient, the epoxy resin of other kind beyond StPNE also can be coordinated.As epoxy resin now, the common epoxy resin in the molecule with the epoxy group(ing) of more than 2 all can use.If enumerate example, then have: dihydroxyphenyl propane, bisphenol S, fluorenes bis-phenol, 4,4 '-xenol, 2,2 yuan of phenols or three-(4-hydroxy phenyl) methane, 1 such as 2 '-xenol, Resorcinol, Resorcinol, 1, the phenols of 2,2-tetra-(4-hydroxy phenyl) ethane, phenol novolacs, o-cresol novolak etc. more than 3 yuan, phenol system aralkyl resin class, biphenyl aralkyl resin class, the halogenated bisphenols class such as naphthols system aralkyl resin class or tetrabromo-bisphenol the glycidyl etherified thing etc. that derives.These epoxy resin can use a kind or mix two or more and use.And when the composition being neccessary composition with StPNE of the present invention, the use level of StPNE can be 50 ~ 100% in epoxy resin integral, be preferably the scope of 60 ~ 100%.
In composition epoxy resin of the present invention, also can be suitable for coordinating the oligopolymer of polyester, polymeric amide, polyimide, polyethers, urethane, petroleum resin, indene resin, indenes coumarone resin, phenoxy resin etc. or macromolecular compound as other properties-correcting agent etc.Relative to epoxy resin 100 weight part, addition is generally the scope of 2 ~ 30 weight parts.
In addition, in composition epoxy resin of the present invention, the additives such as inorganic filler, pigment, fire retardant, thixotropy conferring agents, coupling agent, fluidity improving agent can be coordinated.As inorganic filler, such as can enumerate: SiO 2 powder, alumina powder, the glass powder such as fused silica, crystalline silica of spherical or broken shape, or mica, talcum, calcium carbonate, aluminum oxide, hydrated aluminum oxide etc., be more than 70 % by weight for preferred use level during semiconductor-encapsulating material, more preferably more than 80 % by weight.
As pigment, have: the pigment extender, flakey pigment etc. of organic or inorganic.As thixotropy conferring agents, can enumerate: silicon system, Viscotrol C system, aliphatic amide wax, oxidized polyethlene wax, organobentonite etc.
And then, in composition epoxy resin of the present invention, curing catalyst can be used as required.If enumerate example, then have: amine, imidazoles, organic phosphine class, Lewis acid etc., specifically, have: 1, 8-diazabicyclo (5, 4, 0) hendecene-7, triethylenediamine, benzyl dimethyl amine, trolamine, dimethylaminoethanol, the tertiary amine of three (dimethylaminomethyl) phenol etc., glyoxal ethyline, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, the imidazoles of 2-heptadecyl imidazole etc., tributylphosphine, methyldiphenyl base phosphine, triphenylphosphine, diphenylphosphine, the organic phosphine classes such as Phenylphosphine, tetraphenylphosphoniphenolate tetraphenylborate, tetraphenylphosphoniphenolate ethyl triphenyl boric acid ester, the four Qu Dai Phosphonium four substituted boracic acid esters such as 4-butyl-phosphonium tetrabutyl boric acid ester, 2-ethyl-4-methylimidazole tetraphenylborate, the tetraphenyl boron salt etc. such as N-methylmorpholine tetraphenylborate.Relative to epoxy resin 100 weight part, be generally the scope of 0.2 ~ 5 weight part as addition.
And then, as required, the lubricants etc. such as the low-stress such as fire retardant, silicone oil agent, calcium stearate such as the tinting material such as coupling agent, carbon black, the ANTIMONY TRIOXIDE SB 203 99.8 PCT such as the releasing agent such as carnauba wax, OP wax, γ-glycidoxypropyltrime,hoxysilane can be used in resin combination of the present invention.
Composition epoxy resin of the present invention, after formation is dissolved with the varnish state of organic solvent, after being impregnated in the fibrous materials such as polyester non-woven fabric such as woven fiber glass, aromatic polyamide non-woven fabrics, liquid crystalline polymers, can carrying out solvent removing, and becomes prepreg.In addition, as required, sandwich can be become by being coated on the flaps such as Copper Foil, stainless steel foil, Kapton, polyester film.
If be heating and curing by composition epoxy resin of the present invention, then can become epoxy resin cured product, this cured article is excellent in solidified nature, flame retardant resistance, agent of low hygroscopicity, low elasticity etc.Composition epoxy resin can be formed processing by methods such as casting, compression molding, transfer moulds and obtain by this cured article.Temperature is now generally the scope of 120 ~ 220 DEG C.
Embodiment
Below, by embodiment, further illustrate the present invention.The unit of hydroxyl equivalent and epoxy equivalent (weight) is g/eq..
Synthesis example 1
In the four-hole boiling flask of 1L, add phenol 250g, oxalic acid dihydrate 0.75g as acid catalyst, import nitrogen, while stir, carry out heating and heating up.Start to drip 37.4% formalin 47.4g in 80 DEG C, terminated to drip with 30 minutes.Further temperature of reaction is remained on 92 DEG C, carry out reaction in 3 hours.While carry out heating up, water generation reaction is removed to outside system, be warming up to 110 DEG C.Remaining phenol is under reduced pressure reclaimed in 160 DEG C.Further raising temperature and reclaim the parts of two nucleomes.The hydroxyl equivalent of the multi-hydroxy compound of gained is 104, and softening temperature is 68 DEG C, and the melt viscosity at 150 DEG C is 0.07Pas.The containing ratio of n=l composition that GPC measures gained is the total containing ratio of 8.1%, n=2 and n=3 composition is 71.7%, Mw/Mn=1.10.This resin is called multi-hydroxy compd A.Fig. 1 represents the GPC figure of multi-hydroxy compd A.
Synthesis example 2
In the four-hole boiling flask of 1L, adding phenol 250g, 7.4% formalin 47.4g, 89% phosphatase 11 50g as acid catalyst, carrying out heating and heating up under the basis of the gonorrhoea state formed by being uniformly mixed (2 phase mixture).Remain on reflux temperature further, carry out reaction 6 hours.Then, add methyl iso-butyl ketone (MIBK) and leave standstill after dissolving resin part, being separated into resin solution phase and phosphate aqueous solution phase.Removing phosphoric acid solution mutually after, wash further.Then, remaining phenol is under reduced pressure reclaimed in 160 DEG C.Further raising temperature and reclaim the parts of two nucleomes.The hydroxyl equivalent of the multi-hydroxy compound of gained is 103, and softening temperature is 65 DEG C, and the melt viscosity at 150 DEG C is 0.06Pas.The containing ratio of n=l composition that GPC measures gained is the total containing ratio of 2.0%, n=2 and n=3 composition is 91.5%, Mw/Mn=1.04.This resin is called multi-hydroxy compd B.Fig. 2 represents the GPC figure of multi-hydroxy compd B.
Embodiment 1
In the four-hole boiling flask of 1L, add the multi-hydroxy compd A 104g, the tosic acid 0.053g (300ppm) as acid catalyst that obtain in the synthesis example 1 as multi-hydroxy chemical composition, be warming up to 120 DEG C.Then, stir at 120 DEG C, while dripped vinylbenzene 72.8g (0.7 mole) with 3 hours and make it react.And then, after 1 hour, obtain phenylethene modified multi-hydroxy resin 168g in 120 DEG C of reactions.Its hydroxyl equivalent is 177, and softening temperature is 78 DEG C, and the melt viscosity at 150 DEG C is 0.13Pas.This resin is called modified multicomponent hydroxy resin A (StPN-A).Fig. 4 represents the GPC figure of StPN-A.
Embodiment 2
In the four-hole boiling flask of 1L, add the multi-hydroxy compd B 103g, the tosic acid 0.053g (300ppm) as acid catalyst that obtain in the synthesis example 2 as multi-hydroxy chemical composition, be warming up to 120 DEG C.Then, stir at 120 DEG C, while dripped vinylbenzene 72.8g (0.7 mole) with 3 hours and make it react.And then, after 1 hour, obtain ha styt-ehe modified multicomponent hydroxy resin 167g in 120 DEG C of reactions.Its hydroxyl equivalent is 176, and softening temperature is 78 DEG C, and the melt viscosity at 150 DEG C is 0.13Pa.s.This resin is called modified multicomponent hydroxy resin B (StPN-B).Fig. 5 represents the GPC figure of StPN-B.
Embodiment 3
Add in the four-hole boiling flask of 1L obtain in the synthesis example 1 as multi-hydroxy chemical composition multi-hydroxy compd A 104g, water l.0g, be warming up to 120 DEG C.Then, stir at 120 DEG C, while dripped benzyl chloride 88.6g (0.7 mole) with 3 hours and make it react.And then, after 1 hour, obtain benzyl modified multicomponent hydroxy resin 160g in 120 DEG C of reactions.Its hydroxyl equivalent is 168, and softening temperature is 70 DEG C, and the melt viscosity at 150 DEG C is 0.09Pas.This resin is called modified multicomponent hydroxy resin C (StPN-C).Fig. 6 represents the GPC figure of StPN-C.
Comparative example 1
Phenol novolacs (the Showa electrician system as multi-hydroxy chemical composition is added in the four-hole boiling flask of 1L; BRG-555 is (also referred to as multi-hydroxy Compound C, Fig. 3 represents that GPC schemes), the containing ratio of n=l composition that measures of GPC is 25.4%, the total containing ratio of n=2 and n=3 composition is 32.1%, Mw/Mn=1.45, hydroxyl equivalent 105, softening temperature 67 DEG C, the melt viscosity 0.08Pas at 150 DEG C) 105g, tosic acid 0.055g (300ppm) as acid catalyst, be warming up to 120 DEG C.Then, stir at 120 DEG C, while dripped vinylbenzene 73g (0.7 mole) with 3 hours and make it react.And then, after 1 hour, obtain phenylethene modified multi-hydroxy resin 170g in 120 DEG C of reactions.Its hydroxyl equivalent is 178, and softening temperature is 78 DEG C, and the melt viscosity at 150 DEG C is 0.13Pas.This resin is called modified multicomponent hydroxy resin D (StPN-D).Fig. 7 represents the GPC figure of StPN-D.
Embodiment 4
In four mouthfuls of removable flasks, add the StPN-A 150g, epoxy chloropropane 470g, the diethylene glycol dimethyl ether 71g that obtain in embodiment 1, carry out stirring and dissolving.After dissolving equably, 65 DEG C are remained under the decompression of 130mmHg, 48% aqueous sodium hydroxide solution 70.6g is dripped with 4 hours, in separator tank, the water distillated that refluxes in this dropping is separated with epoxy chloropropane, epoxy chloropropane turns back to reaction vessel, reacts outside water removing to system.After reaction terminates, removing generated salt by filtering, heating up in a steamer epoxy chloropropane after water washing further, obtaining epoxy resin A (StPNE-A) 168g.The epoxy equivalent (weight) of the resin of gained is 241, and softening temperature is 56 DEG C, and the melt viscosity at 150 DEG C is 0.12Pa.s.Fig. 8 represents the GPC figure of StPNE-A.
Embodiment 5
In four mouthfuls of removable flasks, add the StPN-B 150g, epoxy chloropropane 473g, the diethylene glycol dimethyl ether 71g that obtain in embodiment 2, carry out stirring and dissolving.After dissolving equably, 65 DEG C are remained under the decompression of 130mmHg, 48% aqueous sodium hydroxide solution 71.0g is dripped with 4 hours, in separator tank, the water distillated that refluxes in this dropping is separated with epoxy chloropropane, epoxy chloropropane turns back to reaction vessel, reacts outside water removing to system.After reaction terminates, removing generated salt by filtering, heating up in a steamer epoxy chloropropane after water washing further, obtaining epoxy resin B (StPNE-B) 165g.The epoxy equivalent (weight) of the resin of gained is 245, and softening temperature is 55 DEG C, and the melt viscosity at 150 DEG C is 0.11Pas.Fig. 9 represents the GPC figure of StPNE-B.
Embodiment 6
In four mouthfuls of removable flasks, add the StPN-C 150g, epoxy chloropropane 495g, the diethylene glycol dimethyl ether 74g that obtain in embodiment 3, carry out stirring and dissolving.After dissolving equably, 65 DEG C are remained under the decompression of 130mmHg, 48% aqueous sodium hydroxide solution 74.4g is dripped with 4 hours, in separator tank, the water distillated that refluxes in this dropping is separated with epoxy chloropropane, epoxy chloropropane turns back to reaction vessel, reacts outside water removing to system.After reaction terminates, removing generated salt by filtering, heating up in a steamer epoxy chloropropane after water washing further, obtaining epoxy resin C (StPNE-C) 185g.The epoxy equivalent (weight) of the resin of gained is 236, and softening temperature is 52 DEG C, and the melt viscosity at 150 DEG C is 0.08Pas.Figure 10 represents the GPC figure of StPNE-C.
Comparative example 2
In four mouthfuls of removable flasks, add the StPN-D 150g, epoxy chloropropane 468g, the diethylene glycol dimethyl ether 70g that obtain in comparative example 1, carry out stirring and dissolving.After dissolving equably, 65 DEG C are remained under the decompression of 130mmHg, 48% aqueous sodium hydroxide solution 70.3g is dripped with 4 hours, in separator tank, the water distillated that refluxes in this dropping is separated with epoxy chloropropane, epoxy chloropropane turns back to reaction vessel, reacts outside water removing to system.After reaction terminates, removing generated salt by filtering, heating up in a steamer epoxy chloropropane after water washing further, obtaining epoxy resin 185g (StPNE-D).The epoxy equivalent (weight) of the resin of gained is 246, and softening temperature is 56 DEG C, melt viscosity at 150 DEG C is 0.l0Pas.Figure 11 represents the GPC figure of StPNE-D.
Embodiment 7 ~ 9 and example 10 ~ 11 (comparison)
As epoxy resin ingredient, use o-cresol phenolic epoxy varnish (OCNE; Epoxy equivalent (weight) 200, softening temperature 65 DEG C), as solidifying agent, except the StPN-D obtained in the StPN-C obtained in the StPN-B obtained in the StPN-A obtained in embodiment 1, embodiment 2, embodiment 3, comparative example 1, also use phenol novolacs (PN; PSM-4261 (the flourish chemical industry system of group); OH equivalent 103, softening temperature 82 DEG C).Using the mixing silicon-dioxide as weighting agent of the cooperation shown in table 1 (median size 18pm), triphenylphosphine as curing catalyst, obtain composition epoxy resin.Use this composition epoxy resin, form at 175 DEG C, at 175 DEG C, carry out 12 hours after fixing, after obtaining cured article test film, for various physical property measurement.Below represent details, table 2 represents result.
(1) gel permeation chromatography (GPC) measures
Use the equipment in series having TOSOH Co., Ltd TSKgelG4000HXL, TSKgelG3000HXL, TSKgelG2000HXL, column temperature is set to 40 DEG C.In addition, eluant uses tetrahydrofuran (THF), and the flow velocity of setting 1ml/min, detector uses RI (differential refractometer) detector.Sample 0.lg is dissolved in the THF of 10ml.After obtaining weight-average molecular weight (Mw) and number-average molecular weight (Mn) by utilizing the typical curve of polystyrene standard, obtain dispersity (Mw/Mn).
(2) softening temperature
Use automatic softening point measurement device (Ming Feng society ASP-M4SP), according to JIS-K-2207, measure by ring and ball method.
(3) melt viscosity
Use BROOKFIELD CAP2000H type rotational viscosimeter, measure at 150 DEG C.
(4) mensuration of hydroxyl equivalent
Use potential difference titration apparatus, solvent uses Isosorbide-5-Nitrae-diox, carries out acetylize with 1.5mol/L Acetyl Chloride 98Min., with the Acetyl Chloride 98Min. that water decomposition is excessive, uses the potassium hydroxide of 0.5mol/L to carry out titration.
(5) mensuration of epoxy equivalent (weight)
Use potential difference titration apparatus, use methyl ethyl ketone as solvent, add tetraethylammonium bromide acetum, by potential difference titration apparatus, use 0.lmol/L perchloric acid-acetum to measure.
(6) gel time
Be heated to be 175 DEG C gelation trier (day new science (strain) system) plate on add composition epoxy resin, use fluoro-resin rod, stir with the speed that a second 2 encloses, study gelation time required to epoxy resin composition.
(7) hardness during heat
Form under die temperature 175 DEG C, 90 seconds set times, in die sinking after 10 seconds, use Shore D hardness measurement to determine Shore D hardness value, hardness when being set to heat.
(8) glass transition point (Tg), polar expansion number (CTE)
Utilize SEIKO instrument TMA120C type thermomechanical determinator, Tg is obtained under the condition of heat-up rate 10 DEG C/min, for α 1 (CTE of below Tg), obtain the mean value of the scope of 30 ~ 50 DEG C, and for α 2 (CTE of more than Tg), obtain from the mean value of the scope of Tg+20 DEG C ~ 40 DEG C.
(9) flexural strength and the elasticity of flexure
According to JISK 6911, measured at normal temperatures by 3 bend test methods.
(10) water-intake rate
By 25 DEG C, the condition of relative humidity 50% is set to standard state, be set to 85 DEG C, make the weight rate of its moisture absorption after 100 hours under the condition of relative humidity 85%.
(11) flame retardant resistance
The test film that forming thickness is 1/16 inch, evaluates according to UL94V-0 standard, represents with the combustion time of the total of the test films of 5.
Table 1
Table 2
| Embodiment 7 | Embodiment 8 | Embodiment 9 | Example 10 | Example 11 | |
| Ask during gel (sec) | 38 | 35 | 32 | 45 | 25 |
| Hardness during heat | 73 | 76 | 80 | 65 | 86 |
| Tg(℃) | 112 | 114 | 110 | 109 | 165 |
| CTE(<Tg，×10 -5) | 1.1 | 1.1 | 1.1 | 1.1 | 1.1 |
| CTE(>Tg，×10 -5) | 4.4 | 4.4 | 4.5 | 4.5 | 4.3 |
| Flexural strength (MPa) | 120 | 123 | 118 | 111 | 158 |
| Bending elastic modulus (GPa) | 20.5 | 20.9 | 20.0 | 20.2 | 25.7 |
| Water-intake rate (wt%) | 0.23 | 0.23 | 0.24 | 0.23 | 0.26 |
| Combustion time (sec) | 47 | 26 | 45 | 98 | 332 |
Embodiment 12 ~ 14 and example 15 ~ 16 (comparison)
As epoxy resin ingredient, except the StPNE-D obtained in the StPNE-C obtained in the StPNE-B obtained in the StPNE-A obtained in embodiment 4, embodiment 5, embodiment 6, comparative example 2, also use o-cresol phenolic epoxy varnish (OCNE; Epoxy equivalent (weight) 200, softening temperature 65 DEG C), as curing agent component, use phenol aralkyl resin (PA; MEH-7800SS (bright and change into system), OH equivalent 175, softening temperature 67 DEG C).And then, use spherical silicon dioxide (median size 18 μm) as weighting agent, use triphenylphosphine as curing catalyst, obtain composition epoxy resin with the cooperation shown in table 3.The weight part that numeric representation in table coordinates.
Use this composition epoxy resin to form at 175 DEG C, at 175 DEG C, carry out 12 hours after fixing further, after obtaining cured article test film, for various physical property measurement.Table 4 represents result.
Table 3
Table 4
| Embodiment 12 | Embodiment 13 | Embodiment 14 | Example 15 | Example 16 | |
| Ask during gel (sec) | 39 | 37 | 35 | 48 | 27 |
| Hardness during heat | 71 | 73 | 78 | 63 | 87 |
| Tg(℃) | 130 | 132 | 128 | 127 | 138 |
| CTE(<Tg，×10 -5) | 1.1 | 1.1 | 1.1 | 1.1 | 1.1 |
| CTE(>Tg，×10 -e) | 4.9 | 4.8 | 5.0 | 5.1 | 4.8 |
| Flexural strength (MPa) | 140 | 142 | 140 | 137 | 151 |
| Bending elastic modulus (GPa) | 18.0 | 18.5 | 17.9 | 17.8 | 20.2 |
| Water-intake rate (wt%) | 0.22 | 0.22 | 0.23 | 0.22 | 0.26 |
| Combustion time (sec) | 43 | 27 | 40 | 65 | 223 |
The possibility that industry utilizes
When epoxy resin of the present invention and multi-hydroxy resin are applied to composition epoxy resin, solidified nature and mechanical properties are excellent and give flame retardant resistance, wet fastness and low elasticity also excellent cured article, can be suitable for the purposes such as sealing, circuit base material of electric ton parts.Particularly solidified nature and excellent in flame retardance, guarantees excellent plasticity, and does not need or reduce the use of the fire retardant that there is carrying capacity of environment.
Claims (11)
1. an aralkyl modified multi-hydroxy resin, it is characterized in that, it is for making the multi-hydroxy compound shown in following general formula (1) and the reaction of aralkyl agent, on the phenyl ring substituting group being derived from aralkyl agent shown in formula (a) being replaced in multi-hydroxy compound and the aralkyl modified multi-hydroxy resin obtained
As by the multi-hydroxy compound shown in general formula (1), use in the area % of gel permeation chromatography, n=1 composition be less than 15%, n=2 and n=3 composition add up to more than 50%, Mw/Mn be less than 1.2 narrow dispersion multi-hydroxy compound obtain
At this, R
1and R
2represent the alkyl of hydrogen atom or carbon number 1 ~ 6, R
3and R
4represent the alkyl of hydrogen atom or carbon number 1 ~ 6, n represents the number of 1 ~ 5.
2. aralkyl modified multi-hydroxy resin according to claim 1, wherein, aralkyl agent is vinylbenzene.
3. the manufacture method of an aralkyl modified multi-hydroxy resin, it is characterized in that, the aralkyl agent reaction shown in the multi-hydroxy compound shown in following general formula (1) and following formula (c1) or (c2) is made in manufacture, on the phenyl ring substituting group being derived from aralkyl agent shown in formula (a) being replaced in multi-hydroxy compound and the aralkyl modified multi-hydroxy resin obtained time, as the multi-hydroxy compound of general formula (1), use in the area % of gel permeation chromatography, n=l composition is less than 15%, n=2 and n=3 composition add up to more than 50%, Mw/Mn is the narrow dispersion multi-hydroxy compound of less than 1.2, and make above-mentioned reaction under the existence of the acid catalyst of 10 ~ 1000ppm, react temperature of reaction 40 ~ 120 DEG C,
At this, R
1and R
2represent the alkyl of hydrogen atom or carbon number 1 ~ 6, n represents the number of 1 ~ 5,
At this, R
2represent the alkyl of hydrogen atom or carbon number 1 ~ 6, R
3and R
4represent the alkyl of hydrogen atom or carbon number 1 ~ 6, X represents halogen, OH or OR
5, R
5represent the alkyl of carbon number 1 ~ 6,
At this, R
2, R
3and R
4with formula (c1) and (c2) synonym.
4. the manufacture method of aralkyl modified multi-hydroxy resin according to claim 3, is characterized in that, relative to the hydroxyl 1 mole of multi-hydroxy compound, makes aralkyl agent 0.1 ~ 1.5 molar reactive.
5. the manufacture method of aralkyl modified multi-hydroxy resin according to claim 3, it is characterized in that, aralkyl agent is vinylbenzene.
6. a composition epoxy resin, is characterized in that, it contains epoxy resin and solidifying agent, as part or all of solidifying agent, forms using aralkyl modified multi-hydroxy resin according to claim 1 as neccessary composition.
7. an epoxy resin cured product, is characterized in that, is formed by epoxy resin composition according to claim 6.
8. an epoxy resin, is characterized in that, makes aralkyl modified multi-hydroxy resin according to claim 1 and epichlorohydrin reaction and obtains.
9. a manufacture method for epoxy resin, is characterized in that, makes aralkyl modified multi-hydroxy resin according to claim 1 and epichlorohydrin reaction, and the hydroxyl of aralkyl modified multi-hydroxy resin is formed glycidyl ether.
10. a composition epoxy resin, it contains epoxy resin and solidifying agent, wherein, coordinates epoxy resin according to claim 8 to form as neccessary composition.
11. 1 kinds of epoxy resin cured products, form epoxy resin composition according to claim 10.
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| PCT/JP2013/054278 WO2013125620A1 (en) | 2012-02-23 | 2013-02-21 | Polyvalent hydroxy resin, epoxy resin, method for producing same, epoxy resin composition and cured product thereof |
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| CN104945583B (en) * | 2014-03-26 | 2018-09-11 | 新日铁住金化学株式会社 | Modified multicomponent hydroxy resin, epoxy resin, composition epoxy resin and its hardening thing |
| CN109071780A (en) * | 2016-04-28 | 2018-12-21 | 日立化成株式会社 | Composition epoxy resin and electronic part apparatus |
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| TWI595019B (en) * | 2012-11-12 | 2017-08-11 | Ｄｉｃ股份有限公司 | Phenolic hydroxyl group-containing resin, epoxy resin, curable resin composition,cured product thereof and semiconductor encapsulating material |
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Also Published As
| Publication number | Publication date |
|---|---|
| WO2013125620A1 (en) | 2013-08-29 |
| TW201345958A (en) | 2013-11-16 |
| KR101987946B1 (en) | 2019-06-11 |
| KR20140129227A (en) | 2014-11-06 |
| JP6124865B2 (en) | 2017-05-10 |
| JPWO2013125620A1 (en) | 2015-07-30 |
| SG11201405075SA (en) | 2014-10-30 |
| MY169844A (en) | 2019-05-17 |
| TWI548681B (en) | 2016-09-11 |
| CN104334597B (en) | 2016-06-22 |
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Effective date of registration: 20191213 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. |