CN104334597B - Multi-hydroxy resin, epoxy resin, their manufacture method, composition epoxy resin and solidfied material thereof - Google Patents
Multi-hydroxy resin, epoxy resin, their manufacture method, composition epoxy resin and solidfied material thereof Download PDFInfo
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- CN104334597B CN104334597B CN201380010483.7A CN201380010483A CN104334597B CN 104334597 B CN104334597 B CN 104334597B CN 201380010483 A CN201380010483 A CN 201380010483A CN 104334597 B CN104334597 B CN 104334597B
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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
There is provided a kind of curable excellent and give the solidfied material that mechanical strength, anti-flammability, moisture-proof, low elasticity etc. are excellent, being suitable to the epoxy resin of purposes, multi-hydroxy resin and the compositionss thereof such as the sealing of electronic component, circuit base material。This multi-hydroxy resin is that to make 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 react, with aralkyl agents such as phenylethylenes, the aralkyl modified multi-hydroxy resin obtained。It addition, the epoxy resin obtained for making this aralkyl modified multi-hydroxy resin and epichlorohydrin reaction。And, for containing composition epoxy resin as neccessary composition of above-mentioned aralkyl modified multi-hydroxy resin or epoxy resin。
Description
Technical field
The present invention relates to a kind of curable excellent and give the epoxy resin of the also excellent solidfied material of mechanical strength, anti-flammability, moisture-proof, low elasticity, be suitable as the multi-hydroxy resin of its intermediate, their manufacture method, the composition epoxy resin using them and its solidfied material, be suitable for the insulant 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, the representative field of the resin combination being host with epoxy resin there is semiconductor-encapsulating material, raising along with the integrated level of semiconductor element, package dimension is towards large area, slimming, mounting means also shifts towards surface installationization simultaneously, it is desirable to the material of exploitation scolding tin excellent heat resistance。Accordingly, as encapsulant, except low moisture absorption, also it is strongly required the raising at the cementability of the foreign material such as lead frame, chip interface, adaptation。For circuit base material too, from the view point of scolding tin thermostability improves, except agent of low hygroscopicity, high-fire resistance, high adhesion raising except, from the view point of dielectric absorption reduces, it is also desirable to the material that exploitation low-dielectric is excellent。In order to corresponding to these requirements, have studied the epoxy resin of various innovative construction and firming agent。It addition, recently, from the view point of carrying capacity of environment reduces, there is the trend getting rid of halogenated flame retardant, it is desirable to epoxy resin that anti-flammability is more excellent and firming agent。
Therefore, based on above-mentioned background, have studied various epoxy resin and epoxy curing agent。An example as epoxy curing agent, it is known to naphthalene system resin, has illustrated in patent documentation 1 and naphthols aralkyl resin has been applied to semiconductor-encapsulating material, described the excellences such as anti-flammability, agent of low hygroscopicity, low heat expansion。It addition, patent documentation 2 proposes to have the firming agent with biphenyl structure, and describe to anti-flammability raising effectively。But, naphthols aralkyl resin, biphenyl aralkyl resin all have the shortcoming of curable difference, it addition, the effect for anti-flammability raising is sometimes also insufficient。
On the other hand, about epoxy resin, the epoxy resin meeting these requirements is also not yet known。For example it is known that bisphenol-type epoxy resin, owing to being liquid at normal temperatures, operability is excellent, and the mixing with firming agent, additive etc. is easy, is therefore widely used, but on this point of thermostability, moisture-proof existing problems。It addition, as the epoxy resin improving thermostability, it is known to o-cresol phenolic epoxy varnish, but about anti-flammability, for insufficient。
As being used for the countermeasure that do not use halogenated flame retardant and make anti-flammability improve, the method disclosing the fire retardant of interpolation phosphate ester system。But, in using the method for fire retardant of phosphate ester system, moisture-proof is insufficient。It addition, under high temperature, many wet environment, there is the problem that phosphate ester is hydrolyzed, makes to reduce as the reliability of insulant。
As not containing phosphorus atoms, halogen atom and the epoxy resin that makes anti-flammability improve, disclosed in patent documentation 2 and 3, there is the example that the aralkyl-type epoxy resin with biphenyl structure is applied to semiconductor-encapsulating material。The example using the aralkyl-type epoxy resin with naphthalene structure is had disclosed in patent documentation 4。But, these epoxy resin are all insufficient in the arbitrary middle performance of anti-flammability, moisture-proof or thermostability。
As the example of the raising being conceived to thermostability, moisture-proof, crack resistance, there are Benzylation polyphenol and epoxy resin thereof disclosed in patent documentation 5, but these materials are not conceived to anti-flammability。It addition, there is the manufacture method of phenylethene modified novolaks (ノ ボ ラ ッ Network) disclosed in patent documentation 6, but obtain the manufacture method gazed at not as composition epoxy resin。
And then, example as the composition epoxy resin of the raising being conceived to moisture-proof, low stress, there is phenylethene modified phenol resol resins disclosed in patent documentation 7 and 8 and use the composition epoxy resin of this epoxy resin, but they are also without the example that the molecular weight distribution of styrenated phenol novolaks and epoxy resin carries out research in detail。Being explained, molecular weight distribution (dispersion) represents with Mw/Mn。
On the other hand, as the example of the raising being conceived to anti-flammability, there is phenylethene modified phenol resol resins disclosed in patent documentation 9 and use the composition epoxy resin of this epoxy resin。At this, it is conceived to phenylethene modified amount, uses the resin adjusting hydroxyl equivalent or epoxide equivalent by increasing modified amount higher。Think in the solidfied material using such resin, by making the containing ratio being derived from the aliphatic character of epoxy radicals relatively reduce, the anti-flammability of height can be manifested。But, at this also without the example that the molecular weight distribution of multi-hydroxy resin and epoxy resin is carried out research in detail。
Prior art literature
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
It is an object of the invention to, there is provided a kind of in stacking, shaping, casting, the purposes such as bonding curable and mechanical properties excellent and there is the epoxy resin of the also excellent performance such as anti-flammability, moisture-proof, low elasticity, there is provided a kind of curable with excellence and mechanical property and give the also excellent solidfied material such as anti-flammability, moisture-proof, low elasticity to useful composition epoxy resins such as the sealing of electrical/electronic part class, circuit base materials, and provide its solidfied material。
Namely, the present invention relates to a kind of aralkyl modified multi-hydroxy resin, it is characterized in that, it reacts with aralkyl agent for making the multi-hydroxy compound shown in following formula (1), the substituent group being derived from aralkyl agent shown in formula (a) is made to be replaced on the phenyl ring of multi-hydroxy compound the aralkyl modified multi-hydroxy resin obtained, multi-hydroxy compound as formula (1), the area % to measure with gel permeation chromatography (GPC) is used to count n=1 composition for 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。
(this, R1And R2Represent the alkyl of hydrogen atom or carbon number 1～6, R3And R4 represents hydrogen atom or the alkyl of carbon number 1～6, n represents the number of 1～5)
The another way of the present invention is a kind of phenylethene modified multi-hydroxy resin, it is characterized in that, it reacts with phenylethylene for making the multi-hydroxy compound shown in above-mentioned formula (1), the cinnamic substituent group that is derived from shown in formula (a2) is made to be replaced on the phenyl ring of multi-hydroxy compound the phenylethene modified multi-hydroxy resin obtained, multi-hydroxy compound as formula (1), use and count n=l composition for less than 15% with the GPC area % measured, 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。
(this, R2With formula (a) synonym)。
The another way of the present invention is the manufacture method of a kind of aralkyl modified multi-hydroxy resin, it is characterized in that, the multi-hydroxy compound shown in above-mentioned formula (1) is made to react with the aralkyl agent shown in following formula (b1) or (b2) in manufacture, when making the substituent group being derived from aralkyl agent shown in above-mentioned formula (a) be replaced on the phenyl ring of multi-hydroxy compound the aralkyl modified multi-hydroxy resin obtained, multi-hydroxy compound as formula (1), use and count n=l composition for less than 15% with the GPC area % measured, 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 reaction temperature 40～120 DEG C。
(this, R2Represent the alkyl of hydrogen atom or carbon number 1～6, R3And R4Representing the alkyl of hydrogen atom or carbon number 1～6, X represents halogen, OH or OR5, R5Represent the alkyl of carbon number 1～6)。
In the manufacture method of above-mentioned aralkyl modified multi-hydroxy resin, it is preferred to relative to the hydroxyl 1 mole of multi-hydroxy compound, make aralkyl agent 0.1～1.5 molar reactive, or aralkyl agent is styrene。
The another way of the present invention is a kind of composition epoxy resin and solidfied material thereof, described composition epoxy resin is characterised by, comprise epoxy resin and firming agent, as part or all of firming agent, form as neccessary composition using above-mentioned aralkyl modified multi-hydroxy resin。
The another way of the present invention is a kind of epoxy resin, it is characterised in that make above-mentioned aralkyl modified multi-hydroxy resin and epichlorohydrin reaction obtain。It addition, the manufacture method that another way is a kind of epoxy resin, it is characterised in that make above-mentioned aralkyl modified multi-hydroxy resin and epichlorohydrin reaction, the hydroxyl of aralkyl modified multi-hydroxy resin is formed glycidyl ether。
The 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 firming agent, wherein, carries out cooperation using above-mentioned epoxy resin as neccessary composition and forms。
Accompanying drawing explanation
Fig. 1 is the GPC figure of multi-hydroxy compound A。
Fig. 2 is the GPC figure of multi-hydroxy compound 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。
Detailed description of the invention
In epoxy resin cured product, think that the hydroxypropyl generated due to the reaction of epoxy radicals and hydroxyl easily burns, but by multi-hydroxy compound addition aralkyl is improved hydroxyl equivalent, it is derived from the aliphatic carbon rate step-down of the inflammable constituent of epoxy radicals, it is possible to visualise the anti-flammability of height。It addition, the addition of the aralkyl by being imbued with aromatic series, the aromatic series of multi-hydroxy resin improves further, except anti-flammability, the raising of moisture-proof is also effective。
But, on the other hand, the method bringing physical property to improve by increasing the modified ratio of aralkyl has the tendency that the curable caused because of the increase of steric hindrance reduces, makes the mechanical strength of solidfied material reduce。Therefore, by controlling the molecular weight distribution of the multi-hydroxy compound of substrate, in the aralkyl modified ratio not damaging curable, mechanical strength, and then it is found that the aralkyl modified multi-hydroxy resin and epoxy resin that curable, mechanical strength and anti-flammability, moisture-proof and low elasticity are also excellent。
The multi-hydroxy compound used in the present invention is the narrow dispersion multi-hydroxy compound shown in formula (1), therefore, also referred to as multi-hydroxy compound (1) or narrow dispersion multi-hydroxy compound。Further, since be also a kind of novolac resin, so also referred to as phenol novolacs。
When employing the aralkyl modified multi-hydroxy resin using narrow dispersion multi-hydroxy compound as substrate and epoxy resin, the composition epoxy resin that curable, mechanical strength and anti-flammability etc. are excellent can be obtained。That is, when the ratio of the aralkyl modified thing of n=1 (the 2 officials can) composition for multi-hydroxy compound increases, due to the increase of steric hindrance, thus have curable to reduce, tendency that the mechanical strength of solidfied material also reduces。On the other hand, when the multi-hydroxy compound that the ratio using the n=2 as more multifunctional composition (3 officials' energy) and n=3 (4 officials' energy) composition is high, even if due to when having carried out aralkyl modified, the impact of steric hindrance also relatively reduces, thus the solidfied material of curable, mechanical strength can be obtained。It addition, when multifunctional composition increases, owing to the crosslink density of solidfied material increases, thus becoming the solidfied material that heat stability is more excellent, the tendency that display anti-flammability is also excellent。But, when n=4 (5 officials' energy) above composition increases, molecular weight uprises, and accordingly, there exist the tendency of mobility, shaping processability difference。
Therefore, these materials are used can to obtain the composition epoxy resin that curable, mechanical strength and anti-flammability etc. are excellent, especially epoxy resin composition for encapsulating semiconductor。That is, manifest the excellent curable of these compositionss, manifest mechanical strength, high flame retardant, moisture-proof, physical property that low elasticity is excellent simultaneously, use this material can obtain high electric, the sealing of electronic component class of reliability, circuit base material etc.。
First, the aralkyl modified multi-hydroxy resin (StPN) of the present invention is illustrated。The aralkyl modified multi-hydroxy resin of the present invention can pass through to make in the multi-hydroxy compound shown in formula (1), with gel permeation chromatography (GPC；RI) area % during detection count 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 react with aralkyl agent and obtain。
The aralkyl modified multi-hydroxy resin of the present invention is called StPN, the multi-hydroxy compound shown in the formula (1) used to obtain StPN is called multi-hydroxy compound or narrow dispersion multi-hydroxy compound。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)。It addition, sometimes represent aralkyl agent with styrene, 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%, it is preferred to the scope of less than 10%。It addition, the containing ratio of n=2 and n=3 composition range for more than 50%, more preferably more than 60%, the more preferably scope of more than 70%。By reducing the containing ratio of n=l composition, it is possible to improve the physical property such as curable, mechanical strength, anti-flammability。And then, dispersion (Mw/Mn) range preferably from less than 1.2, 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 curable, mechanical strength。Being explained, owing to GPC area % and wt% is generally proportionate, therefore GPC area % can be considered wt%。
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 removes low molecular weight compositions obtain。
The mol ratio aldehydes of phenols and aldehydes represents relative to the mol ratio of phenols 1 mole, manufactures with the scope of 0.1～0.9, in mol ratio hour, more generate n=l～3 composition, when mol ratio is big, more generating the high molecular weight components of more than n=4, n=l～3 composition tails off。
Method that the narrow dispersion multi-hydroxy compound used in the present invention can pass through the operation that makes phenols and aldehydes under the existence of phosphorus acid catalyst, utilize nonuniformity system to make it react and obtain, utilize various solvent poorly soluble from the thick multi-hydroxy compound obtained the method for more than removing n=l composition and/or n=4 composition high molecular weight components, in aqueous alkali, dissolve two nucleomes (two nucleomes) and the method etc. that carries out removing obtains but it also may obtained by other well-known separation method。
The StPN of the present invention obtains by making the narrow dispersion multi-hydroxy compound shown in formula (1) and aralkyl agent carry out additive reaction。Now, ratio as multi-hydroxy compound and aralkyl agent, if considering the anti-flammability of obtained solidfied material and the balance of curable, then aralkyl agent is preferably the scope of 0.1～1.5 mole relative to the usage ratio of multi-hydroxy compound 1 mole, it is more preferably 0.1～1.0 mole, more preferably the scope of 0.3～0.8 mole。When less than this scope, for the state that the character of the multi-hydroxy compound of raw material does not improve, when more than this scope, functional group densities excessively step-down and have the tendency that curable reduces。
In the reaction, addition on the aralkyl agent aromatic ring with OH base in multi-hydroxy compound, the aralkyl shown in above-mentioned formula (a) replaces。In formula (a), R3And R4Represent the alkyl of hydrogen atom or C1～6。Alkyl is preferably methyl。More preferably R3And R4In a side or two sides be hydrogen atom or methyl, it is preferred that a side or two sides are hydrogen atom。When two sides are hydrogen atom, it is benzyl, when a side is hydrogen atom, is alpha-alkyl substituted benzyl。Substituent R can also be had at the benzene substitution in ring of this benzyl or alpha-alkyl substituted benzyl2。The Adding sites of aralkyl is in the ortho position in the room of multi-hydroxy compound and/or para-position, but is mainly para-position。
It addition, the melt viscosity at the 150 of the StPN of the present invention DEG C is preferably the scope of 0.01～10.0Pa s。From the viewpoint of operability, melt viscosity is more low more good in above-mentioned scope。
And then, softening point can be 40～150 DEG C, it is preferred to the scope of 50～100 DEG C。At this, softening point refers to the softening point that the ring and ball method based on JIS-K-2207 measures。If lower than this softening point, then when coordinating StPN in the epoxy, the thermostability of solidfied material reduces, if higher than this softening point, then mobility when shaping reduces。
The addition amount of aralkyl can be adjusted, generally for the phenyl ring addition 0.1～2.5 of multi-hydroxy compound according to the consumption that makes of aralkyl agent。This refers to the average (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, the order with 0.1～1.5 mole, 0.1～1.0 mole, 0.3～0.8 mole is preferred。It is explained, owing to 4 aralkyl can be replaced at most on the phenol ring of two ends, middle phenol ring can replace at most 3 aralkyl, therefore, when n is 1,8 aralkyl can be replaced at most。
In formula (a), R2Represent the alkyl of hydrogen or carbon number 1～6, it is preferred to the alkyl of hydrogen or carbon number 1～3, more preferably hydrogen。This R2Can be determined by the aralkyl agent used as reaction raw materials。
In formula (1), n represents the number of 1～5, it is preferable that average (quantity is average) is the scope of 1.9～3.4, the more preferably scope of 2.0～3.0, but must is fulfilled for above-mentioned dispersion。From another viewpoint, n is the composition of 1～5 can be main constituent。Main constituent refers to more than 80wt%, it is preferred to more than 90wt%, is more preferably essentially all。In formula (1), R1Represent the alkyl of hydrogen atom or carbon number 1～6, it is preferable that represent the alkyl of hydrogen atom or carbon number 1～4。
Then, the manufacture method of the StPN of the present invention is illustrated。As the multi-hydroxy compound that the formula (1) used in the method manufacturing StPN of the present invention represents, phenol novolacs class is suitable。Phenol novolacs can be obtained by phenols and aldehydes。
As being used for obtaining the phenols of this multi-hydroxy compound, it is mainly phenol。This phenols can also contain other a small amount of phenol composition。Such as can enumerate orthoresol, metacresol, paracresol, ethyl phenols, isopropyl phenols, tert-butyl group phenols, pi-allyl phenols, phenyl phenols etc.。These phenols can be used alone, it is also possible to and use two or more。Be explained, if on a small quantity, then can coordinate 2，6-xylenol, 2,6-diethyl phenol, hydroquinone, resorcinol, catechol, 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, can be limited to below 30wt%, preferred below 20wt%。
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 phenylethylene。Phenylethylene is the styrene of the alkyl replacement of styrene or carbon number 1～6。In formula (c1), R3Alkyl for hydrogen or carbon number 1～6, it is preferred to hydrogen。This phenylethylene can also contain other a small amount of reacted constituent, as other reacted constituent, can enumerate the composition containing unsaturated bond such as divinylbenzene, indenes, coumarone, benzothiophene, indole, vinyl naphthalene。When coordinating these materials, can be limited to less than 30%, preferred below 20wt%。
In above-mentioned formula (c2), R2、R3And R4R with formula (a)2、R3And R4Synonym。X is halogen atom, the alkoxyl of carbon number 1～6 or hydroxyl。In formula (c1), R2、R3R with formula (a)2、R3Synonym。
As the aralkyl agent shown in above-mentioned formula (c2), when X is halogen atom, can enumerate: benzyl chloride, benzyl bromide a-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, it is preferred to the alkoxyl of carbon number 1～4, can enumerate: benzyl methyl ether, adjacent methyl-benzyl methyl ether, between methyl-benzyl methyl ether, to methyl-benzyl methyl ether, to Ethylbenzyl methyl ether, benzylisoeugenol, 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: benzyl alcohol, o-methyl-benzene methanol, between methylbenzyl alcohol, to methylbenzyl alcohol, to ethylo benzene methanol, cumyl alcohol, to butyl-benzyl alcohol, to cyclohexyl benzene methanol, to phenyl benzil alcohol, α-methylbenzylalcohol, alpha, alpha dimethyl benzyl alcohol etc.。As the aralkyl agent shown in formula (c1), can enumerate: styrene, have the ring-alkylated styrenes of alkyl of C1～6, alpha-alkyl phenylethylene class etc. at cinnamic benzene substitution in ring, it is preferred to alkylbenzene second is rare or benzene second is rare, more preferably benzene second is rare。
The aralkyl glycosylation reaction adopting aralkyl agent can carry out in the presence of acid catalyst, and this catalytic amount uses with the scope of 10～1000ppm (wt), it is preferred to the scope of 100～500ppm。If higher than this scope, then the methylene-crosslinked key of multi-hydroxy compound becomes to be easily broken off, and due to the secondary monohydric phenol composition generated of cleavage reaction institute, and makes curable and thermostability reduction。On the other hand, if lower than scope, then reactive reduction, makes unreacted aralkyl agent remaining in a large number。It addition, catalytic amount said here refers to the amount of total weight of multi-hydroxy compound that catalyst uses relative to reaction and aralkyl agent。
As acid catalyst, it is possible to suitable selection from well-known mineral acid, organic acid。Such as can enumerate: the mineral acids such as hydrochloric acid, sulphuric acid, phosphoric acid, the organic acid such as formic acid, oxalic acid, trifluoracetic acid, p-methyl benzenesulfonic acid, dimethyl sulfate, diethyl sulphuric acid, the solid acid etc. such as lewis acid or ion exchange resin, active hargil, silica-alumina, zeolite such as zinc chloride, aluminum chloride, iron chloride, boron trifluoride。
It addition, the reaction temperature in this reaction carries out in the scope of 40～120 DEG C。If lower than this scope, then reactive reduction, the response time becomes long-time。If it addition, higher than this scope, then the methylene-crosslinked key of multi-hydroxy compound becomes to be easily broken off, make curable and thermostability reduction due to the secondary monohydric phenol composition generated of cleavage reaction institute。
It addition, this reaction generally carries out 1～20 hour。And then, when reacting, the alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, ethyl cellosolve can be used, the ketones such as acetone, methyl ethyl ketone, methylisobutylketone, the ethers such as dimethyl ether, Anaesthetie Ether, Di Iso Propyl Ether, oxolane, dioxane, aromatic compound such as benzene, toluene, chlorobenzene, dichloro-benzenes etc. is as solvent。
As the concrete grammar implementing this reaction, whole raw materials are loaded in the lump, directly reacts at specified temperatures, or multi-hydroxy compound and catalyst are loaded, while being maintained at the temperature of regulation, dripping aralkyl agent, it is general for making its method reacted simultaneously。Now, time for adding is preferably less than 5 hours, is generally 1～10 hour。After reaction, when using solvent, it is possible to after eliminating catalyst component, evaporate solvent and obtain the resin of the present invention, when not using solvent, by directly discharging when heat, it is possible to obtain goal object。
Then, the epoxy resin (StPNE) of the present invention is illustrated。
The epoxy resin (StPNE) of the present invention can by obtaining StPN epoxidation。
For the StPNE of the present invention, by making above-mentioned StPN and epichlorohydrin reaction manufacture and be advantageous for。Make StPN can carry out in the same manner as common epoxidation reaction with the reaction of epichlorohydrin reaction。
Such as can enumerate after making above-mentioned StPN be dissolved in excessive epoxychloropropane, 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 consumption hydroxyl relative to StPN 1 mole that makes of alkali metal hydroxide now is 0.8～1.5 mole, it is preferred to the scope of 0.9～1.2 mole。It addition, epoxychloropropane uses relative to hydroxyl 1 molar excess in StPN, the hydroxyl 1 mole being commonly angled relative in StPN is 1.5～30 moles, it is preferred to the scope of 2～15 moles。Reaction evaporates excessive epoxychloropropane, is dissolved in by residue in toluene, methyl iso-butyl ketone (MIBK) equal solvent, and filters, wash after terminating, and removes inorganic salt, then evaporates solvent, it is hereby achieved that the epoxy resin of purpose。
The composition epoxy resin of the present invention at least contains epoxy resin and firming agent, has following 3 kinds。
1) the above-mentioned StPNE some or all of compositions as epoxy resin it is combined with。
2) the above-mentioned StPN some or all of compositions as firming agent it is combined with。
3) above-mentioned StPNE and the StPN some or all of compositions as epoxy resin and firming agent it is combined with。
When above-mentioned 2) and 3) compositions, containing StPN as neccessary composition。It is 2～200 weight portions that the use level of StPN is commonly angled relative to epoxy resin 100 weight portion, it is preferred to the scope of 5～80 weight portions。If lower than this scope, then the effect that anti-flammability and moisture-proof improve is little, if higher than this scope, then there is the problem that the intensity of formability and solidfied material reduces。
When use StPN is as the total amount of firming agent, the use level of usual StPN considers that the OH base of StPN coordinates with the equivalent balanced of the epoxy radicals in epoxy resin。The equivalent proportion of epoxy resin and firming agent is generally the scope of 0.2～5.0, it is preferred to the scope of 0.5～2.0。If bigger than this scope or little, then the curable of composition epoxy resin reduces, and the thermostability of solidfied material, mechanical strength etc. reduce simultaneously。
As firming agent, it is possible to and with the firming agent beyond StPN。The use level of other firming agent the use level of StPN is generally remained in relative to epoxy resin 100 weight portion be 2～200 weight portions, be preferably 5～80 weight portions scope scope in determine。If the use level of StPN is lower than this scope, then the effect that agent of low hygroscopicity, adaptation and anti-flammability improve is little, if higher than this scope, then there is the problem that the intensity of formability and solidfied material reduces。In this case, the equivalent proportion of epoxy resin and firming agent (total) is set to above-mentioned scope。
As the firming agent beyond StPN, the material known generally as the firming agent of epoxy resin all can use, and has: dicyanodiamide, anhydrides, polyatomic phenol, aromatic series and aliphatic amine etc.。Wherein, the field of high electrical insulating properties is required at semiconductor-encapsulating material etc., it is preferred to use polyatomic phenol is as firming agent。When the compositions using the StPN of the present invention as neccessary composition, the use level of StPN can be 50～100% in firming agent entirety, be preferably the scope of 60～100%。Hereinafter, the concrete example of the firming agent beyond expression StPN。
As anhydride curing agent, for instance that phthalic anhydride, tetrabydrophthalic anhydride, methyl tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl-5-norborene-2,3-dicarboxylic anhydride (acid of メ チ Le water Ha イ ミ ッ Network), dodecenyl succinic (De デ シ ニ Le) succinic anhydrides, Na Dike (Na ジ ッ Network) anhydride, trimellitic anhydride etc.。
As polyatomic phenol, for instance that bisphenol-A, Bisphenol F, bisphenol S, fluorenes bis-phenol, 4,4 '-xenol, 2,2 yuan of phenols such as 2 '-xenol, hydroquinone, 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, bisphenol-A, Bisphenol F, bisphenol S, fluorenes bis-phenol, 4, the polynary phenoloid etc. of the condensing agent synthesis such as 2 yuan of phenols such as 4 '-xenol, 2,2 '-xenol, hydroquinone, resorcinol, naphthalenediol and formaldehyde, acetaldehyde, benzaldehyde, hydroxy benzaldehyde, terephthaldehyde's base dichloro, dichloride methyl biphenyl, dichloride methyl naphthalene。
As amine, have: 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino-diphenyl propane, 4, the aliphatic amine such as the aromatic amine of 4 '-diamino diphenyl sulfone, m-diaminobenzene., terephthaldehyde's base diamidogen etc., ethylenediamine, hexamethylene diamine, Diethylenetriamine, three second tetramines。
In above-mentioned composition, it is possible to use a kind of these firming agent or mix two or more and use。
As in above-mentioned composition use epoxy resin, have from 1 molecule more than 2 epoxy radicals epoxy resin in selection。Such as can enumerate: bisphenol-A, 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 bicyclopentadiene 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) compositions, containing StPNE as neccessary composition。In this composition epoxy resin, as epoxy resin ingredient, it is also possible to the epoxy resin of other kind beyond cooperation StPNE。As epoxy resin now, the common epoxy resin of the epoxy radicals in the molecule with more than 2 all can use。If enumerating example, then have: bisphenol-A, bisphenol S, fluorenes bis-phenol, 4,4 '-xenol, 2,2 yuan of phenols such as 2 '-xenol, hydroquinone, resorcinol or three-(4-hydroxy phenyl) methane, 1,1, the glycidyl etherified thing etc. that the halogenated bisphenols classes such as 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, naphthols system aralkyl resin class or tetrabromobisphenol A are derived。These epoxy resin can use a kind or mix two or more and use。And, when with the StPNE of the present invention compositions being neccessary composition, the use level of StPNE can be 50～100% in epoxy resin entirety, it is preferred to the scope of 60～100%。
In the composition epoxy resin of the present invention, it is also possible to be suitable for the modifying agent etc. coordinating the oligomer of polyester, polyamide, polyimides, polyethers, polyurethane, Petropols, indene resin, indenes coumarone resin, phenoxy resin etc. or macromolecular compound as other。Relative to epoxy resin 100 weight portion, addition is generally the scope of 2～30 weight portions。
It addition, in the composition epoxy resin of the present invention, it is possible to coordinate the additives such as inorganic filler, pigment, fire retardant, thixotropy conferring agents, coupling agent, fluidity improving agent。As inorganic filler, such as can enumerate: spherical or SiO 2 powder, alumina powder, the glass powder such as the fused silica of broken shape, crystalline silica, or Muscovitum, Talcum, calcium carbonate, aluminium oxide, hydrated alumina etc., preferred use level during for semiconductor-encapsulating material is more than 70 weight %, more preferably more than 80 weight %。
As pigment, have: the extender pigment of organic or inorganic, flakey pigment etc.。As thixotropy conferring agents, can enumerate: silicon system, Oleum Ricini system, aliphatic amide wax, OPE, organobentonite etc.。
And then, in the composition epoxy resin of the present invention, it is possible to use curing accelerator as required。If enumerating example, then have: amine, imidazoles, organic phosphine class, lewis acid etc., specifically, have: 1, 8-diazabicyclo (5, 4, 0) hendecene-7, triethylenediamine, benzyldimethylamine, 2,4, triethanolamine, dimethylaminoethanol, the tertiary amine of three (dimethylaminomethyl) phenol etc., 2-methylimidazole, 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, tetraphenyl tetraphenylborate, tetraphenyl ethyl triphenyl borate, tetrabutyl tetrabutyl borates etc. four replace four substituted boracic acid esters, 2-ethyl-4-methylimidazole tetraphenylborate, the tetraphenyl boron salt etc. such as N-methylmorpholine tetraphenylborate。Relative to epoxy resin 100 weight portion, it is generally the scope of 0.2～5 weight portion as addition。
And then, as required, it is possible in the resin combination of the present invention, use the lubricants etc. such as the low stress agent such as fire retardant, silicone oil, calcium stearate such as the coloring agent such as coupling agent, white carbon black, antimony trioxide such as the releasing agent such as Brazil wax, OP wax, γ-glycidoxypropyltrime,hoxysilane。
The composition epoxy resin of the present invention, it is possible to after forming the varnish state being dissolved with organic solvent, after being impregnated in the fibrous materials such as polyester non-woven fabric such as glass cloth, aromatic polyamide non-woven fabrics, liquid crystal polymer, carry out solvent removing, and become prepreg。It addition, as required, it is possible to by being coated on, the tablets such as Copper Foil, stainless steel foil, Kapton, mylar become sandwich。
If being heating and curing by the composition epoxy resin of the present invention, then can becoming epoxy resin cured product, this solidfied material is excellent in curable, anti-flammability, agent of low hygroscopicity, low elasticity etc.。Composition epoxy resin can be formed processing by methods such as casting, compression molding, transfer modlings and obtain by this solidfied material。Temperature now is generally the scope of 120～220 DEG C。
Embodiment
Hereinafter, by embodiment, further illustrate the present invention。The unit of hydroxyl equivalent and epoxide equivalent is g/eq.。
Synthesis example 1
The four-hole boiling flask of 1L adds phenol 250g, oxalic acid dihydrate 0.75g as acid catalyst, imports nitrogen, while being stirred, being heated and heating up。Start to drip 37.4% formalin 47.4g in 80 DEG C, terminated dropping with 30 minutes。Further reaction temperature is maintained at 92 DEG C, carries out reaction in 3 hours。While carrying out heating up, water generation reaction being removed to system, being warming up to 110 DEG C。The phenol of remaining is under reduced pressure reclaimed in 160 DEG C。Further improve temperature and reclaim the parts of two nucleomes。The hydroxyl equivalent of the multi-hydroxy compound of gained is 104, and softening point is 68 DEG C, and the melt viscosity at 150 DEG C is 0.07Pa s。The containing ratio of the n=l composition that GPC measures gained is 8.1%, and the total containing ratio of n=2 and n=3 composition is 71.7%, Mw/Mn=1.10。This resin is called multi-hydroxy compound A。Fig. 1 represents the GPC figure of multi-hydroxy compound A。
Synthesis example 2
The four-hole boiling flask of 1L adds phenol 250g, 7.4% formalin 47.4g, 89% phosphatase 11 50g as acid catalyst, is heated under passing through the basis stirring the nebulousurine state (2 phase mixture) mixed and formed and heats up。It is maintained at reflux for temperature further, reacts 6 hours。Then, add methyl iso-butyl ketone (MIBK) and stand after dissolving resin part, be separated into resin solution phase and phosphate aqueous solution phase。Remove phosphoric acid solution mutually after, wash further。Then, the phenol of remaining is under reduced pressure reclaimed in 160 DEG C。Further improve temperature and reclaim the parts of two nucleomes。The hydroxyl equivalent of the multi-hydroxy compound of gained is 103, and softening point is 65 DEG C, and the melt viscosity at 150 DEG C is 0.06Pa s。The containing ratio of the n=l composition that GPC measures gained is 2.0%, and the total containing ratio of n=2 and n=3 composition is 91.5%, Mw/Mn=1.04。This resin is called multi-hydroxy compound B。Fig. 2 represents the GPC figure of multi-hydroxy compound B。
Embodiment 1
The four-hole boiling flask of 1L adds as the multi-hydroxy compound A104g obtained in the synthesis example 1 of multi-hydroxy chemical composition, as the p-methyl benzenesulfonic acid 0.053g (300ppm) of acid catalyst, be warming up to 120 DEG C。Then, it is stirred at 120 DEG C, while dripping styrene 72.8g (0.7 mole) with 3 hours and making it react。And then, after reacting 1 hour in 120 DEG C, obtain phenylethene modified multi-hydroxy resin 168g。Its hydroxyl equivalent is 177, and softening point is 78 DEG C, and the melt viscosity at 150 DEG C is 0.13Pa s。This resin is called modified multicomponent hydroxy resin A (StPN-A)。Fig. 4 represents the GPC figure of StPN-A。
Embodiment 2
The four-hole boiling flask of 1L adds as the multi-hydroxy compound B-11 03g obtained in the synthesis example 2 of multi-hydroxy chemical composition, as the p-methyl benzenesulfonic acid 0.053g (300ppm) of acid catalyst, be warming up to 120 DEG C。Then, it is stirred at 120 DEG C, while dripping styrene 72.8g (0.7 mole) with 3 hours and making it react。And then, after reacting 1 hour in 120 DEG C, obtain ha styt-ehe modified multicomponent hydroxy resin 167g。Its hydroxyl equivalent is 176, and softening point 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
The four-hole boiling flask of 1L adds as the multi-hydroxy compound A104g obtained in the synthesis example 1 of multi-hydroxy chemical composition, water l.0g, be warming up to 120 DEG C。Then, it is stirred at 120 DEG C, while dripping benzyl chloride 88.6g (0.7 mole) with 3 hours and making it react。And then, after reacting 1 hour in 120 DEG C, obtain benzyl modified multicomponent hydroxy resin 160g。Its hydroxyl equivalent is 168, and softening point is 70 DEG C, and the melt viscosity at 150 DEG C is 0.09Pa s。This resin is called modified multicomponent hydroxy resin C (StPN-C)。Fig. 6 represents the GPC figure of StPN-C。
Comparative example 1
The four-hole boiling flask of 1L adds phenol novolacs (the Showa electrician's system as multi-hydroxy chemical composition；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 be 25.4%, the total containing ratio of n=2 and n=3 composition is 32.1%, Mw/Mn=1.45, hydroxyl equivalent 105, softening point 67 DEG C, melt viscosity 0.08Pa s) 105g at 150 DEG C, p-methyl benzenesulfonic acid 0.055g (300ppm) as acid catalyst, it is warming up to 120 DEG C。Then, it is stirred at 120 DEG C, while dripping styrene 73g (0.7 mole) with 3 hours and making it react。And then, after reacting 1 hour in 120 DEG C, obtain phenylethene modified multi-hydroxy resin 170g。Its hydroxyl equivalent is 178, and softening point is 78 DEG C, and the melt viscosity at 150 DEG C is 0.13Pa s。This resin is called modified multicomponent hydroxy resin D (StPN-D)。Fig. 7 represents the GPC figure of StPN-D。
Embodiment 4
Four mouthfuls of removable flasks add the StPN-A150g, epoxychloropropane 470g, the diethylene glycol dimethyl ether 71g that obtain in embodiment 1, is stirred dissolving。After dissolving equably, 65 DEG C it are maintained under the decompression of 130mmHg, 48% sodium hydrate aqueous solution 70.6g is dripped with 4 hours, the water distillated refluxing in this dropping in separating tank and epoxychloropropane are easily separated, epoxychloropropane returns to reaction vessel, is removed by water and reacts to system。After reaction terminates, remove, by filtering, the salt generated, evaporate epoxychloropropane further after water washing, obtain epoxy resin A (StPNE-A) 168g。The epoxide equivalent of the resin of gained is 241, and softening point 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
Four mouthfuls of removable flasks add the StPN-B150g, epoxychloropropane 473g, the diethylene glycol dimethyl ether 71g that obtain in embodiment 2, is stirred dissolving。After dissolving equably, 65 DEG C it are maintained under the decompression of 130mmHg, 48% sodium hydrate aqueous solution 71.0g is dripped with 4 hours, the water distillated refluxing in this dropping in separating tank and epoxychloropropane are easily separated, epoxychloropropane returns to reaction vessel, is removed by water and reacts to system。After reaction terminates, remove, by filtering, the salt generated, evaporate epoxychloropropane further after water washing, obtain epoxy resin B (StPNE-B) 165g。The epoxide equivalent of the resin of gained is 245, and softening point is 55 DEG C, and the melt viscosity at 150 DEG C is 0.11Pa s。Fig. 9 represents the GPC figure of StPNE-B。
Embodiment 6
Four mouthfuls of removable flasks add the StPN-C150g, epoxychloropropane 495g, the diethylene glycol dimethyl ether 74g that obtain in embodiment 3, is stirred dissolving。After dissolving equably, 65 DEG C it are maintained under the decompression of 130mmHg, 48% sodium hydrate aqueous solution 74.4g is dripped with 4 hours, the water distillated refluxing in this dropping in separating tank and epoxychloropropane are easily separated, epoxychloropropane returns to reaction vessel, is removed by water and reacts to system。After reaction terminates, remove, by filtering, the salt generated, evaporate epoxychloropropane further after water washing, obtain epoxy resin C (StPNE-C) 185g。The epoxide equivalent of the resin of gained is 236, and softening point is 52 DEG C, and the melt viscosity at 150 DEG C is 0.08Pa s。Figure 10 represents the GPC figure of StPNE-C。
Comparative example 2
Four mouthfuls of removable flasks add the StPN-D150g, epoxychloropropane 468g, the diethylene glycol dimethyl ether 70g that obtain in comparative example 1, is stirred dissolving。After dissolving equably, 65 DEG C it are maintained under the decompression of 130mmHg, 48% sodium hydrate aqueous solution 70.3g is dripped with 4 hours, the water distillated refluxing in this dropping in separating tank and epoxychloropropane are easily separated, epoxychloropropane returns to reaction vessel, is removed by water and reacts to system。After reaction terminates, remove, by filtering, the salt generated, evaporate epoxychloropropane further after water washing, obtain epoxy resin 185g (StPNE-D)。The epoxide equivalent of the resin of gained is 246, and softening point is 56 DEG C, melt viscosity at 150 DEG C is 0.l0Pa s。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；Epoxide equivalent 200, softening point 65 DEG C), as firming 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 (group's honor chemical industry system)；OH equivalent 103, softening point 82 DEG C)。Using the mixing silicon dioxide as filler of the cooperation (mean diameter 18pm) shown in table 1, the triphenylphosphine as curing accelerator, obtain composition epoxy resin。Use this composition epoxy resin, form at 175 DEG C, solidify after carrying out at 175 DEG C 12 hours, after obtaining solidfied material test film, for various physical property measurements。Following presentation details, table 2 represents result。
(1) gel permeation chromatography (GPC) measures
Using the equipment in series having TOSOH Co., Ltd TSKgelG4000HXL, TSKgelG3000HXL, TSKgelG2000HXL, column temperature is set to 40 DEG C。It addition, eluant uses oxolane, setting the flow velocity of 1ml/min, detector uses RI (differential refractometer) detector。Sample 0.lg is dissolved in the THF of 10ml。After utilizing the standard curve of polystyrene standard to obtain weight average molecular weight (Mw) and number-average molecular weight (Mn), obtain dispersion (Mw/Mn)。
(2) softening point
Use automatic softening point measurement device (Ming Feng society ASP-M4SP), according to JIS-K-2207, be measured by ring and ball method。
(3) melt viscosity
Use BROOKFIELD CAP2000H type rotating cylinder viscometer, be measured at 150 DEG C。
(4) mensuration of hydroxyl equivalent
Using potential difference titration appratus, solvent uses Isosorbide-5-Nitrae-dioxane, carries out acetylation with 1.5mol/L chloroacetic chloride, with the chloroacetic chloride that water decomposition is excessive, uses the potassium hydroxide of 0.5mol/L to carry out titration。
(5) mensuration of epoxide equivalent
Use potential difference titration appratus, use methyl ethyl ketone as solvent, add tetraethylammonium bromide acetum, by potential difference titration appratus, use 0.lmol/L perchloric acid-acetum to be measured。
(6) gel time
Be heated to be 175 DEG C gelation testing machine (day new science (strain) system) plate on add composition epoxy resin, use fluororesin rod, it is stirred with the speed of one second 2 circle, the gelation time that research is required to epoxy resin composition。
(7) hardness during heat
Form under mold temperature 175 DEG C, 90 seconds hardening times, after die sinking 10 seconds, use Shore D hardness measurement to determine Shore D hardness value, it is set to hardness during heat。
(8) glass transition point (Tg), line expand number (CTE)
Utilize SEIKO instrument TMA120C type thermomechanical determinator, Tg is obtained when programming rate 10 DEG C/min, for α 1 (CTE of below Tg), obtain the meansigma methods of the scope of 30～50 DEG C, and for α 2 (CTE of more than Tg), obtain from the meansigma methods of the scope of Tg+20 DEG C～40 DEG C。
(9) bending strength and the elasticity of flexure
According to JISK6911, it is measured at normal temperatures by 3 bend test methods。
(10) water absorption rate
The condition of 25 DEG C, relative humidity 50% is set to standard state, be set to 85 DEG C, relative humidity 85% when make its moisture absorption 100 hours after weight rate。
(11) anti-flammability
The test film that forming thickness is 1/16 inch, is evaluated according to UL94V-0 standard, represents with the burning time of the total of the test film of 5。
Table 1
Table 2
| Embodiment 7 | Embodiment 8 | Embodiment 9 | Example 10 | Example 11 | |
| (sec) is asked during gel | 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 |
| Bending strength (MPa) | 120 | 123 | 118 | 111 | 158 |
| The modulus of elasticity in static bending (GPa) | 20.5 | 20.9 | 20.0 | 20.2 | 25.7 |
| Water absorption rate (wt%) | 0.23 | 0.23 | 0.24 | 0.23 | 0.26 |
| Burning 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；Epoxide equivalent 200, softening point 65 DEG C), as curing agent component, use phenol aralkyl resin (PA；MEH-7800SS (bright and chemical conversion system), OH equivalent 175, softening point 67 DEG C)。And then, use spherical silicon dioxide (mean diameter 18 μm) as filler, use triphenylphosphine as curing accelerator, obtain composition epoxy resin with the cooperation shown in table 3。The weight portion that numeric representation in table coordinates。
Use this composition epoxy resin to form at 175 DEG C, solidify after carrying out at 175 DEG C 12 hours further, after obtaining solidfied material test film, for various physical property measurements。Table 4 represents result。
Table 3
Table 4
| Embodiment 12 | Embodiment 13 | Embodiment 14 | Example 15 | Example 16 | |
| (sec) is asked during gel | 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 |
| Bending strength (MPa) | 140 | 142 | 140 | 137 | 151 |
| The modulus of elasticity in static bending (GPa) | 18.0 | 18.5 | 17.9 | 17.8 | 20.2 |
| Water absorption rate (wt%) | 0.22 | 0.22 | 0.23 | 0.22 | 0.26 |
| Burning time (sec) | 43 | 27 | 40 | 65 | 223 |
The probability utilized in industry
When the epoxy resin of the present invention and multi-hydroxy resin are applied to composition epoxy resin, curable and mechanical properties are excellent and give the solidfied material that anti-flammability, moisture-proof and low elasticity are also excellent, it is possible to be suitable for the purposes such as the sealing of electric ton parts, circuit base material。Particularly curable and excellent in flame retardance, it is ensured that excellent formability, and the use of the fire retardant that there is carrying capacity of environment or need not be reduced。
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 formula (1) and the reaction of aralkyl agent, the substituent group being derived from aralkyl agent shown in formula (a) is replaced on the phenyl ring of multi-hydroxy compound the aralkyl modified multi-hydroxy resin obtained
As the multi-hydroxy compound shown in formula (1), use in area %, the n=1 composition of gel permeation chromatography as less than 10%, n=2 and n=3 composition add up to more than 60%, Mw/Mn be less than 1.2 narrow dispersion multi-hydroxy compound obtain
This, R1And R2Represent the alkyl of hydrogen atom or carbon number 1～6, R3And R4Representing 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 styrene。
3. the manufacture method of an aralkyl modified multi-hydroxy resin, it is characterized in that, make the aralkyl agent shown in the multi-hydroxy compound shown in following formula (1) and following formula (c1) or (c2) react in manufacture, when the substituent group being derived from aralkyl agent shown in formula (a) is replaced on the phenyl ring of multi-hydroxy compound the aralkyl modified multi-hydroxy resin obtained, multi-hydroxy compound as formula (1), use the area % in gel permeation chromatography, n=l composition is less than 10%, n=2 and n=3 composition add up to more than 60%, 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 reaction temperature 40～120 DEG C,
This, R1And R2Representing the alkyl of hydrogen atom or carbon number 1～6, n represents the number of 1～5,
This, R2Represent the alkyl of hydrogen atom or carbon number 1～6, R3And R4Representing the alkyl of hydrogen atom or carbon number 1～6, X represents halogen, OH or OR5, R5Represent the alkyl of carbon number 1～6,
This, R2、R3And R4With formula (c1) and (c2) synonym。
4. the manufacture method of aralkyl modified multi-hydroxy resin according to claim 3, it is characterised in that relative to the hydroxyl 1 mole of multi-hydroxy compound, make aralkyl agent 0.1～1.5 molar reactive。
5. the manufacture method of aralkyl modified multi-hydroxy resin according to claim 3, it is characterised in that aralkyl agent is styrene。
6. a composition epoxy resin, it is characterised in that it contains epoxy resin and firming agent, as part or all of firming agent, forms using the aralkyl modified multi-hydroxy resin described in claim 1 as neccessary composition。
7. an epoxy resin cured product, it is characterised in that the epoxy resin composition described in claim 6 is formed。
8. an epoxy resin, it is characterised in that make the aralkyl modified multi-hydroxy resin described in claim 1 and epichlorohydrin reaction obtain。
9. the manufacture method of an epoxy resin, it is characterised in that make the aralkyl modified multi-hydroxy resin described in claim 1 and epichlorohydrin reaction, forms glycidyl ether by the hydroxyl of aralkyl modified multi-hydroxy resin。
10. a composition epoxy resin, it contains epoxy resin and firming agent, wherein, coordinates the epoxy resin described in claim 8 to form as neccessary composition。
11. an epoxy resin cured product, the epoxy resin composition described in claim 10 is formed。
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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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|---|---|---|---|---|
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102010343A (en) * | 2009-09-08 | 2011-04-13 | 新日铁化学株式会社 | Polyhydroxy compound, method for manufacturing the same and epoxy resin composition, cured product thereof |
| CN102206326A (en) * | 2010-03-29 | 2011-10-05 | 新日铁化学株式会社 | Multielement hydroxyl resin, epoxy resin, methods of manufacturing multielement hydroxyl resin and epoxy resin, epoxy resin composition and cured resin comprising multielement hydroxyl resin and epoxy resin |
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| WO2013125620A1 (en) | 2013-08-29 |
| KR101987946B1 (en) | 2019-06-11 |
| JPWO2013125620A1 (en) | 2015-07-30 |
| JP6124865B2 (en) | 2017-05-10 |
| MY169844A (en) | 2019-05-17 |
| KR20140129227A (en) | 2014-11-06 |
| CN104334597A (en) | 2015-02-04 |
| SG11201405075SA (en) | 2014-10-30 |
| TWI548681B (en) | 2016-09-11 |
| TW201345958A (en) | 2013-11-16 |
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