CN104892905B - The manufacturing method of compositions of thermosetting resin, solidfied material and modified phenolic resin - Google Patents
The manufacturing method of compositions of thermosetting resin, solidfied material and modified phenolic resin Download PDFInfo
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- CN104892905B CN104892905B CN201510067709.8A CN201510067709A CN104892905B CN 104892905 B CN104892905 B CN 104892905B CN 201510067709 A CN201510067709 A CN 201510067709A CN 104892905 B CN104892905 B CN 104892905B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
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- Compositions Of Macromolecular Compounds (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The present invention provides the manufacturing method of compositions of thermosetting resin, solidfied material and modified phenolic resin.The subject of the invention is to provide the compositions of thermosetting resin of the solidfied material with high shrinkage when available solidification and have the solidfied material of excellent heat resistance and anti-flammability concurrently.A kind of compositions of thermosetting resin, it includes modified phenolic resin (A) shown in logical formula (I) and epoxy resin (B), total content of alkali metal, alkaline-earth metal in above-mentioned modified phenolic resin (A) relative to the total amount of above-mentioned phenol resin (A) is 0.1 mass % hereinafter, and the content of amine compound in above-mentioned modified phenolic resin (A) relative to the total amount of above-mentioned phenol resin (A) is 0.1 mass % or less.(in formula, R1For group, whole R shown in hydrogen atom or following formula (II)s1Middle R1Ratio for hydrogen atom is 20% less than 80%.R2And R3Each independently represent the aliphatic or aromatic hydrocarbyl of hydrogen atom or carbon atom number 1~20.N indicates 0~40 integer.)(in formula, R4For hydrogen atom or methyl.).
Description
Technical field
The present invention relates to the manufacturing methods of compositions of thermosetting resin, solidfied material and modified phenolic resin.
Background technology
About the compositions of thermosetting resin for being combined with epoxy resin and phenol resin (curing agent), due to such thermosetting property
Heat resistance, adaptation, the electrical insulating property of the solidfied material of resin combination etc. are excellent, therefore are used in various fields.For example, using
The interlayer dielectic resin combination used in printed base plate resin combination, printed base plate and copper foil with resin
Object, the sealing timber-used resin combination of electronic unit, resist ink, the conductive paste containing conductive filler agent, coating, bonding
Agent, composite material etc..
Semiconductor integrated level in a manner of following Moore's Law improves year by year.And due to semiconductor packages also with semiconductor
Highly integrated correspondence, therefore in addition to it is previous used the encapsulation of lead frame other than, develop the ball connected by convex block
The single facers such as grid array (hereinafter referred to as BGA) encapsulate, further by three-dimension packaging made of its lamination.On the other hand, it partly leads
Body sealing material has also carried out cooperation research, the improvement of forming method of the compositions of thermosetting resin suitable for various encapsulation.Such as
The face that is sealed is only one side in single facer encapsulation, thus when being molded due to substrate-side and the shrinking percentage of sealing material side it
Warpage poor and occurring becomes project, it is desirable that inhibits the compositions of thermosetting resin of the warpage.
For such requirement, various solutions are had studied.As one of the solution, for example, as it is known that as set about
Section.Compositions of thermosetting resin typically contains various fillers, it is known that inhibits the side of warpage by increasing filler usage amount
Method.
It is furthermore well known that improving crosslink density by increasing the functional group number of the resin component in compositions of thermosetting resin
Method.For example, have studied by using with triphenylmethane structure epoxy resin or phenol resin or use with four
The epoxy resin or phenol resin of phenol ethane structure inhibits the method for warpage.
As showing the document of such means, for example, recorded in patent document 1 by coordinate inorganic filler 85~
95 weight % reduce the warpage of encapsulation.
In addition, for example, being recorded in patent document 2, by with after the low sealing material molding of glass transition temperature, using glass
Glass transition temperature high sealing material is coating to inhibit warpage.
On the other hand, it records in patent document 3, is coordinated in (methyl) polyacryl novolac resin by making
Hardening resin composition is at 50 DEG C or more made of compound, aliphatic tertiary amine in molecule with 2 or more epoxy groups
100 DEG C or less are mixed to thicken, and (methyl) the polyacryl novolac resin is characterized in that, by making phenolic aldehyde
The phenolic hydroxyl group of varnish gum and to be that equivalent (methyl) glycidyl acrylate below carries out relative to the phenolic hydroxyl group anti-
It answers and obtains, and there is phenolic hydroxyl group in molecule.
In addition, having been recorded in patent document 4 other than miniaturization that single facer type encapsulates, slimming, semiconductor core
The proprietary area of piece increases, and is improved hence for the demand for the project for solving the convexity warp under opposite room temperature.
Existing technical literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 11-1541 bulletins
Patent document 2：Japanese Unexamined Patent Publication 10-112515 bulletins
Patent document 3：Japanese Unexamined Patent Publication 2000-198832 bulletins
Patent document 4：Japanese Unexamined Patent Publication 2012-72209 bulletins
Invention content
Problems to be solved by the invention
In order to reduce warpage, there is that the shrinking percentage when solidification for making compositions of thermosetting resin is small as possible, or improves thermosetting property
The rigidity of resin combination is come the method for resisting warpage itself etc..
In this case, it as shown in patent document 1 and 2, has studied and increases the use level of inorganic filler to improve
Elasticity modulus, or in order to make the solidfied material of compositions of thermosetting resin until temperature high as possible glass all small in linear expansion coefficient
The state in glass region and the method for improving the glass transition temperature of solidfied material.
However, such method shown in patent document 1 and 2, the warpage for the recessed direction of chip mounting surface be it is effective,
But the warpage of the convex direction for occurring in thin encapsulation has the opposite effect.I.e. for the warpage of convex direction, in order to offset base
The warpage of plate needs the shrinking percentage for increasing compositions of thermosetting resin.
In addition, even if as recorded in patent document 3 by making the compositions of thermosetting resin of specific composition in specific temperature
Degree range mixes to thicken, and for the warpage of convex direction, is still difficult to inhibit the warpage of substrate.
The purpose of the present invention is to provide the compositions of thermosetting resin of the high solidfied material of shrinking percentage when available solidification,
The manufacturing method of solidfied material and modified phenolic resin for being cured and being obtained.
The method used for solving the problem
That is, the present invention is constituted as follows.
(1) a kind of compositions of thermosetting resin, which is characterized in that include modified phenolic resin (A) and ring shown in logical formula (I)
Oxygen resin (B), total content of alkali metal, alkaline-earth metal in above-mentioned modified phenolic resin (A) is relative to above-mentioned phenol resin (A)
Total amount be 0.1 mass % hereinafter, also, amine compound in above-mentioned modified phenolic resin (A) content relative to above-mentioned phenol tree
The total amount of fat (A) is 0.1 mass % or less.
(in formula, R1For group shown in hydrogen atom or following formula (II)s, and whole R1Middle R1It is for the ratio of hydrogen atom
20% less than 80%.R2And R3Each independently represent the aliphatic or aromatic series of hydrogen atom or carbon atom number 1~20
Alkyl.N indicates 0~40 integer.)
(in formula, R4For hydrogen atom or methyl.)
(2) according to the compositions of thermosetting resin described in (1), alkali metal, alkaline earth in above-mentioned compositions of thermosetting resin
Total content of metal be 0.05 mass % hereinafter, also, amine compound in above-mentioned compositions of thermosetting resin content
For 0.05 mass % or less.
(3) according to the compositions of thermosetting resin described in (1) or (2), the weight average molecular weight of above-mentioned modified phenolic resin (A) is
250~5000.
(4) according to any one of them compositions of thermosetting resin of (1)~(3), relative in above-mentioned epoxy resin (B)
1.0 equivalent of epoxy group, the hydroxyl of above-mentioned modified phenolic resin (A) is the range of the equivalent of 0.6 equivalent~1.2.
(5) according to any one of them compositions of thermosetting resin of (1)~(4), above-mentioned epoxy resin (B's) divides equally again
Son amount is 300~5000.
(6) according to any one of them compositions of thermosetting resin of (1)~(5), including filler.
(7) a kind of solidfied material is obtained by curing any one of them compositions of thermosetting resin of (1)~(6).
(8) according to the solidfied material described in (7), shrinking percentage is 0.15%~0.40%.
(9) a kind of manufacturing method of modified phenolic resin, which is characterized in that make phenol resin and (methyl) glycidyl
Ester is reacted in the presence of organophosphorus compound, is obtained and is led to modified phenolic resin (A) shown in formula (I).
(in formula, R1For group shown in hydrogen atom or following formula (II)s, and whole R1Middle R1It is for the ratio of hydrogen atom
20% less than 80%.R2And R3Each independently represent the aliphatic or aromatic series of hydrogen atom or carbon atom number 1~20
Alkyl.N indicates 0~40 integer.)
(in formula, R4For hydrogen atom or methyl.)
(10) according to the manufacturing method of the modified phenolic resin described in (9), the usage amount of organophosphorus compound is relative to phenol
100 mass parts of resin are that 0.001 mass parts or more 10 are below mass part.
The effect of invention
According to the present invention, compositions of thermosetting resin, the solidification of the high solidfied material of shrinking percentage when can get solidification are provided
The manufacturing method of object and compositions of thermosetting resin.
Specific implementation mode
＜ compositions of thermosetting resin ＞
The compositions of thermosetting resin of the present invention includes modified phenolic resin (A) and epoxy resin (B).
The compositions of thermosetting resin of the present invention can also include filling in the limit of effect for not damaging the present invention
Agent, compounding agent etc..
Hereinafter, explaining the compositions of thermosetting resin of the present invention in detail.
In addition, the numberical range that "~" shows is used to indicate the front and back recorded numerical value point comprising "~" in this specification
Range not as minimum value and maximum value.
(modified phenolic resin (A))
Modified phenolic resin (A), which fits through, makes phenol resin with (methyl) glycidyl acrylate in organophosphorus compound
In the presence of reacted to obtain.
(phenol resin)
As phenol resin used in the present invention, be not particularly limited, can use make phenols and aldehydes in acidic catalyst
Well known novolak type phenol resin obtained by being reacted in the presence of agent.
As the concrete example of phenols, can enumerate for example, phenol, cresols, ethyl -phenol, dimethlbenzene, butylphenol, octyl
Phenol, nonyl phenol, phenylphenol, cyclohexylphenol, pseudocuminol, bisphenol-A, catechol, resorcinol, quinhydrones, naphthols,
Pyrogallol etc., from the viewpoint of the shrinking percentage of the thermosetting resin of gained, preferably phenol, cresols, as cresols, preferably
For o-cresol.
As the concrete example of aldehydes, can enumerate formaldehyde, acetaldehyde, paraformaldehyde, propionic aldehyde, butyraldehyde, valeral, hexanal, benzaldehyde,
Hydroxy benzaldehyde, 4-dihydroxy benzaldehyde, hydroxymethylbenzaldehyde, glyoxal, crotonaldehyde, glutaraldehyde etc., from the thermosetting property of gained
From the perspective of the shrinking percentage of resin, preferably formaldehyde, benzaldehyde.
As phenol resin, can use for example, phenol resol resins can be enumerated as phenol resol resins
Trade name " シ ョ ウ ノ ー Le BRG-558 " (phenol novolacs, Showa Denko K. K's system, hydroxyl equivalent 104g/eq.,
" シ ョ ウ ノ ー Le " is the trade mark of Showa Denko K. K), trade name " シ ョ ウ ノ ー Le CRG-951 " (o-cresol phenolic aldehyde
Varnish, Showa Denko K. K's system, hydroxyl equivalent 118g/eq., " シ ョ ウ ノ ー Le " are the quotient of Showa Denko K. K
Mark).
(manufacturing method of modified phenolic resin (A))
The manufacturing method of the modified phenolic resin of the present invention is to make phenol resin with (methyl) glycidyl acrylate organic
It is reacted in the presence of phosphorus series compound, obtains the method for leading to modified phenolic resin (A) shown in formula (I).
In formula, R1For group shown in hydrogen atom or following formula (II)s, and whole R1Middle R1Ratio for hydrogen atom is 20%
Less than 80%.R2And R3Each independently represent the aliphatic or aromatic hydrocarbon of hydrogen atom or carbon atom number 1~20
Base.N indicates 0~40 integer.
(in formula, R4For hydrogen atom or methyl.)
N+2 whole R in the general formula of modified phenolic resin (A)1In R1Ratio for hydrogen atom be 20% less than
80%, preferably 30~70%, more preferably 40~60%.
The R in general formula by making modified phenolic resin (A)1The ratio of hydrogen atom be 20% less than 80%, from
And shrinking percentage when including the solidification of the compositions of thermosetting resin of modified phenolic resin (A) and aftermentioned epoxy resin (B) increases.
In above-mentioned formula (I), R2And R3Each independently represent the aliphatic or fragrance of hydrogen atom or carbon atom number 1~20
Race's alkyl.
As the aliphatic alkyl of carbon atom number 1~20, the saturated alkyl or unsaturation on chain or branch can be enumerated
Alkyl, preferably carbon atom number 1~12, more preferably carbon atom number 1~6.Specifically, methyl, ethyl, isopropyl can be enumerated
Base, n-octyl, vinyl, cyclobutenyl etc., but not limited thereto.From the viewpoint of versatility, reaction easiness, preferably first
Base, ethyl.
As the aromatic hydrocarbyl of carbon atom number 1~20, phenyl, naphthalene etc. can be enumerated.
From the viewpoint of versatility, reaction easiness, preferably R2And R3It is each independently methyl, ethyl.
In above-mentioned formula (I), n indicates 0~40 integer, preferably 0~30, more preferably 0~20.If above-mentioned formula (I)
In n be 0~40 integer, then can by the weight average molecular weight of modified phenolic resin (A) control in particular range, from mobility
From the perspective of be suitable.
Here, modified phenolic resin (A) can be by making phenol resin with (methyl) glycidyl acrylate in base catalysis
It is reacted under agent to obtain.
Molal quantity of the usage amount of (methyl) glycidyl acrylate relative to the hydroxyl in phenol resin, preferably 20~
90 moles of %, more preferably 30~80 moles of %.By making the usage amount of (methyl) glycidyl acrylate be 20 moles of %
Above 90 moles of % are hereinafter, then can be by the R in the general formula of modified phenolic resin (A)1The ratio of hydrogen atom adjust to specified amount.
As basic catalyst, hydroxide, organophosphorus compound for example, alkali (soil) metal can be enumerated.
However, in the case where having used the hydroxide of alkali (soil) metal, the remaining metal ion in modified phenolic resin.
In such as electronic material possibility on the way having due to being mixed into for metal ion and occurring undesirable condition, it is therefore desirable to catalyst
Removal step.Catalyst removal step is for example to carry out the washing of modified phenolic resin repeatedly, or neutralized generation with acid
Salt is washed with water to remove.Such process generates a large amount of waste water and activity time is elongated, therefore not preferably.
If using amine compound as basic catalyst, the remaining amine compound in modified phenolic resin.Amine system
Compound works as the curing agent of epoxy resin, it is however generally that its reaction temperature is warmer than phenol resin and reacting for epoxy resin
It spends low.The modified phenolic resin in process (A) is collapsed with the balance of reacting of epoxy resin (B) afterwards, therefore not preferably.Such as it is using
In the case that hexa is as amine compound, there is modified phenolic resin to be combined each other with methylene and carry out crosslinked work
With, therefore modified phenolic resin (A) becomes inadequate with reacting for epoxy resin (B), therefore not preferably.
(organophosphorus compound)
Therefore, organophosphorus compound is used in the present invention as basic catalyst.
As organophosphorus compound, ethyl phosphine, propyl phosphine, butyl phosphine, Phenylphosphine, trimethyl-phosphine, triethyl group can be enumerated
Phosphine, tributylphosphine, tri octyl phosphine, triphenylphosphine, tricyclohexyl phosphine, triphenylphosphine/triphenylborane complex, tetraphenyl
Boron tetraphenylDeng.They can be used alone, can also two kinds or more be used in combination, if it is considered that as thermosetting resin combine
The characteristic of object, then preferably triphenylphosphine.
The usage amount of organophosphorus compound is relative to 100 mass parts of phenol resin, the mass of preferably 0.001 mass parts~10
Part, the mass parts of more preferably 0.01 mass parts~8, the mass parts of further preferably 0.1 mass parts~5.
If the usage amount of organophosphorus compound is 0.001 mass parts or more relative to 100 mass parts of phenol resin, can
The reaction time for being used to obtain modified phenolic resin (A) is foreshortened to usage range.In addition, if organophosphorus compound makes
Dosage is 10 below mass part relative to 100 mass parts of phenol resin, then the control of the reaction speed of compositions of thermosetting resin becomes
It must be easy.
(other additives)
As needed, from the viewpoint of the storage stability of composition, polymerization inhibitor can be added.It, can as polymerization inhibitor
Enumerate quinhydrones, methylnaphthohydroquinone etc..
Method for making phenol resin be reacted with (methyl) glycidyl acrylate, is not particularly limited, can lift
Go out for example, making phenol resin that the method reacted be added together with (methyl) glycidyl acrylate and basic catalyst；Or
Phenol resin and basic catalyst is added, the method that (methyl) glycidyl acrylate is added under defined reaction temperature.
At this point, reaction temperature preferably 30 DEG C~120 DEG C range carry out, more preferably 60 DEG C~110 DEG C range into
Row.
By make reaction temperature be 30 DEG C or more, so as to so that reaction carry out be difficult to it is slow.In addition, by making reaction
Temperature is 120 DEG C hereinafter, so as to inhibit the free radical polymerization of (methyl) glycidyl acrylate.
Reaction time is not particularly limited, as long as according to the amount of (methyl) glycidyl acrylate and catalyst, reaction
Temperature suitably adjust.
When reaction, organic solvent can be used.
(organic solvent)
As such organic solvent, alcohols, ethylene glycol, the propylene glycol such as methylol, ethyl alcohol, propyl alcohol, butanol etc. two
Alcohols, ethylene glycol single methyl ether, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl, butanediol monomethyl
The ketone such as glycol ethers, acetone, methyl ethyl ketone, the methyl iso-butyl ketone (MIBK)s such as ether, butanediol list ethylether, butanediol list propyl ether
Class, ethyl acetate, propyl acetate, butyl acetate, ethyl lactate, ethylene glycol single methyl ether acetic acid esters, propylene glycol monomethyl ether second
The esters such as acid esters, 1,4- bis-Ethers such as alkane etc. can be used alone, or can be used in combination with two kinds or more.
Above-mentioned organic solvent can be to be preferably mass parts of 0 mass parts~1,000, more relative to 100 mass parts of phenol resin
The mode of the mass parts of the mass parts of preferably 10 mass parts~100, further preferably 10 mass parts~50 or so uses.
Can organic solvent be removed by distilling after the reaction by the modification phenol that reaction obtains, it in addition can basis
It is washed to remove catalyst.
Furthermore, it is possible to carry out vacuum distillation or steam distillation remove unreacted phenols.
Total content of alkali metal, alkaline-earth metal in modified phenolic resin (A) or the content of amine compound are relative to upper
The total amount for stating phenol resin (A) is 0.1 mass % hereinafter, preferably 0.05 mass % is hereinafter, more preferably 0.01 mass % or less.
It as amine compound, is not particularly limited, the amine system from basic catalyst when obtaining modified phenolic resin (A) can be enumerated
Compound etc. can be enumerated for example, aromatic amines such as the aliphatic amines such as hexa, m-xylene diamines.
By making the total amount relative to above-mentioned phenol resin (A), alkali metal, total content of alkaline-earth metal or amine compound
Content be 0.1 mass % hereinafter, so as to reduce gained modified phenolic resin washing times, as a result, shorten manufacture
Activity time, in addition, the modified phenolic resin (A) after inhibiting in process is collapsed with the balance of epoxy resin (B) reacted.
In addition, total content or amine compound as alkali metal, alkaline-earth metal in compositions of thermosetting resin
Content, the total amount relative to above-mentioned compositions of thermosetting resin are 0.05 mass % or less.At this point, in compositions of thermosetting resin
Including in the case of filler, since it is not involved in curing reaction, consider relative to from the total of compositions of thermosetting resin
The amount after filler, total content of alkali metal, alkaline-earth metal or the content of amine compound are removed in amount.
Alkali metal, alkaline-earth metal in modified phenolic resin (A) are quantified using atomic absorption spectrophotometer (AAS)
It measures.In addition, the amine compound in modified phenolic resin (A) carries out quantitative analysis using gas chromatographic analysis device (GC).
Analysis condition etc. is described in detail in embodiment.
About the weight average molecular weight of modified phenolic resin (A), if it is considered that the mobility of compositions of thermosetting resin, then preferably
It is 250~5000, more preferably 300~4000, further preferably 400~3000.
The weight average molecular weight of resin can be for example measured by gel permeation chromatography (GPC).As the specific of GPC
Determination condition, can enumerate for example,
Column：By trade name " KF-801 ", " KF-802 ", " KF-802 " and " KF-803 " (Showa Denko K. K's system,
Shodex (trade mark) series) connection use.
Detector：Trade name " RI-71 " (Showa Denko K. K's system, differential refractometer " Shodex " (trade mark))
Solvent：Tetrahydrofuran
Flow：1ml/ minutes
Deng.
(epoxy resin (B))
It as epoxy resin used in the present invention, is not particularly limited, well known epoxy resin can be used.As ring
The concrete example of oxygen resin can enumerate bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, bisphenol-A D types
Epoxy resin, resorcinol type epoxy resin, hydroquinone type epoxy resin, catechol-type epoxy resin, dihydroxy naphthlene type asphalt mixtures modified by epoxy resin
Epoxy resin, the phenol novolacs derived from divalent phenols such as fat, biphenyl type epoxy resin, tetramethyl biphenyl type epoxy resin
Type epoxy resin, cresol novolak type epoxy resin, triphenylmethane type epoxy resin, tetraphenyl ethane type epoxy resin,
Dicycldpentadiene-phenol modified version epoxy resin, phenol aralkyl type epoxy resin, biphenyl aralkyl-type epoxy resin, naphthols
Phenolic resin varnish type epoxy resin, naphthols aralkyl-type epoxy resin, naphthols-phenol cocondensation phenolic resin varnish type epoxy resin, naphthols-
Cresols cocondensation phenolic resin varnish type epoxy resin, aromatic hydrocarbon formaldehyde resin modified phenolic resin type epoxy resin, biphenyl modified phenolic
The epoxy resin, the epoxy resin being modified by organophosphorus compound derived from the above phenols of trivalent such as type epoxy resin
Deng.Wherein it is preferably triphenylmethane type epoxy resin.In addition these epoxy resin can be used alone, can also be two kinds or more
It is used in combination.Wherein, preferably bisphenol-type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin,
Triphenylmethane type epoxy resin, biphenyl aralkyl-type epoxy resin, more preferably biphenyl aralkyl-type epoxy resin.
About the weight average molecular weight of epoxy resin (B), from the mobility of compositions of thermosetting resin and the balance of heat resistance
From the perspective of, preferably 300~5000, more preferably 400~3500, further preferably 400~3000.
Epoxy resin (B) and the mixed proportion of phenol resin (A) are worked as relative to the epoxy group 1.0 in epoxy resin (B)
Amount, the hydroxyl in phenol resin (A) are preferably the range of the equivalent of 0.5 equivalent~1.3, the model of the equivalent of more preferably 0.6 equivalent~1.2
It encloses, the range of the equivalent of further preferably 0.7 equivalent~1.1.
It, can also be suitable for using curing accelerator for the purpose of promoting curing reaction in compositions of thermosetting resin.
As curing accelerator, can enumerate for example, imidazole compound, organophosphorus compound, lewis acid etc..They
Can be used alone, can also two kinds or more be used in combination.
As imidazole compound, can enumerate imidazoles, 2-methylimidazole, 2- ethyl imidazol(e)s, 2-ethyl-4-methylimidazole,
2- phenylimidazoles, 2- undecyl imidazoles, 1 benzyl 2 methyl imidazole, 2- heptadecyl imidazoles, 4,5- diphenyl-imidazoles, 2-
Methylimidazole quinoline, 2- benzylimidazolines, 2- undecyl imidazoles quinoline, 2- heptadecyl imidazoles quinoline, 2 isopropyl imidazole, 2,4- bis-
Methylimidazole, 2- phenyl -4-methylimidazole, 2- ethyl imidazol(e)s quinoline, 2 isopropyl imidazole quinoline, 2,4- methylimidazoles quinoline, 2- benzene
Base -4-methylimidazole quinoline etc..
Imidazole compound can be masked by screening agent.
As screening agent, acrylonitrile, phenylene diisocyanate, toluidine isocyanate (ト Le イ ジ Application イ ソ シ can be enumerated
ア ネ ー ト), naphthalene diisocyanate, Methylene bis phenyl isocyanates, melamine acrylate etc..
As organophosphorus compound, ethyl phosphine, propyl phosphine, butyl phosphine, Phenylphosphine, trimethyl-phosphine, triethyl group can be enumerated
Phosphine, tributylphosphine, tri octyl phosphine, triphenylphosphine, tricyclohexyl phosphine, triphenylphosphine/triphenylborane complex, tetraphenyl
Boron tetraphenylDeng.
In these curing accelerators, preferably triphenylphosphine.
(filler)
In the compositions of thermosetting resin of the present invention, for the purpose of anti-flammability imparting, thermal expansion inhibition etc., preferably cooperation is filled out
Fill agent.As concrete example, can enumerate for example, fused silica, crystalline silica, aluminium oxide, zircon, calcium silicates, carbonic acid
Calcium, silicon carbide, silicon nitride, boron nitride, zirconium oxide, forsterite, steatite, spinelle, titanium dioxide, aluminium hydroxide, hydrogen-oxygen
Change the inorganic fillers such as magnesium.
Fused silica can use broken shape, spherical any, in order to improve the use level of fused silica,
And inhibit the rising of the melt viscosity of moulding material, preferably mainly use spherical fused silica.In addition, in order to improve ball
The size distribution of spherical silicon dioxide is preferably suitably adjusted the use level of compositions of thermosetting resin by shape silica
It is whole.The fit rate of fused silica desired model according to the applicable purposes and desired characteristic of compositions of thermosetting resin
Enclose difference.For example, in the case where compositions of thermosetting resin is used for encapsulating semiconductor timber-used way, if in view of thermosetting property tree
The linear expansion coefficient of the solidfied material of oil/fat composition, anti-flammability, then the fit rate of preferred molten silica is high.Specifically, phase
It is preferably 50 mass % or more for compositions of thermosetting resin total amount, more preferably 60 mass % or more, further preferably
70 mass of mass %~90 % or so.
In addition, by compositions of thermosetting resin for the purposes such as conductive paste, conductive film, as filler,
The conductive fillers agent such as silver powder, copper powder can be used.
In addition, the compositions of thermosetting resin of the present invention can contain the thermosetting property tree used as modifying agent as needed
The various compounding agents such as fat and thermoplastic resin, pigment, silane coupling agent, releasing agent.
The thermosetting resin and thermoplastic resin used as modifying agent can use well known various substances.
As thermosetting resin and thermoplastic resin, can make as needed within the scope of the effect of the invention
With for example, phenoxy resin, polyamide, polyimide resin, polyetherimide resin, polyethersulfone resin, polyphenylene oxide tree
Fat, polyphenylene sulfide polyester resin, polystyrene resin, pet resin etc..
As silane coupling agent, amino silane based compound, vinyl silanes based compound, polystyrene silane can be enumerated
The silane coupling agents such as compound, metering system acyloxy silane based compound.
In addition, as releasing agent, can enumerate stearic acid, zinc stearate, calcium stearate, aluminum stearate, magnesium stearate and bar
Western palm wax etc..
The compositions of thermosetting resin containing modified phenolic resin (A) and epoxy resin (B) of the present invention obtains when curing
The high solidfied material of shrinking percentage.
In the case where the sealing timber-used resin combination as electronic unit uses, especially from inhibition thin encapsulation
From the perspective of convexity warp, shrinking percentage when compositions of thermosetting resin being made to cure is preferably 0.15%~0.40%, more preferably
It is 0.20%~0.40%, further preferably 0.25%~0.40%.
The compositions of thermosetting resin of the present invention is especially the sealing timber-used resin combination that can be suitable for electronic unit
Interlayer dielectic resin group used in object, printed base plate resin combination, printed base plate and copper foil with resin
Close object, the conductive paste containing conductive filler agent, coating, bonding agent and composite material.
＜ solidfied materials ＞
The solidfied material of the present invention is to obtain the compositions of thermosetting resin solidification of the present invention.
The curing of compositions of thermosetting resin is not particularly limited, as long as example, in heating temperature 170 DEG C~250
DEG C, compositions of thermosetting resin is heated under conditions of 60 minutes~20 hours heating time.Heating temperature is more excellent
It is selected as 170 DEG C~220 DEG C, further preferably 170 DEG C~200 DEG C.Heating time is more preferably 60 minutes~10 hours, into one
Step preferably 90 minutes~8 hours.
Additionally, it is preferred that compositions of thermosetting resin is press-formed before the manufacture of solidfied material.When extrusion forming
Pressure is preferably 2~20MPa, more preferably 4~15MPa, further preferably 5~12MPa.In addition, temperature when extrusion forming
Preferably 170~250 DEG C of degree, more preferably 170~220 DEG C, further preferably 170~200 DEG C.
Embodiment
Hereinafter, illustrate the present invention in further detail by embodiment, but the present invention is not limited thereto, embodiment and compares
In example " part " and " % " is quality criteria.
Production Example 1 (synthesis of modified phenolic resin A)
In having the flask of cooling tube and blender, trade name " the シ ョ ウ ノ as phenol resol resins are added
ー Le (trade mark) BRG-558 " (Showa Denko K. K's system, hydroxyl equivalent 104g/eq.) 104g, methyl ethyl ketone 50g, hydrogen
Quinone 0.04g and glycidyl methacrylate 43g carries out mixing at 60 DEG C until becoming uniform.40 DEG C are cooled to hereinafter, so
Addition triphenylphosphine 2g afterwards.It is reacted 5 hours at 100 DEG C, then under 120 DEG C, the decompression of 50mmHg, removes and evaporate from product
Point, obtain the modified phenolic resin A of 147g light brown blocks.The softening point of the modified phenolic resin A of gained is 83 DEG C, weight average molecular weight
It is 1900.
Production Example 2~3, comparison manufacturing example 2~4
It using the composition of table 1, in addition to this, is carried out similarly and reacts with Production Example 1, obtain modified phenol shown in table 2,3
Resin B~C, J~L.
Production Example 4
In having the flask of cooling tube and blender, addition Bisphenol F 200g, methyl ethyl ketone 100g make them dissolve,
Be subsequently added into quinhydrones 0.08g, glycidyl methacrylate 56g carries out mixing until become uniform, then add triphenyl
Phosphine 2g.It is reacted 5 hours at 100 DEG C, then under 120 DEG C, the decompression of 50mmHg, fraction is removed from product, is modified
Phenol resin D256g.
Production Example 5
In the flask for having cooling tube, blender, o-cresol 100g, benzaldehyde 49g, p-methyl benzenesulfonic acid 10g is added,
100 DEG C are reacted 8 hours.Then, after being neutralized with sodium hydrate aqueous solution, 5 washings are carried out with pure water 100g, except desalting.
Then fraction is removed under 180 DEG C, the decompression of 50mmHg, be then dissolved in methyl ethyl ketone 39g.It is subsequently added into
Quinhydrones 0.04g, glycidyl methacrylate 19g carry out mixing until becoming uniform, then add triphenylphosphine 2g.
100 DEG C are reacted 5 hours, and fraction is then removed under 120 DEG C, the decompression of 50mmHg, obtain 98g modified phenolic resins E.
Production Example 6
It using the composition of table 1, in addition to this, is carried out similarly and reacts with Production Example 5, obtain resin F.
Production Example 7,8
Using the composition of table 1, without neutralization step after reaction in the first stage, 2 washings are carried out with pure water 100g,
In addition to this, it is carried out similarly and reacts with Production Example 5, obtain resin G, H.
Comparison manufacturing example 1
Operated in the same manner as Production Example 5, implement the reaction of first stage, carry out the removing of salt, the removing of fraction and obtain
Phenol resol resins are set to resin I.Without reacting for second stage and glycidyl methacrylate.
[table 1]
BRG-558：Phenol resol resins, trade name " シ ョ ウ ノ ー Le (trade mark) BRG-558 ", Showa electrician's strain
Formula commercial firm system, hydroxyl equivalent 104g/eq.
CRG-951：O-cresol novolak, trade name " シ ョ ウ ノ ー Le (trade mark) CRG-951 ", Showa electrician's strain formula
Commercial firm's system, hydroxyl equivalent 118g/eq.
The analysis method of modified phenolic resin and phenol resin is as follows.
(1) softening point (DEG C)
Using エ レ ッ Network ス science society system, gas phase softening point measurement device EX-719PD is measured.Heating rate is set as
2.5 DEG C/min.
(2) weight average molecular weight
It is measured by gel permeation chromatography (GPC).
Column is configured to make Showa electrician society system, and trade name " KF-801 ", " KF-802 ", " KF-802 " and " KF-803 " is even
It connects, using tetrahydrofuran as solvent, is measured within 1ml/ minutes with flow.Detector commodity in use name " RI-71 " (Showa electricity
Work Co. Ltd. system, differential refractometer " Shodex " (trade mark)).Molecular weight is calculated with polystyrene conversion.
(3) R of the general formula of modified phenolic resin1Hydrogen atom ratio
Using nuclear magnetic resonance (NMR) device (BRUKER societies system, product name " AVANCE400 "), by phenol resin before modified
NMR figure (from phenyl ring 6.5~7.5ppm chemical shift with from phenolic hydroxyl group 8.0~10.0ppm chemistry
The ratio between displacement) it is compared with the NMR of modified phenolic resin figure (be same as above), calculate the R of logical formula (I)1Hydrogen ratio.
(4) alkali metal in modified phenolic resin (A), alkaline-earth metal use atomic absorption spectrophotometer (AAS) (Thermo
Scientrific societies system, product name " iCE3000 ") it is quantitative determined.
(5) amine compound in modified phenolic resin (A) uses gas phase chromatographic device (GC) (Shimadzu Scisakusho Ltd
System, product name " GC-8APF "), quantitative analysis is carried out under the following conditions.
＜ GC ＞
Column：Port ラ パ ッ Network Q columns (80~100 mesh)
Carrier gas：Nitrogen
Flow：40ml/ minutes
Column temperature：230℃
About each analysis result, it is shown in table 2 and table 3.
Embodiment 1~15 and comparative example 1~6
(modulation of compositions of thermosetting resin)
About each modified phenolic resin and phenol resin by Production Example 1~8 and the acquisition of comparison manufacturing example 1~4, with table 2, table
Shown in 3 cooperation mixed, carry out melting mixing under conditions of 90 DEG C of temperature, 5 minutes time, obtain embodiment 1~
15 and comparative example 1~6 compositions of thermosetting resin.
The cooperation of ingredient shown in table 2, table 3 carries out as follows.
For measuring the epoxy resin (weight average molecular weight 1000) of (for example, being 10 parts in embodiment 1) shown in table 2, table 3,
The modified phenolic resin and phenol resin of hydroxyl equivalent/epoxide equivalent ratio recorded in mixture table 2, table 3, the three of 0.1 part of addition
Phenylphosphine (curing accelerator), to obtain resin component.Next, so that the side that the containing ratio in composition is 80 mass %
Formula mixes fused silica (inorganic filler) into above-mentioned resin component, using double roller (western village マ シ Na リ ー societies system,
NS-155 (S) type), it is kneaded 5 minutes at 100 DEG C, modulates compositions of thermosetting resin.
(manufacture of solidfied material)
The compositions of thermosetting resin of acquisition is utilized into mold specified in JIS K-6911 (circle of diameter 90mm, thickness
Spend 5mm, and the mold of the sample of the protrusion of the range of 76~80mm of diameter with height 3mm can be produced on), 150 DEG C, 40
It is press-formed under conditions of minute, pressure 10MPa.Then, heated 5 hours at 180 DEG C, by compositions of thermosetting resin into
Row solidification, produces the testing piece of solidfied material.
About the testing piece of acquisition, shrinking percentage is evaluated by the following method.
(6) shrinking percentage
It is evaluated using method specified in JIS K-6911.
The measurement knot of the shrinking percentage of the testing piece made by embodiment 1~15 and comparative example 1~6 is shown in table 3, table 2
Fruit.
[table 2]
[table 3]
It confirmed by table 2, table 3, the solidfied material (testing piece) of compositions of thermosetting resin of the invention shows high shrinkage.
I.e. it is found that the shrinking percentage of the testing piece of embodiment is much excellent compared with the previous solidfied material obtained using novolac resin
It is different.
Claims (13)
1. a kind of compositions of thermosetting resin, which is characterized in that include modified phenolic resin (A) and asphalt mixtures modified by epoxy resin shown in logical formula (I)
Fat (B),
Total content of alkali metal, alkaline-earth metal in the modified phenolic resin (A) is relative to the total amount of the phenol resin (A)
0.1 mass % hereinafter, also,
The content of amine compound in the modified phenolic resin (A) is 0.1 mass % relative to the total amount of the phenol resin (A)
Hereinafter,
In formula, R1For group shown in hydrogen atom or following formula (II)s, and whole R1Middle R1Ratio for hydrogen atom is 20% or more
And it is less than 80%, R2And R3Each independently represent the aliphatic or aromatic hydrocarbyl of hydrogen atom or carbon atom number 1~20, n tables
Show 0~40 integer,
In formula, R4For hydrogen atom or methyl.
2. compositions of thermosetting resin according to claim 1, alkali metal, alkaline earth in the compositions of thermosetting resin
Total content of metal be 0.05 mass % hereinafter, also,
The content of amine compound in the compositions of thermosetting resin is 0.05 mass % or less.
3. the weight average molecular weight of compositions of thermosetting resin according to claim 1 or 2, the modified phenolic resin (A) is
250~5000.
4. compositions of thermosetting resin according to claim 1 or 2, relative to the epoxy group in the epoxy resin (B)
1.0 equivalents, the hydroxyl of the modified phenolic resin (A) are the range of the equivalent of 0.6 equivalent~1.2.
5. compositions of thermosetting resin according to claim 3, relative to the epoxy group 1.0 in the epoxy resin (B)
Equivalent, the hydroxyl of the modified phenolic resin (A) are the range of the equivalent of 0.6 equivalent~1.2.
6. the weight average molecular weight of compositions of thermosetting resin according to claim 1 or 2, the epoxy resin (B) is 300
~5000.
7. compositions of thermosetting resin according to claim 3, the weight average molecular weight of the epoxy resin (B) is 300~
5000。
8. compositions of thermosetting resin according to claim 1 or 2, including filler.
9. compositions of thermosetting resin according to claim 3, including filler.
10. a kind of solidfied material is obtained by curing any one of them compositions of thermosetting resin of claim 1~9.
11. solidfied material according to claim 10, shrinking percentage is 0.15%~0.40%.
12. a kind of manufacturing method of modified phenolic resin, which is characterized in that phenol resin is made to exist with (methyl) glycidyl acrylate
It is reacted in the presence of organophosphorus compound, obtains and lead to modified phenolic resin (A) shown in formula (I),
In formula, R1For group shown in hydrogen atom or following formula (II)s, and whole R1Middle R1Ratio for hydrogen atom is 20% or more
And it is less than 80%, R2And R3Each independently represent the aliphatic or aromatic hydrocarbyl of hydrogen atom or carbon atom number 1~20, n tables
Show 0~40 integer,
In formula, R4For hydrogen atom or methyl.
13. the manufacturing method of modified phenolic resin according to claim 12, the usage amount of organophosphorus compound relative to
100 mass parts of phenol resin are that 0.001 mass parts or more 10 are below mass part.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014041807A JP6497639B2 (en) | 2014-03-04 | 2014-03-04 | Thermosetting resin composition, cured product and method for producing modified phenolic resin |
| JP2014-041807 | 2014-03-04 |
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| CN101045839A (en) * | 2007-04-10 | 2007-10-03 | 深圳市容大电子材料有限公司 | Liquid photosensitive ink and applied in printing circuit board |
| CN101220224A (en) * | 2008-01-23 | 2008-07-16 | 深圳市容大电子材料有限公司 | UV solidified alkali resistant etching ink composition and uses thereof |
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| JPH0551507A (en) * | 1991-08-26 | 1993-03-02 | Soken Kagaku Kk | Thermosetting acrylate composition |
| JPH10180403A (en) * | 1996-12-26 | 1998-07-07 | Sumitomo Bakelite Co Ltd | Resin composition, permanent resist resin composition, and hardened resin thereof |
| JP4244421B2 (en) * | 1999-01-06 | 2009-03-25 | 住友ベークライト株式会社 | Curable resin composition and thickening method thereof |
| JP4514011B2 (en) * | 2001-09-13 | 2010-07-28 | 日本化薬株式会社 | Resin composition, solder resist resin composition, and cured products thereof |
| JP2005082782A (en) * | 2003-09-11 | 2005-03-31 | Showa Highpolymer Co Ltd | Electroconductive curable resin composition |
| US20090156715A1 (en) * | 2007-12-14 | 2009-06-18 | Thomas Eugene Dueber | Epoxy compositions comprising at least one elastomer and methods relating thereto |
| KR101248008B1 (en) * | 2012-05-02 | 2013-03-27 | 주식회사 이녹스 | Adhesive film composition for semiconductor package |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101045839A (en) * | 2007-04-10 | 2007-10-03 | 深圳市容大电子材料有限公司 | Liquid photosensitive ink and applied in printing circuit board |
| CN101220224A (en) * | 2008-01-23 | 2008-07-16 | 深圳市容大电子材料有限公司 | UV solidified alkali resistant etching ink composition and uses thereof |
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| KR20150104026A (en) | 2015-09-14 |
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| TW201544538A (en) | 2015-12-01 |
| JP2015166437A (en) | 2015-09-24 |
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