WO2018221373A1 - ブロック共重合体とその製造方法、エポキシ樹脂組成物、およびその硬化物ならびに半導体封止材 - Google Patents
ブロック共重合体とその製造方法、エポキシ樹脂組成物、およびその硬化物ならびに半導体封止材 Download PDFInfo
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Definitions
- the present invention relates to a block copolymer and a production method thereof, an epoxy resin composition containing the block copolymer, a cured product thereof, and a semiconductor encapsulant.
- a semiconductor encapsulant that protects a semiconductor from heat and impact is generally composed of an epoxy resin, a curing agent, a filler, and various additives such as a low stress agent and a flame retardant.
- semiconductors have been highly integrated and the semiconductor chip size has increased accordingly.
- semiconductor packages have been reduced in size and thickness. Therefore, there are problems that cracking due to thermal shock during molding of the package and damage to the package due to peeling of the lead frame or chip from the sealing resin are likely to occur.
- further improvements in low-stress properties, fluidity, heat resistance, etc. are required for semiconductor encapsulants with higher operating temperatures, such as automotive semiconductors and power semiconductors that will increase in the future. It has been. Under such circumstances, a technique for reducing the elastic modulus of a semiconductor sealing material using silicone particles as a stress reducing agent has been disclosed (Patent Document 1).
- Patent Document 2 an ABA type triblock copolymer in which polyalkylene glycol chains are modified at both ends of silicone, and a functional group A method for imparting a glycidyl group to a terminal of a multiblock copolymer composed of silicone and polyalkylene glycol is disclosed (Patent Document 3).
- JP 2013-189490 A Japanese Patent Laid-Open No. 10-182831 Japanese Patent Laid-Open No. 4-359023
- the fluidity is improved to improve the work efficiency of manufacturing the semiconductor encapsulant, and the matrix resin is used for higher strength Further added value is required such as fine dispersion.
- ABA-type triblock copolymers modified with polyalkylene glycol chains at both ends of silicone, and copolymers of silicone and polyalkylene glycol having no functional group are coarsely dispersed in matrix resin and cured with epoxy resin. There were problems such as bleed out from things.
- the present invention has high dispersibility in an epoxy resin without impairing heat resistance, and when added to an epoxy resin composition, suppresses a decrease in fluidity and reduces the stress of the resulting cured epoxy resin and It is an object of the present invention to provide a block copolymer that achieves improved toughness, is finely dispersed, and bleed-out is also suppressed.
- the present invention “ ⁇ 1> a polysiloxane (A) having any functional group selected from a carboxylic anhydride group, a hydroxyl group, an epoxy group, a carboxyl group, and an amino group, and a carboxylic anhydride group, a hydroxyl group, a carboxyl group, A polysiloxane-polyalkylene glycol block copolymer obtained by reacting a polyalkylene glycol (B) having any functional group selected from an amino group, an epoxy group, a thiol group, and an isocyanate group.
- a polysiloxane (A) having any functional group selected from a carboxylic anhydride group, a hydroxyl group, an epoxy group, a carboxyl group, and an amino group and a carboxylic anhydride group, a hydroxyl group, a carboxyl group
- a polysiloxane-polyalkylene glycol block copolymer obtained by reacting a polyalkylene glyco
- the amount of emission (A) is not more than 90% by weight to 20% by weight polysiloxane - method for producing a polyalkylene glycol block copolymer.
- An epoxy resin composition comprising the above polysiloxane-polyalkylene glycol block copolymer and an epoxy resin.
- An epoxy resin cured product obtained by curing the above epoxy resin composition.
- a semiconductor sealing material comprising the cured epoxy resin. Is.
- the polysiloxane-polyalkylene glycol block copolymer of the present invention (hereinafter sometimes simply referred to as a block copolymer) has a functional group and is incompatible with an epoxy resin but has excellent flexibility. It is a multi-block copolymer that has a siloxane block and a polyalkylene glycol block that has a functional group and is compatible with an epoxy resin and has excellent flexibility, and is excellent in flexibility and epoxy resin without impairing heat resistance. Both dispersibility is achieved.
- the block copolymer of the present invention When the block copolymer of the present invention is blended with an epoxy resin, it can be finely dispersed homogeneously in the epoxy resin, and the bleed out of the block copolymer from the resulting cured epoxy resin can be suppressed, and the cured epoxy resin The stress can be reduced and the toughness can be improved. Moreover, the fall of the fluidity
- Example 3 is a cross-sectional TEM photograph of the cured epoxy resin obtained in Example 2.
- 4 is a cross-sectional TEM photograph of the cured epoxy resin obtained in Example 7.
- the polysiloxane-polyalkylene glycol block copolymer of the present invention includes a polysiloxane (A) having any functional group selected from a carboxylic anhydride group, a hydroxyl group, an epoxy group, a carboxyl group, and an amino group, and A block copolymer obtained by reacting a polyalkylene glycol (B) having any functional group selected from a carboxylic acid anhydride group, a hydroxyl group, a carboxyl group, an amino group, an epoxy group, a thiol group, and an isocyanate group
- the content of the polysiloxane (A) -derived structure is 20% by mass to 90% by mass.
- reacting the polysiloxane (A) having a functional group with the polyalkylene glycol (B) having a functional group means that the polysiloxane (A) having a functional group, the polyalkylene glycol (B) having a functional group, and May be directly reacted and bonded to each other.
- the polysiloxane (A) having a functional group and the polyalkylene glycol (B) having a functional group may react with both the component (A) and the component (B). You may couple
- the target block copolymer is obtained even when the polysiloxane (A) having a functional group and the polyalkylene glycol (B) having a functional group do not react directly. Obtainable.
- the functional group is a carboxylic acid anhydride group and the other functional group is a hydroxyl group, an epoxy group or an amino group
- one of the functional groups of polysiloxane (A) and polyalkylene glycol (B) is a hydroxyl group
- the other functional group is a carboxylic acid anhydride group, a carboxyl group, an amino group, an epoxy group or an isocyanate group
- one of the functional groups of the polysiloxane (A) and the polyalkylene glycol (B) is An epoxy group
- the other functional group is a carboxylic acid anhydride group
- it is a boxyl group, an amino group or a thiol group
- one of the functional groups of the polysiloxane (A) and the polyalkylene glycol (B) is a carboxyl group
- the other functional group is a hydroxyl group, an amino group or an epoxy group Or when it is a thiol group or an isocyanate group
- one of the functional groups of polysiloxane (A) and polyalkylene glycol (B) is a carboxylic acid anhydride group and the other functional group is a hydroxyl group
- a new carboxyl group is generated after the reaction.
- functional group of polysiloxane (A) or polyalkylene glycol (B) is an epoxy group and the other functional group is a hydroxyl group
- a new hydroxyl group is generated after the reaction.
- the carboxyl group or hydroxyl group newly generated by these reactions contributes to improvement in dispersibility in the epoxy resin and improvement in heat resistance.
- the newly generated functional group is most preferably a carboxyl group from the viewpoint that when added to an epoxy resin to obtain a cured product, the functional group is immobilized on the epoxy resin and bleed out can be suppressed.
- the functional group of the polysiloxane (A) is preferably a carboxylic anhydride group and / or a hydroxyl group.
- the functional group of polysiloxane (A) and the functional group of polyalkylene glycol (B) reacts to form an ester.
- a bond selected from a bond, an ether bond, an amide bond, a urethane bond and a thioester bond is formed.
- the bonding portion of the resulting block copolymer may contain a newly generated carboxyl group and / or hydroxyl group depending on the combination of the functional group of polysiloxane (A) and the functional group of polyalkylene glycol (B). good.
- polysiloxane (A) having the functional group it is preferable to use a polysiloxane represented by the general formula (1).
- n represents the number of repeating units of 5 to 100.
- X is any functional group selected from a carboxylic anhydride group, a hydroxyl group, an epoxy group, a carboxyl group, and an amino group.
- the carboxylic anhydride group includes cyclic groups such as maleic anhydride, phthalic anhydride, and succinic anhydride.
- R 1 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group.
- R 2 is a group selected from a single bond, a divalent aliphatic or aromatic hydrocarbon group having 1 to 10 carbon atoms, and a divalent hydrocarbon ether group having 1 to 10 carbon atoms.
- the single bond means that R 2 does not exist and silicon and X are directly bonded.
- R 2 is preferably butylene, propylene or ethylene, and most preferably propylene or ethylene.
- X is a cyclic carboxylic anhydride group
- the bonding position between X and R 2 or a silicon atom may be any position.
- the divalent hydrocarbon ether group is preferably a group represented by — (CH 2 ) a —O— (CH 2 ) b — and 1 ⁇ a + b ⁇ 10. All R 1 and R 2 and X may be the same or different.
- R 1 in the general formula (1) is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, and does not react with any of X, Y, and the copolymer component (C).
- R 1 and any of X, Y and the copolymer component (C) react with each other, the reaction between X and Y is inhibited or a crosslinking reaction proceeds, which is not preferable.
- the chain length of R 1 is too long, in the fluidity of the resulting block copolymer when added to the epoxy resin to become bad.
- R 1 is preferably any of a propyl group, an ethyl group and a methyl group, more preferably an ethyl group or a methyl group, and most preferably a methyl group. Further, all R 1 may be different or the same.
- polysiloxane (A) having a functional group polyorganosiloxane having a functional group is preferable, and polydimethylsiloxane having a functional group is particularly preferable.
- the weight average molecular weight of the polysiloxane (A) having a functional group is not particularly limited, but the lower limit thereof is preferably 500 or more, more preferably 800 or more, and further preferably 1,000 or more. . Moreover, as an upper limit of a weight average molecular weight, 8,000 or less is preferable, More preferably, it is 5,000 or less, More preferably, it is 4,000 or less, Most preferably, it is 3,000 or less. When the weight average molecular weight of the polysiloxane (A) having a functional group is small, the effect of reducing the elastic modulus is low even when the resulting block copolymer is added to the epoxy resin.
- the weight average molecular weight of the polysiloxane (A) having a functional group is large, the polysiloxane (A) having a functional group and the polyalkylene glycol (B) having a functional group are phase-separated, and the reaction in a uniform state Therefore, the reactivity with the polyalkylene glycol (B) having a functional group is deteriorated. Moreover, since the functional group content of the obtained block copolymer becomes low, the dispersibility improvement effect to the epoxy resin mentioned later becomes low.
- the weight average molecular weight of polysiloxane (A) having a functional group refers to a weight average molecular weight measured by gel permeation chromatography using tetrahydrofuran (THF) as a solvent and converted to polymethyl methacrylate.
- the polysiloxane (A) having a functional group is commercially available from Shin-Etsu Chemical Co., Ltd., X-22-168AS, KF-105, X-22-163A, X-22-163B, X-22-163C.
- polyalkylene glycol (B) having the functional group it is preferable to use a polyalkylene glycol represented by the general formula (2).
- Y is any functional group selected from a carboxylic anhydride group, a hydroxyl group, a carboxyl group, an amino group, an epoxy group, a thiol group, and an isocyanate group.
- the carboxylic anhydride group includes cyclic groups such as maleic anhydride, phthalic anhydride, and succinic anhydride.
- R 3 is a linear or branched alkyl group having 2 to 10 carbon atoms. When the carbon number of R 3 is larger than 10, the polyalkylene glycol (B) having a functional group is not compatible with the epoxy resin, and the dispersibility between the obtained block copolymer and the epoxy resin is poor.
- the strain at break of the cured epoxy resin mixed and cured is reduced, and the effect of improving toughness due to the addition of the block copolymer is reduced.
- the number of carbon atoms of R 3 is small is not preferable because the flexibility is reduced.
- a preferred carbon number of R 3 is 3 or 4. All R 3 and Y may be the same or different.
- polyalkylene glycol (B) having a functional group when the functional group of the polysiloxane (A) is a carboxylic acid anhydride group, Y is a hydroxyl group and R 3 is a linear butylene group. Methylene glycol and / or polypropylene glycol which is a propylene group branched from R 3 is excellent in reactivity with the polysiloxane (A) having a functional group, and the reaction proceeds without using a metal catalyst as a reaction accelerator, Moreover, it is preferable because the polysiloxane (A) and the polyalkylene glycol (B) can be reacted to obtain a homogeneous block copolymer without using an organic solvent. In particular, polytetramethylene glycol is more preferable from the viewpoint of improving heat resistance.
- the weight average molecular weight of the polyalkylene glycol (B) having a functional group is not particularly limited, but the lower limit thereof is preferably 300 or more, more preferably 500 or more, and further preferably 1,000 or more. is there. Further, the upper limit of the weight average molecular weight is preferably 20,000 or less, more preferably 10,000 or less, still more preferably 5,000 or less, and most preferably 3,000 or less. When the weight average molecular weight of the polyalkylene glycol (B) having a functional group is small, the effect of improving toughness when the obtained block copolymer is added to the epoxy resin is low.
- the weight average molecular weight of the polyalkylene glycol (B) having a functional group is large, the polysiloxane (A) having a functional group and the polyalkylene glycol (B) having a functional group are phase-separated, and the reaction in a homogeneous system Therefore, the reactivity with the polysiloxane (A) having a functional group is deteriorated. Moreover, since the functional group content of the obtained block copolymer becomes low, the dispersibility improvement effect to the outstanding epoxy resin becomes low.
- the weight average molecular weight of the polyalkylene glycol (B) having a functional group refers to a weight average molecular weight measured by gel permeation chromatography using tetrahydrofuran (THF) as a solvent and converted into polymethyl methacrylate.
- a copolymer component (C) capable of reacting with these is included in the range in which the flexibility of the resulting block copolymer and good adhesion to the epoxy resin are not impaired. Furthermore, you may make it react.
- the copolymerization component (C) is a molecule having at least one functional group that reacts with the functional group of the polysiloxane (A) and / or the functional group of the polyalkylene glycol (B).
- the obtained block copolymer has a structure derived from the copolymer component (C) in addition to the structure derived from the polysiloxane (A) and the structure derived from the polyalkylene glycol (B).
- copolymer component (C) is dissolved in both the polysiloxane (A) and the polyalkylene glycol (B) during the reaction because the reaction is likely to proceed.
- a plurality of copolymer components (C) may be used.
- the copolymer component (C) has two or more functional groups and the molecular weight is 2,000 or less, the reason is unclear, but only the polysiloxane (A) and the polyalkylene glycol (B) are reacted. It was found that the resulting block copolymer has a higher molecular weight than that of the polymer.
- the number of functional groups in the copolymerization component (C) may be two or more, but if it is three or more, a three-dimensional crosslinking reaction proceeds, leading to a decrease in flexibility. Therefore, polysiloxane (A) and / or Alternatively, the number of functional groups that react with the polyalkylene glycol (B) is preferably two.
- the molecular weight of the copolymerization component (C) is preferably small, preferably 1,500 or less, more preferably 1,000 or less, It is preferably 800 or less, particularly preferably 600 or less, and most preferably 500 or less.
- the molecular weight of the resulting block copolymer decreases as the addition amount increases.
- the copolymer component (C) is preferably one in which the reaction proceeds and the reaction system is uniformly mixed without using a metal catalyst as a reaction accelerator.
- a metal catalyst as a reaction accelerator.
- the functional group of the polysiloxane (A) is a carboxylic acid anhydride group
- the functional group of the polyalkylene glycol (B) is a hydroxyl group, a monovalent or divalent carboxylic acid anhydride, diol, alcohol And phenols.
- divalent carboxylic acid anhydride examples include pyromellitic dianhydride, 4,4′-oxydiphthalic anhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2′-dimethyl-3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 5,5′-dimethyl-3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic acid Dianhydride, 2,3,3 ′, 4′-diphenyl ether tetracarboxylic dianhydride, 2,2 ′, 3,3′-diphenyl ether
- the functional group of the polysiloxane (A) is a carboxylic acid anhydride group and the polyalkylene glycol (B) is polytetramethylene glycol, or the functional group of the polysiloxane (A) is a hydroxyl group and the polyalkylene
- the glycol (B) is polypropylene glycol, it dissolves in the polysiloxane (A) and polytetramethylene glycol or polypropylene glycol and has a low molecular weight, so that the reactivity is increased.
- Pyromellitic dianhydride 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 4,4 ′-(4,4′-isopropylidenediphenoxy) diphthalic anhydride, 4,4 Select from '-oxydiphthalic anhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride At least one is preferable. Among them, pyromellitic acid is easily dissolved in polysiloxane (A) and polyalkylene glycol (B), the system is in a uniform state, and the reaction proceeds without using a metal catalyst as a reaction accelerator. A dianhydride is preferred.
- monovalent carboxylic acid anhydrides include succinic anhydride, phthalic anhydride, maleic anhydride, acetic anhydride, propionic anhydride, oxalic anhydride, and benzoic anhydride.
- the functional group of the polysiloxane (A) is a carboxylic acid anhydride group and the polyalkylene glycol (B) is polytetramethylene glycol, it is dissolved in the polysiloxane (A) and the polytetramethylene glycol and is reactive.
- at least one selected from succinic anhydride, phthalic anhydride, and maleic anhydride is preferable.
- diols examples include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, and 1,5-pentanediol. 1,8-octanediol, 1,9-nonanediol, 1,4-cyclohexanediol, diethylene glycol and the like. In the case of such a hydrocarbon-based alcohol, it is preferable that the molecular chain is long because the flexibility of the resulting block copolymer is not impaired.
- alcohols examples include methanol, ethanol, isopropyl alcohol, butanol, pentanol, hexanol, octanol, dodecanol, tetradecanol, hexadecanol, and octadecanol.
- the functional group of the polysiloxane (A) is a carboxylic acid anhydride group and the polyalkylene glycol (B) is polytetramethylene glycol, it is dissolved in the polysiloxane (A) and the polytetramethylene glycol and is reactive. From the viewpoint of improving at least one selected from octanol and dodecanol.
- phenols examples include phenol, bisphenol A, dibutylhydroxytoluene, cresol, eugenol, guaiacol, thymol, methyl salicylate, propofol and the like.
- the addition amount of a copolymerization component (C) In order not to affect the physical property of the block copolymer of this invention, the one where it is smaller is preferable.
- the upper limit is 100% by mass of the block copolymer, preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less, and most preferably 10% by mass or less.
- the addition amount is larger than this range, the flexibility of the resulting block copolymer is impaired, and the presence of the unreacted copolymer component (C) promotes the curing reaction with the epoxy resin, and the flow This is not preferable because the properties are reduced and the effect of improving toughness is lowered.
- Copolymer component (C) (hereinafter sometimes referred to as copolymer component (C ′)) is added, and polysiloxane (A), polyalkylene glycol (B) and copolymer component (C ′) are reacted. You may use the method of making it.
- a block copolymer can be obtained.
- the polysiloxane (A) and the polyalkylene glycol having a functional group (B) can be homogeneously mixed only with the raw material, uniformly from the copolymerizable polyalkylene glycol polypropylene glycol is a propylene group which R 3 is branched Most preferably used as (B).
- polypropylene glycol is preferable as the polyalkylene glycol (B) because the resulting block copolymer is more finely dispersed in the epoxy resin and more effective in lowering the elastic modulus.
- the polysiloxane (A), which is a block component, and polypropylene glycol can be mixed homogeneously, in the obtained block copolymer, the property of the polysiloxane (A), which is incompatible with the epoxy resin, By improving the compatibility with polypropylene glycol having good compatibility, fine dispersion in the epoxy resin becomes possible, and it is considered that the reduction in the elastic modulus is more noticeably exhibited.
- both the functional group of the polysiloxane (A) and the functional group of the polyalkylene glycol (B) are hydroxyl groups, use a compound in which both ends are carboxylic anhydride groups as the copolymerization component (C ′).
- the block copolymer of the present invention containing a carboxyl group can be obtained without using a metal catalyst of a reaction accelerator causing a side reaction.
- copolymerization component (C ′) among those exemplified as the copolymerization component (C), it reacts with both the polysiloxane (A) having a functional group and the polyalkylene glycol (B) having a functional group.
- pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride in that the reaction can proceed without using an organic solvent, From 4,4 '-(4,4'-isopropylidenediphenoxy) diphthalic anhydride, 4,4'-oxydiphthalic anhydride, and 3,3', 4,4'-biphenyltetracarboxylic dianhydride It is preferably any carboxylic anhydride selected. Pyromellitic dianhydride is most preferable from the viewpoint that flexibility can be imparted to the obtained block copolymer and copolymerization can be performed without using an organic solvent. Two or more copolymerization components (C ′) may be used.
- the content of the structure derived from the copolymer component (C ′) in the block copolymer is preferably 30% by mass or less, based on 100% by mass of the block copolymer.
- the content of the structure derived from the copolymer component (C ′) is large, the effect of lowering the elastic modulus of the block copolymer is impaired, which is not preferable.
- the content is small, it is not preferable because fine dispersion does not occur and bleed out occurs.
- the content is preferably 25% by mass or less, more preferably 20% by mass or less, particularly preferably 15% by mass or less, and most preferably 10% by mass or less.
- the polysiloxane-polyalkylene glycol block copolymer of the present invention is preferably a multi-block copolymer including a structure represented by the general formula (3).
- n is 5 to 100
- m is 3 to 300
- p is 5 to 100 repeating units.
- R 1 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a phenyl group, which may be the same or different.
- Z is a bond formed by the reaction of the polysiloxane (A) having a functional group and the polyalkylene glycol (B) having a functional group.
- the residue obtained by reacting the X of the polysiloxane (A) and the Y of the polyalkylene glycol (B) is the bond Z. Become.
- the X of the polysiloxane (A), the polyalkylene glycol (B) is a bond Z.
- the bonding part Z has any bond selected from an ester bond, an ether bond, an amide bond, a urethane bond, and a thioester bond.
- Z newly includes a carboxyl group and / or a hydroxyl group when a carboxyl group and / or a hydroxyl group is newly generated as a result of this reaction. All Z may be the same or different.
- R 2 is a group selected from a single bond, a divalent aliphatic or aromatic hydrocarbon group having 1 to 10 carbon atoms, and a divalent hydrocarbon ether group having 1 to 10 carbon atoms.
- R 2 may be the same or different.
- R 3 is a linear or branched alkyl group having 2 to 10 carbon atoms, and R 3 may be the same or different. Examples of preferred R 1 , R 2 and R 3 are as described above.
- multiblock copolymer means that the number of repeating units p is 2 or more, and preferably p is 5 or more.
- AB-type diblock copolymers and ABA-type triblock copolymers having p of 1 are not called multiblock copolymers.
- the block copolymer of the present invention has a functional group copolymerization component of the polysiloxane (A) and the polyalkylene glycol (B) described above in the block copolymer, and in some cases, the polysiloxane. Since (A) and a polyalkylene glycol (B) have a functional group newly generated by reaction, compared with a copolymer having a functional group only at both ends, in any range from low molecular weight to high molecular weight Have a high functional group content.
- the block copolymer even when the block copolymer has a high molecular weight, it can contain many functional groups, so it has excellent dispersibility in the epoxy resin and suppresses bleed out of the block copolymer from the cured epoxy resin. As a result, the effects of high stress reduction and high toughness can be obtained.
- the block copolymer having the weight average molecular weight and the functional group amount within the following preferred ranges can maintain the fluidity in the epoxy resin composition and improve the heat resistance of the block copolymer. Decrease in glass transition temperature Tg and increase in linear expansion coefficient of the cured epoxy resin can be suppressed.
- the weight average molecular weight (M w ) of the block copolymer of the present invention is not particularly limited, but the lower limit is preferably from the viewpoint of mechanical properties and fluidity of the cured epoxy resin added with the block copolymer. It is 5,000 or more, More preferably, it is 10,000 or more, More preferably, it is 15,000 or more, More preferably, it is 20,000 or more, Especially preferably, it is 30,000 or more.
- the upper limit is preferably 500,000 or less, more preferably 200,000 or less, more preferably 150,000 or less, still more preferably 100,000 or less, and most preferably 80,000 or less. 000 or less.
- the weight average molecular weight is smaller than this range, the effect of lowering the elastic modulus and improving the toughness of the cured epoxy resin to which the block copolymer is added is reduced.
- the weight average molecular weight is larger than this range, the fluidity of the epoxy resin composition added to the epoxy resin is lowered, and it is not possible to penetrate into the details when molding the sealing material, which is preferable because it causes cracks. Absent.
- the weight average molecular weight of the block copolymer mentioned here refers to a weight average molecular weight measured by gel permeation chromatography using tetrahydrofuran (THF) as a solvent and converted to polymethyl methacrylate.
- THF tetrahydrofuran
- the molecular weight distribution (M w / M n ) of the block copolymer of the present invention is preferably 5 or less, more preferably 3 or less, and further preferably 2 or less.
- the lower limit is 1.
- the molecular weight distribution (M w / M n ) is calculated from the weight average molecular weight (M w ) and the number average molecular weight (M n ) measured as described above using gel permeation chromatography.
- the block copolymer of the present invention preferably has a functional group content of 0.1 mmol / g or more and 3.0 mmol / g or less.
- the lower limit is more preferably 0.2 mmol / g or more, and still more preferably 0.3 mmol / g or more.
- the upper limit is more preferably 3.0 mmol / g or less, still more preferably 2.8 mmol / g or less, and particularly preferably 2.5 mmol / g or less.
- the functional group content is higher than this range, when the epoxy resin composition is produced, fluidity deterioration due to side reaction with the epoxy resin and heat resistance decrease due to the functional group are not preferable.
- the functional group content is lower than this range, the dispersibility in the epoxy resin is lowered, and the block copolymer from the epoxy resin composition or the cured product is coarsely dispersed in the epoxy resin composition or the cured product. This is not preferable because bleed out occurs.
- the functional group content includes the functional group derived from the polysiloxane (A) having a functional group, the functional group derived from the polyalkylene glycol (B) having a functional group, and a copolymer component (included in the block copolymer).
- This is the sum of the contents of all of the functional groups derived from C) and the functional groups newly generated by the reaction thereof.
- the block copolymer contains only a carboxyl group as a functional group, the content of the carboxyl group is the functional group content.
- a block copolymer contains several functional groups like a carboxyl group and a hydroxyl group, let the sum total of each functional group content be the functional group content contained in a block copolymer.
- the functional group content can be determined by a known titration method.
- the block copolymer when quantifying the carboxyl group, the block copolymer is dissolved in toluene or tetrahydrofuran, and titrated with 0.1 mol / L alcoholic potassium hydroxide using phenolphthalein as an indicator.
- an epoxy group when quantifying an epoxy group, it can be quantified by the method according to JIS K 7236, and when quantifying a hydroxyl group, it can be quantified by a method according to JIS K 0070.
- the functional group content of the resulting block copolymer is adjusted by adjusting the weight average molecular weight of the polysiloxane (A) having a functional group as a raw material and / or the polyalkylene glycol (B) having a functional group. It is possible.
- the functional group in the block copolymer is a carboxyl group
- a method of performing esterification by heating under reduced pressure in the presence of a monohydric alcohol and an acid catalyst, and JP-A 2000-119520 are exemplified.
- the method of protecting a carboxyl group using N, N-dimethylformamide dialkyl acetal is most useful because it can be processed under mild conditions without using a metal catalyst.
- the block copolymer of the present invention has an effect that no bleed out from the cured epoxy resin occurs as described above. Whether or not the block copolymer bleeds out from the cured epoxy resin can be determined by the following method. As a simple confirmation method, an ultrathin section of a cured epoxy resin is prepared, the ultrathin section is impregnated in hexane for 15 minutes, and then observed with a scanning electron microscope. When bleed-out has occurred, the portion where the block copolymer was present is extracted with hexane, becomes a cavity, and spherical irregularities are observed. If irregularities are observed, it is determined that there is a bleed-out, and if not observed, it is determined that there is no bleed-out.
- the mass of the block copolymer dissolved in chloroform was measured, and the block copolymer in the cured epoxy resin calculated from the composition was used.
- the mass of the block copolymer dissolved in chloroform is 5% by mass or more with respect to the mass of 5% by mass, it is judged that there is bleed out, and when it is less than 5% by mass, there is no bleed out.
- a smaller bleed-out is preferable from the viewpoint of improving quality in addition to lowering the elastic modulus and improving toughness of the cured epoxy resin.
- the bleed out is preferably 3% by mass or less, more preferably 2% by mass or less, and further preferably 1% by mass or less.
- the content of the polysiloxane (A) -derived structure in the block copolymer of the present invention is 100% by mass with respect to the entire block copolymer, and the lower limit is 20% by mass or more, more preferably 30% by mass or more. is there. Moreover, as an upper limit, it is 90 mass% or less, More preferably, it is 80 mass% or less, More preferably, it is 70 mass% or less.
- the content of the structure derived from polysiloxane (A) is too small, the effect of lowering the modulus of elasticity by adding the block copolymer is sufficient even if a block copolymer is added to the epoxy resin to produce a cured product. The function as a stress reducing agent is not sufficient.
- the block copolymer of the present invention has an effect that heat resistance is not impaired while improving dispersibility in an epoxy resin.
- the heat resistance mentioned here can be evaluated by measuring the thermal decomposition temperature of the block copolymer. Specifically, the block copolymer is measured using a thermogravimetric apparatus (TGA), and the temperature when the mass is reduced by 5 mass% with respect to the mass at 30 ° C. is evaluated as the 5% weight reduction temperature. The higher the 5% weight loss temperature, the better the heat resistance.
- the 5% weight loss temperature is preferably 250 ° C. or higher, more preferably 280 ° C. or higher, further preferably 300 ° C. or higher, most preferably 350 ° C. or higher, and most preferably 400 ° C. or higher.
- the 5% weight loss temperature is lower than 250 ° C., when used as a stress reducing agent, the polymer may be decomposed during the operation of the semiconductor to cause breakage of the package, which is not preferable.
- the block copolymer of the present invention can be produced by reacting the polysiloxane (A) having the functional group and the polyalkylene glycol (B) having the functional group.
- the reaction method include a method in which a polysiloxane (A) having a functional group and a polyalkylene glycol (B) having a functional group are mixed and reacted by heating, and an organic solvent can be used if necessary. You may go inside. Moreover, you may make it react in nitrogen atmosphere as needed, and you may carry out under reduced pressure in order to accelerate
- the mixing ratio of the functional group-containing polysiloxane (A) and the functional group-containing polyalkylene glycol (B) can be adjusted as appropriate, but the functional group-containing polysiloxane (A) and the functional group-containing polysiloxane are not limited.
- the mixing ratio is preferably such that the stoichiometric equivalent ratio is between 0.1 and 10.
- the stoichiometric equivalent ratio refers to the ratio of the number of moles of functional groups contained in the polyalkylene glycol (B) to the number of moles of functional groups contained in the polysiloxane (A).
- the equivalent ratio is more preferably 0.2 to 5, more preferably 0.5 to 3, and more preferably 0.8 to 1 in that the weight average molecular weight of the resulting block copolymer increases. .5 is most preferred, and 1 is significantly preferred.
- the polysiloxane (A) having a functional group and the polyalkylene glycol (B) having a functional group do not react directly, and the copolymer component (C ′) has a polysiloxane (A) having a functional group and a functional group.
- the copolymer component (C ′) with respect to the total number of moles of functional groups contained in the polysiloxane (A) and the polyalkylene glycol (B) having a functional group is more preferably from 0.2 to 5, more preferably from 0.5 to 3, most preferably from 0.8 to 1.5, 1 is extremely preferred.
- the said polysiloxane (A) in order to make content of the structure derived from polysiloxane (A) contained in 100 mass% of obtained block copolymers into 20 mass% or more and 90 mass% or less, the said polysiloxane (A), the said poly The raw materials are mixed and reacted so that the total of the alkylene glycol (B) and the copolymer component (C) is 100% by mass, and the amount of the polysiloxane (A) is 20% by mass or more and 90% by mass or less. It is preferable.
- the organic solvent is preferably a good solvent of polysiloxane (A) having a functional group and polyalkylene glycol (B) having a functional group.
- hydrocarbon solvents such as toluene, xylene, benzene, 2-methylnaphthalene
- ester solvents such as ethyl acetate, methyl acetate, butyl acetate, butyl propionate, butyl butyrate, ethyl acetoacetate
- Halogenated hydrocarbons such as carbon tetrachloride, 1,2-dichloroethane, 1,1,1-trichloroethane, chlorobenzene, 2,6-dichlorotoluene, 1,1,1,3,3,3-hexafluoroisopropanol Solvents
- ketone solvents such as acetone, methyl ethyl ketone, methyl
- toluene, xylene or ethyl acetate is preferred from the viewpoint of the reaction rate and the balance of solvent removal after the reaction.
- organic solvents may be used alone or in combination of two or more.
- an organic solvent when making it react in an organic solvent, an organic solvent can be removed and refine
- the use of no organic solvent does not require a purification step for removing the organic solvent, the production process is simple, the reaction temperature can be increased, and the reaction accelerator metal Even in a system that does not use a catalyst, the reaction rate can be increased, which is preferable because productivity is improved.
- the temperature at which the polysiloxane (A) having a functional group and the polyalkylene glycol (B) having a functional group are reacted is not particularly limited because it depends on the combination of the functional groups of each, but side reactions and polymer decomposition are suppressed. Therefore, it is preferably 220 ° C. or lower, more preferably 200 ° C. or lower, further preferably 180 ° C. or lower, and particularly preferably 150 ° C. or lower. In addition, when the reaction proceeds at room temperature or lower, it is difficult to stably store at room temperature. Therefore, it is preferable that the reaction does not proceed at room temperature.
- the lower limit of the reaction temperature is preferably 50 ° C. or higher, more preferably 70 ° C. or higher, and further preferably 100 ° C. or higher.
- reaction accelerator or the like may be added at the time of reaction, but depending on the combination of the functional group of polysiloxane (A) and the functional group of polyalkylene glycol (B), it is easy without adding a reaction accelerator. It is possible to obtain the desired block copolymer.
- the functional group of the polysiloxane (A) is an epoxy group and the functional group of the polyalkylene glycol (B) is a hydroxyl group
- sodium, sodium hydroxide, sodium methoxy can be used as a reaction accelerator.
- sodium ethoxide and potassium hydroxide when the functional group of the polysiloxane (A) is a carboxyl group and the functional group of the polyalkylene glycol (B) is a hydroxyl group, an acidic metal catalyst such as titanium or zinc, sulfuric acid or phosphoric acid is used as a reaction accelerator.
- Catalysts such as hydrochloric acid, alumina and zeolite.
- a metal catalyst as a reaction accelerator in order to obtain a block copolymer.
- a metal catalyst as a reaction accelerator
- the metal catalyst remains, It is not preferable because it may adversely affect Therefore, as described above, it is preferable to carry out the reaction without using a metal catalyst which is a reaction accelerator.
- the reaction time depends on the combination of the functional group of the polysiloxane (A) and the functional group of the polyalkylene glycol (B), but is preferably within 20 hours, more preferably within 15 hours from the viewpoint of productivity. More preferably, it is within 10 hours.
- the block copolymer of the present invention is produced by reacting two kinds of flexible polymers, by adding to the epoxy resin, the cured product can exhibit a low elastic modulus effect and a toughness improving effect. Can do.
- the epoxy resin cured product is efficiently reduced in elastic modulus and improved toughness, Internal stress can be relaxed.
- the block copolymer of the present invention is compatible or finely dispersed in the epoxy resin, the resulting epoxy resin composition is excellent in fluidity and handling properties are improved.
- the epoxy resin composition of the present invention is a mixture of the epoxy resin described later and the block copolymer of the present invention, and refers to a mixture before the curing reaction.
- a preferable amount of the block copolymer contained in the epoxy resin composition of the present invention is 0.1 to 50 parts by mass, preferably 0.1 to 40 parts by mass with respect to 100 parts by mass of the epoxy resin. More preferably, it is 0.5 to 30 parts by mass, and still more preferably 0.5 to 20 parts by mass.
- an epoxy resin it does not restrict
- the glycidyl ether type epoxy resin examples include bisphenol A type epoxy resin obtained by reaction of bisphenol A and epichlorohydrin, bisphenol F type epoxy resin obtained by reaction of bisphenol F and epichlorohydrin, 4, 4 Bisphenol S epoxy resin obtained by reaction of '-dihydroxydiphenylsulfone and epichlorohydrin, biphenyl epoxy resin obtained by reaction of 4,4'-biphenol and epichlorohydrin, resorcinol and epichlorohydrin Resorcinol type epoxy resin obtained by reaction, phenol novolak type epoxy resin obtained by reaction of phenol and epichlorohydrin, other polyethylene glycol type epoxy resin, polypropylene glycol Type epoxy resins, naphthalene type epoxy resins, and substitutions at these regioisomers and alkyl group or halogen.
- bisphenol A type epoxy resins include “jER” (registered trademark) 825, “jER” (registered trademark) 826, “jER” (registered trademark) 827, “jER” (registered trademark) 828 (and above, Mitsubishi). Chemical Co., Ltd.), “Epiclon” (registered trademark) 850 (DIC Corporation), “Epototo” (registered trademark) YD-128 (Nippon Steel & Sumikin Chemical Co., Ltd.), D.C. E.
- R-331 TM (Dow Chemical), “Bakelite” EPR154, “Bakelite” EPR162, “Bakelite” EPR172, “Bakelite” EPR173, and “Bakelite” (registered trademark) EPR174 (above, manufactured by Bakelite AG) and the like can be mentioned.
- biphenyl type epoxy resins include “jER” (registered trademark) YX4000, “jER” (registered trademark) YX4000K, “jER” (registered trademark) YX4000H, “jER” (registered trademark) YX4000HK, “jER” ( Registered trademark) YL6121H, “jER” (registered trademark) YL6121HN (manufactured by Mitsubishi Chemical Corporation), and the like.
- Examples of commercially available resorcinol-type epoxy resins include “Denacol” (registered trademark) EX-201 (manufactured by Nagase ChemteX Corporation).
- phenol novolac epoxy resins include “jER” (registered trademark) 152, “jER” (registered trademark) 154 (manufactured by Mitsubishi Chemical Corporation), and “Epicron” (registered trademark) 740 (DIC ( And EPN179, EPN180 (manufactured by Huntsman Advanced Materials), and the like.
- glycidylamine type epoxy resin examples include tetraglycidyldiaminodiphenylmethanes, glycidyl compounds of aminophenol, glycidylanilines, and glycidyl compounds of xylenediamine.
- tetraglycidyldiaminodiphenylmethanes include “Sumiepoxy” (registered trademark) ELM434 (manufactured by Sumitomo Chemical Co., Ltd.), “Araldite” (registered trademark) MY720, “Araldite” (registered trademark) MY721, “Araldite” ( (Registered trademark) MY9512, “Araldite” (registered trademark) MY9612, “Araldite” (registered trademark) MY9634, “Araldite” (registered trademark) MY9663 (manufactured by Huntsman Advanced Materials), “jER” (registered trademark) 604 (manufactured by Mitsubishi Chemical Corporation), “Bakelite” (registered trademark) EPR494, “Bakelite” (registered trademark) EPR495, “Bakelite” (registered trademark) EPR496, and “Bakelite” (registered trademark) EPR4
- glycidyl compounds of aminophenol include “jER” (registered trademark) 630 (manufactured by Mitsubishi Chemical Corporation), “Araldite” (registered trademark) MY0500, “Araldite” (registered trademark) MY0510 (above Huntsman Advanced Materials Co., Ltd.), “Sumiepoxy” (registered trademark) ELM120, and “Sumiepoxy” (registered trademark) ELM100 (manufactured by Sumitomo Chemical Co., Ltd.).
- Examples of commercially available glycidyl anilines include GAN, GOT (manufactured by Nippon Kayaku Co., Ltd.) and “Bakelite” (registered trademark) EPR493 (manufactured by Bakelite AG).
- Examples of the glycidyl compound of xylenediamine include TETRAD-X (Mitsubishi Gas Chemical Co., Ltd.).
- glycidyl ester type epoxy resin examples include diglycidyl phthalate, diglycidyl hexahydrophthalate, diglycidyl isophthalate, diglycidyl dimer, and various isomers thereof.
- Examples of commercial products of diglycidyl phthalate include "Epomic” (registered trademark) R508 (manufactured by Mitsui Chemicals) and “Denacol” (registered trademark) EX-721 (manufactured by Nagase ChemteX Corporation). It is done.
- Examples of commercially available hexahydrophthalic acid diglycidyl ester include “Epomic” R540 (manufactured by Mitsui Chemicals) and AK-601 (manufactured by Nippon Kayaku Co., Ltd.).
- dimer acid diglycidyl ester examples include “jER” (registered trademark) 871 (manufactured by Mitsubishi Chemical Corporation) and “Epototo” (registered trademark) YD-171 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.). It is done.
- alicyclic epoxy resins include “Celoxide” (registered trademark) 2021P (manufactured by Daicel Corporation), CY179 (manufactured by Huntsman Advanced Materials), “Celoxide” (registered trademark) 2081 ((stock) ) Manufactured by Daicel), and “Celoxide” (registered trademark) 3000 (manufactured by Daicel Corporation).
- the epoxy resin is preferably a resin selected from biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin and bisphenol S type epoxy resin from the viewpoint of heat resistance, toughness and low reflow property. Or a bisphenol A type epoxy resin is more preferable, and a biphenyl type epoxy resin is still more preferable.
- the said epoxy resin may be used independently, or may use 2 or more types together.
- a curing agent and / or a curing accelerator can be added to the epoxy resin composition.
- Epoxy resin curing agents include aliphatic polyamine curing agents such as diethylenetriamine and triethylenetriamine; alicyclic polyamine curing agents such as mensendiamine and isophoronediamine; aromatic polyamines such as diaminodiphenylmethane and m-phenylenediamine Curing agent; polyamide, modified polyamine, phthalic anhydride, acid anhydride curing agent such as pyromellitic anhydride and trimellitic anhydride; polyphenol curing agent such as phenol novolac resin and phenol aralkyl resin; polymercaptan, 2, 4 Anionic catalysts such as 2,6-tris (dimethylaminomethyl) phenol, 2-ethyl-4-methylimidazole and 2-phenyl-4-methylimidazole; Cationic catalysts such as boron trifluoride monoethylamine complex; Njiamido, like latent curing agent such as aromatic diazonium salts and molecular sieves
- a curing agent selected from an aromatic amine curing agent, an acid anhydride curing agent and a polyphenol curing agent is preferably used in terms of providing an epoxy resin cured product having excellent mechanical properties.
- a curing agent selected from a phenol novolac resin and a phenol aralkyl resin because of its excellent storage stability.
- aromatic amine curing agents include metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, metaxylylenediamine, diphenyl-p-dianiline, and various derivatives such as alkyl substituents thereof and the position of the amino group. Different isomers are mentioned.
- acid anhydride curing agents include methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic acid anhydride, hydrogenated methylnadic acid anhydride, trialkyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride.
- acid anhydride curing agents include acid, hexahydrophthalic anhydride, dodecenyl succinic anhydride, benzophenone tetracarboxylic dianhydride, and the like.
- polyphenol curing agent examples include phenol novolak resin, phenol aralkyl resin, 1-naphthol aralkyl resin, o-cresol novolac epoxy resin, dicyclopentadiene phenol resin, terpene phenol resin, naphthol novolak type resin and the like.
- the optimum value of the addition amount of the curing agent varies depending on the type of the epoxy resin and the curing agent, but the stoichiometric equivalent ratio is 0.5 to 1.% relative to the total epoxy groups contained in the epoxy resin composition. 4 is preferable, and 0.6 to 1.4 is more preferable.
- the equivalent ratio is less than 0.5, the curing reaction does not occur sufficiently, and curing failure may occur or the curing reaction may take a long time.
- the equivalent ratio is larger than 1.4, the curing agent that is not consumed at the time of curing becomes a defect, which may deteriorate the mechanical properties.
- the curing agent can be used in either monomer or oligomer form, and may be in either powder or liquid form when mixed. These curing agents may be used alone or in combination of two or more. Moreover, you may use together a hardening accelerator.
- curing accelerator examples include amine compound-based curing accelerators represented by 1,8-diazabicyclo (5.4.0) undecene-7; imidazoles represented by 2-methylimidazole and 2-ethyl-4-methylimidazole Compound-based curing accelerators: Phosphorus compound-based curing accelerators typified by triphenyl phosphite can be used. Of these, phosphorus compound-based curing accelerators are most preferable.
- additives such as flame retardants other than epoxy resins and block copolymers, fillers, colorants, mold release agents and the like may be added as necessary.
- the filler is not particularly limited, and powders and fine particles such as fused silica, crystalline silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, aluminum nitride, boron nitride, beryllia, zirconia are used. These fillers may be used alone or in combination of two or more. Among them, it is preferable to use fused silica because it lowers the linear expansion coefficient.
- the shape of the filler is preferably spherical from the viewpoint of fluidity and wear during molding.
- the blending amount of the filler is preferably 20 to 2000 parts by mass, more preferably 50 to 2000 parts by mass with respect to 100 parts by mass of the epoxy resin from the viewpoint of lowering the moisture absorption rate, reducing the linear expansion coefficient, and improving the strength.
- Parts more preferably 100 to 2000 parts by mass, particularly preferably 100 to 1000 parts by mass, and most preferably 500 to 800 parts by mass.
- additives examples include carbon black, calcium carbonate, titanium oxide, silica, aluminum hydroxide, glass fiber, hindered amine-based degradation inhibitor, hindered phenol-based degradation inhibitor, and the like.
- additives are preferably added before the epoxy resin composition is cured, and may be added in any form of powder, liquid, and slurry.
- the epoxy resin composition of the present invention has good fluidity and excellent handleability. When used for a semiconductor encapsulant, if the fluidity is poor, the epoxy resin composition cannot be filled in detail, which may cause voids and damage the package. When the block copolymer of the present invention is added to an epoxy resin, an increase in viscosity due to the addition is small, and an epoxy resin composition excellent in fluidity can be obtained.
- the fluidity in the present invention can be evaluated by measuring the viscosity with a rheometer. Specifically, at 175 ° C., which is near the molding temperature of the semiconductor sealing material, the viscosity of the epoxy resin composition not containing the block copolymer and the block copolymer of 15 parts per 100 parts by mass of the epoxy resin composition. The viscosity of the epoxy resin composition containing part by mass is measured. In addition, when an epoxy resin hardening
- the fluidity is evaluated by the rate of increase in the viscosity of the composition when 15 parts by mass of the block copolymer is included relative to the case where the block copolymer is not included.
- the upper limit of the specific increase rate of the viscosity is preferably 15 times or less, more preferably 13 times or less, still more preferably 10 times or less, and most preferably 8 times or less.
- the lower limit is 1 time or more, more preferably 1.5 times or more, still more preferably 2 times or more, and most preferably 2.5 times or more.
- the rate of increase in viscosity is large, the resulting epoxy resin composition has poor fluidity and cannot be penetrated into details during molding of the sealing material, which is not preferable because it causes cracks.
- the increase rate of a viscosity is small, since the elasticity modulus fall effect and toughness improvement effect of the epoxy resin hardened
- the epoxy resin composition of the present invention can be prepared by adding the block copolymer to an epoxy resin and / or a curing agent and kneading the mixture using a generally known kneader.
- kneader include a three-roll kneader, a self-revolving mixer, a planetary mixer, and the like.
- the cured epoxy resin of the present invention is obtained by curing reaction of the above epoxy resin composition.
- a temperature may be applied as necessary.
- the temperature at that time is preferably room temperature to 250 ° C., more preferably 50 to 200 ° C., further preferably 70 to 190 ° C., and particularly preferably 100 to 180 ° C.
- the rate of temperature rise at that time is not particularly limited, but is preferably 0.5 to 20 ° C./min, more preferably 0.5 to 10 ° C./min, and further preferably 1.0 to 5 ° C. / Min.
- the pressure during curing is preferably 1 to 100 kg / cm 2 , more preferably 1 to 50 kg / cm 2 , still more preferably 1 to 20 kg / cm 2 , and particularly preferably 1 to 5 kg / cm 2 .
- the block copolymer is uniformly finely dispersed inside. Whether it is uniformly and finely dispersed can be determined by staining the cured resin plate with ruthenium tetroxide and confirming the cross section with a photograph obtained with a transmission electron microscope.
- the polysiloxane domain is dyed by dyeing with ruthenium tetroxide.
- the finer the average domain diameter of the polysiloxane domain the better the effect of improving toughness.
- the average domain diameter of the polysiloxane domain can be calculated by specifying the diameter of 100 arbitrary domains from the above transmission electron microscope (TEM) photograph and calculating the arithmetic average according to the following equation. When the domain is not spherical, the maximum diameter of the domain is taken as its diameter.
- Ri domain individual diameter
- n number of measurements 100
- Dn average domain diameter
- the average domain diameter of the polysiloxane domain determined by this method is preferably 20 ⁇ m or less, more preferably 5 ⁇ m or less, further preferably 1 ⁇ m or less, particularly preferably 500 nm or less, and particularly preferably 200 nm. Or less, and most preferably 100 nm or less.
- the dispersion state of the block copolymer in the cured epoxy resin can be confirmed using energy dispersive X-ray analysis (EDX). Specifically, the cross-section of the cured epoxy resin to which the block copolymer has been added is observed using EDX, and mapping with silicon is performed to determine the dispersion state of the block copolymer.
- EDX energy dispersive X-ray analysis
- the semiconductor sealing material of the present invention is made of the cured epoxy resin of the present invention.
- the cured epoxy resin of the present invention is used as a material suitable for a semiconductor encapsulant because the block copolymer dispersed therein functions as a stress reducing agent.
- semiconductor sealing material refers to a material that seals in order to protect electronic components such as semiconductor elements from external stimuli.
- the block copolymer of the present invention is a reaction between the polysiloxane (A) having a flexible functional group and the polyalkylene glycol (B) having a flexible functional group compatible with the epoxy resin. Even if it has a high molecular weight, it is possible to have abundant functional groups in the molecule, so that the dispersibility in the epoxy resin is extremely excellent. Moreover, the epoxy resin composition containing the block copolymer and the epoxy resin of the present invention has excellent fluidity, has a small decrease in fluidity due to the addition of the block copolymer, and is excellent in handleability.
- the cured epoxy resin obtained by curing this epoxy resin composition has the added block copolymer dispersed finely, bleed-out is suppressed, and not only lowering the elastic modulus of the cured epoxy resin but also improving toughness Are also expressed. From these facts, the block copolymer of the present invention is extremely useful as a stress reducing agent for epoxy resins.
- the 5% weight reduction temperature of the block copolymer, the polysiloxane (A) having a functional group, and the polyalkylene glycol (B) having a functional group is determined by a thermogravimetry apparatus (Inc. It was measured and evaluated under the following conditions using Shimadzu Shimadzu automatic differential and thermogravimetric simultaneous measurement device DTG-60).
- Viscosity measurement The viscosity of the composition in which the epoxy resin and the epoxy resin curing agent were mixed at the mixing ratio shown in each example was measured using a rheometer (MCR501 manufactured by Anton Paar) under the following conditions. The viscosity at ° C was determined. Next, the viscosity of the epoxy resin composition in which 15 parts by mass of the block copolymer was added to 100 parts by mass of the same epoxy resin and epoxy resin curing agent was measured in the same manner. The magnification of the rate of increase in the viscosity of the composition in the case of containing 15 parts by mass of the block copolymer relative to the case of not containing the block copolymer was determined.
- Ri domain individual diameter
- n number of measurements 100
- Dn average domain diameter
- the obtained block copolymer is a colorless and transparent liquid
- the content of the structure derived from the polysiloxane (A) is 50% by mass
- the weight average molecular weight is 46,000
- the 5% weight reduction temperature is 309 ° C.
- the carboxylic acid The content was 1.01 mmol / g.
- the content of the structure derived from the polysiloxane (A) of the obtained block copolymer is 50% by mass, the weight average molecular weight is 49,000, the 5% weight reduction temperature is 313 ° C., and the carboxylic acid content is 1.01 mmol / g.
- the content of the structure derived from the polysiloxane (A) of the obtained block copolymer is 25% by mass, the weight average molecular weight is 30,000, the 5% weight reduction temperature is 325 ° C., and the carboxylic acid content is 0.51 mmol / g.
- the obtained block copolymer is a colorless and transparent liquid.
- the content of the structure derived from the polysiloxane (A) is 33% by mass, the weight average molecular weight is 53,000, the 5% weight reduction temperature is 311 ° C., and the carboxylic acid. The content was 0.71 mmol / g.
- the obtained block copolymer is a colorless and transparent liquid.
- the content of the structure derived from the polysiloxane (A) is 61% by mass, the weight average molecular weight is 49,000, the 5% weight reduction temperature is 312 ° C., and the carboxylic acid. The content was 0.68 mmol / g.
- the content of the structure derived from the polysiloxane (A) was 20% by mass, the weight average molecular weight was 106,000, the 5% weight reduction temperature was 285 ° C., and the carboxylic acid content was 0.98 mmol / g.
- the content of the structure derived from the polysiloxane (A) was 20% by mass, the weight average molecular weight was 182,000, the 5% weight reduction temperature was 289 ° C., and the carboxylic acid content was 0.98 mmol / g.
- the content of the structure derived from the polysiloxane (A) was 50% by mass, the weight average molecular weight was 33,000, the 5% weight reduction temperature was 312 ° C., and the carboxylic acid content was 1.11 mmol / g.
- Example 1 (Production of cured epoxy resin) 9.0 g of the block copolymer obtained in Production Example 1, 38.25 g of biphenyl type epoxy resin (manufactured by Mitsubishi Chemical Corporation, “jER” (registered trademark) YX4000H) as an epoxy resin, and phenol novolac type curing as a curing agent 21.75 g of the agent (M-1 Kasei Co., Ltd., H-1) was weighed into a 150 cc stainless steel beaker and dissolved in a 120 ° C. oven to make it uniform.
- biphenyl type epoxy resin manufactured by Mitsubishi Chemical Corporation, “jER” (registered trademark) YX4000H
- phenol novolac type curing as a curing agent 21.75 g of the agent (M-1 Kasei Co., Ltd., H-1) was weighed into a 150 cc stainless steel beaker and dissolved in a 120 ° C. oven to make it uniform.
- the uncured epoxy resin composition was cast into an aluminum mold in which a 4 mm thick “Teflon” (registered trademark) spacer and a release film were set, and placed in an oven.
- the oven temperature was set to 80 ° C., held for 5 minutes, then heated to 175 ° C. at a rate of 1.5 ° C./min and cured for 4 hours to obtain a cured epoxy resin having a thickness of 4 mm.
- the obtained cured epoxy resin was cut into a width of 10 mm and a length of 80 mm, and 3 points according to JIS K7171 (2008) using a Tensilon universal testing machine (TENSILON TRG-1250, manufactured by A & D).
- TENSILON TRG-1250 manufactured by A & D.
- a bending test was conducted and the flexural modulus and the strain at break were measured.
- the flexural modulus was 2.5 GPa and the strain at break was 13%.
- the uncured epoxy resin composition was finely dispersed, its viscosity was 0.125 Pa ⁇ s, the rate of increase in viscosity was 5.2 times, and the average domain diameter of the polysiloxane in the cured product was 50 nm.
- the soluble content was 0.7%, and no bleed-out occurred.
- Table 1 The results are shown in Table 1.
- Example 2 (Production of cured epoxy resin 2) A cured epoxy resin was obtained in the same manner as in Example 1 except that the block copolymer was replaced with 9.0 g of the block copolymer obtained in Production Example 2. Bleed-out did not occur, and the flexural modulus and strain at break of the obtained cured epoxy resin were measured and found to be 2.5 GPa in flexural modulus and 11% strain at break.
- the uncured epoxy resin composition is finely dispersed, its viscosity is 0.139 Pa ⁇ s, the rate of increase in viscosity is 5.8 times, and the average domain diameter of polysiloxane in the cured product is 53 nm (FIG. 1). ), The soluble content was 0.2%, and no bleed out occurred. The results are shown in Table 1.
- Example 3 (Production of cured epoxy resin 3) A cured epoxy resin was obtained in the same manner as in Example 1 except that the block copolymer was replaced with 9.0 g of the block copolymer obtained in Production Example 4. Bleed-out did not occur, and the flexural modulus and strain at break of the obtained cured epoxy resin were measured. As a result, the flexural modulus was 2.4 GPa and the strain at break was 15%.
- the uncured epoxy resin composition is finely dispersed, its viscosity is 0.106 Pa ⁇ s, the rate of increase in viscosity is 4.4 times, the average domain diameter of polysiloxane in the cured product is 40 nm, and soluble The minute was 0.5%, and no bleed out occurred. The results are shown in Table 1.
- Example 4 (Production of cured epoxy resin 4) A cured epoxy resin was obtained in the same manner as in Example 1 except that the block copolymer was replaced with 9.0 g of the block copolymer obtained in Production Example 5. No bleed-out occurred, and the flexural modulus and strain at break of the obtained cured epoxy resin were measured. As a result, the flexural modulus was 2.4 GPa and the strain at break was 11%.
- the uncured epoxy resin composition is finely dispersed, its viscosity is 0.064 Pa ⁇ s, the rate of increase in viscosity is 2.7 times, and the average domain diameter of polysiloxane in the cured product is 65 nm, soluble. The minute was 1.2% and no bleed out occurred. The results are shown in Table 1.
- Example 5 (Production of cured epoxy resin 5) A cured epoxy resin was obtained in the same manner as in Example 1 except that the block copolymer was replaced with 9.0 g of the block copolymer obtained in Production Example 6. No bleed-out occurred, and the flexural modulus and strain at break of the obtained epoxy resin cured product were measured. As a result, the flexural modulus was 3.0 GPa and the strain at break was 12%.
- the uncured epoxy resin composition is finely dispersed, its viscosity is 0.356 Pa ⁇ s, the rate of increase in viscosity is 14.8 times, and the average domain diameter of polysiloxane in the cured product is 60 nm, soluble. The minute was 0.2% and no bleed out occurred. The results are shown in Table 1.
- Example 6 (Production of cured epoxy resin 6) A cured epoxy resin was obtained in the same manner as in Example 1 except that the block copolymer was replaced with 9.0 g of the block copolymer obtained in Production Example 8. No bleed-out occurred, and the flexural modulus and strain at break of the obtained cured epoxy resin were measured. As a result, the flexural modulus was 2.6 GPa and the strain at break was 15%.
- the uncured epoxy resin composition is finely dispersed, its viscosity is 0.06 Pa ⁇ s, the rate of increase in viscosity is 2.5 times, and the average domain diameter of polysiloxane in the cured product is 63 nm, soluble. The minute was 0.5%, and no bleed out occurred. The results are shown in Table 1.
- Example 7 (Production of cured epoxy resin 7) A cured epoxy resin was obtained in the same manner as in Example 1 except that the block copolymer was replaced with 9.0 g of the block copolymer obtained in Production Example 9. No bleed-out occurred, and the flexural modulus and strain at break of the obtained cured epoxy resin were measured. As a result, the flexural modulus was 2.3 GPa and the strain at break was 10%.
- the uncured epoxy resin composition is finely dispersed, its viscosity is 0.104 Pa ⁇ s, the rate of increase in viscosity is 4.3 times, and the average domain diameter of polysiloxane in the cured product is 51 nm (FIG. 2). ), The soluble content was 0.2%, and no bleed out occurred.
- Table 1 The results are shown in Table 1.
- Example 8 (Production of cured epoxy resin 8) A cured epoxy resin was obtained in the same manner as in Example 1 except that the block copolymer was replaced with 9.0 g of the block copolymer obtained in Production Example 10. Bleed-out did not occur, and the flexural modulus and strain at break of the obtained epoxy resin cured product were measured. The flexural modulus was 2.5 GPa and the strain at break was 12%. The uncured epoxy resin composition is finely dispersed, its viscosity is 0.072 Pa ⁇ s, the rate of increase in viscosity is 3.0 times, and the average domain diameter of polysiloxane in the cured product is 80 nm, soluble. The minute was 0.8% and no bleed out occurred. The results are shown in Table 1.
- Example 9 (Production of cured epoxy resin 9) A cured epoxy resin was obtained in the same manner as in Example 1 except that the block copolymer was replaced with 9.0 g of the block copolymer obtained in Production Example 11. Bleed-out did not occur, and the flexural modulus and strain at break of the obtained epoxy resin cured product were measured. As a result, the flexural modulus was 2.4 GPa and the strain at break was 10%.
- the uncured epoxy resin composition is finely dispersed, its viscosity is 0.087 Pa ⁇ s, the rate of increase in viscosity is 3.6 times, and the average domain diameter of polysiloxane in the cured product is 60 nm, soluble. The minute was 1.0% and no bleed out occurred. The results are shown in Table 1.
- Example 10 (Production of cured epoxy resin 10) A cured epoxy resin was obtained in the same manner as in Example 1 except that the block copolymer was replaced with 9.0 g of the block copolymer obtained in Production Example 12. Bleed-out did not occur, and the flexural modulus and strain at break of the obtained cured epoxy resin were measured. As a result, the flexural modulus was 2.0 GPa and the strain at break was 13%.
- the uncured epoxy resin composition is finely dispersed, its viscosity is 0.075 Pa ⁇ s, the rate of increase in viscosity is 3.1 times, and the average domain diameter of polysiloxane in the cured product is 163 nm, soluble The minute was 0.8% and no bleed out occurred.
- Table 1 The results are shown in Table 1.
- the uncured epoxy resin composition is separated into two phases, the viscosity is 0.032 Pa ⁇ s, the rate of increase in viscosity is 1.3 times, and the average domain diameter of polysiloxane in the cured product is 100 ⁇ m. It was coarse, the soluble content was 0.3%, and no bleed out occurred.
- Table 1 The results are shown in Table 1.
- the uncured epoxy resin composition is finely dispersed, its viscosity is 0.021 Pa ⁇ s, the rate of increase in viscosity is 0.9 times, and the soluble content in the cured product is 11.0% bleed out. There has occurred.
- Table 1 The results are shown in Table 1.
- Example 3 Example 1 except that the block copolymer was replaced with 9.0 g of polydimethylsiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., KF-96-200cs, weight average molecular weight 18000, carboxylic acid content 0 mmol / g).
- An epoxy resin cured product was prepared.
- the uncured epoxy resin composition was separated into two phases, the viscosity was 0.029 Pa ⁇ s, and the rate of increase in viscosity was 1.2 times. The results are shown in Table 1.
- Example 4 A cured epoxy resin was prepared in the same manner as in Example 1 except that the block copolymer was replaced with 9.0 g of silicone particles (“Trefil” (registered trademark) EP2601 manufactured by Toray Dow Corning Co., Ltd.).
- Tefil registered trademark
- EP2601 manufactured by Toray Dow Corning Co., Ltd.
- the bending elastic modulus was 2.3 GPa and the strain at break was 7.2%.
- the uncured epoxy resin composition is separated into silicone particles and epoxy compositions, the viscosity is 0.49 Pa ⁇ s, the rate of increase in viscosity is 20.4 times, and the average of the silicone particles in the cured product The domain diameter was 10 ⁇ m.
- Table 1 The results are shown in Table 1.
- Example 5 A cured epoxy resin was prepared in the same manner as in Example 1 except that the block copolymer was not blended. When a three-point bending test was carried out using the obtained cured epoxy resin, the flexural modulus was 2.9 GPa and the strain at break was 9.5%. The viscosity of the uncured epoxy resin composition was 0.024 Pa ⁇ s. The results are shown in Table 1.
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Abstract
Description
「<1>カルボン酸無水物基、水酸基、エポキシ基、カルボキシル基、およびアミノ基から選ばれるいずれかの官能基を有するポリシロキサン(A)、ならびに、カルボン酸無水物基、水酸基、カルボキシル基、アミノ基、エポキシ基、チオール基、およびイソシアネート基から選ばれるいずれかの官能基を有するポリアルキレングリコール(B)を反応させて得られるポリシロキサン-ポリアルキレングリコールブロック共重合体であって、ブロック共重合体を100質量%として、ポリシロキサン(A)由来の構造の含有量が20質量%以上90質量%以下であるポリシロキサン-ポリアルキレングリコールブロック共重合体。
<2>カルボン酸無水物基、水酸基、エポキシ基、カルボキシル基、およびアミノ基から選ばれるいずれかの官能基を有するポリシロキサン(A)、ならびに、カルボン酸無水物基、水酸基、カルボキシル基、アミノ基、エポキシ基、チオール基、およびイソシアネート基から選ばれるいずれかの官能基を有するポリアルキレングリコール(B)、ならびに必要に応じて前記ポリシロキサン(A)の官能基および/または前記ポリアルキレングリコール(B)の官能基に反応する共重合成分(C)を反応させてポリシロキサン-ポリアルキレングリコールブロック共重合体を製造する方法であって、前記ポリシロキサン(A)、前記ポリアルキレングリコール(B)および前記共重合成分(C)の合計を100質量%として、前記ポリシロキサン(A)の量が20質量%以上90質量%以下であるポリシロキサン-ポリアルキレングリコールブロック共重合体の製造方法。
<3>上記のポリシロキサン-ポリアルキレングリコールブロック共重合体およびエポキシ樹脂を含むエポキシ樹脂組成物。
<4>上記のエポキシ樹脂組成物を硬化させてなるエポキシ樹脂硬化物。
<5>上記のエポキシ樹脂硬化物からなる半導体封止材。」である。
ブロック共重合体および官能基を有するポリシロキサン(A)および官能基を有するポリアルキレングリコール(B)の重量平均分子量は、ゲルパーミエーションクロマトグラフィ法を用いて、下記条件にて測定し、ポリメタクリル酸メチルによる較正曲線と対比させて分子量を算出した。
カラム:昭和電工株式会社 KF-806L×2
流速:1.0mL/min
移動相:テトラヒドロフラン
検出:示差屈折率計
カラム温度:40℃。
ブロック共重合体0.5gをテトラヒドロフラン10gに溶解し、0.1mol/Lのアルコール性水酸化カリウムでフェノールフタレインを指示薬として滴定し、カルボン酸含有量を定量した。
ブロック共重合体および官能基を有するポリシロキサン(A)および官能基を有するポリアルキレングリコール(B)の5%重量減少温度は、熱重量測定装置(株式会社島津製作所製 島津自動示差・熱重量同時測定装置DTG-60)を用いて下記条件にて測定し、評価した。
測定温度:20℃~500℃
昇温速度:10℃/分
雰囲気:窒素。
各実施例に示した混合比でエポキシ樹脂およびエポキシ樹脂硬化剤を混合した組成物の粘度を、レオメーター(Anton Paar社製 MCR501)を用いて下記条件にて測定し、175℃における粘度を求めた。次に同じエポキシ樹脂およびエポキシ樹脂硬化剤の合計100質量部に対して、ブロック共重合体を15質量部添加したエポキシ樹脂組成物の粘度を、同様に測定した。ブロック共重合体を含まない場合に対する、ブロック共重合体を15質量部含む場合の、組成物の粘度の上昇割合の倍率を求めた。
周波数:0.5Hz
ひずみ:100%
ギャップ:1mm
測定温度:70℃~220℃
昇温速度:10℃/分
雰囲気:窒素。
ブロック共重合体が分散したエポキシ樹脂硬化物を幅10mm、長さ80mm、厚さ4mmにカットし試験片を得た。テンシロン万能試験機(TENSIRON TRG-1250、エー・アンド・デイ社製)を用い、JIS K7171(2008)に従い、支点間距離64mm、試験速度2mm/分の条件で3点曲げ試験を行い、曲げ弾性率および破断点歪みを測定した。測定温度は室温(23℃)、測定数はn=5とし、その平均値を求めた。
ブロック共重合体が分散したエポキシ樹脂硬化物を四酸化ルテニウムにて染色し、その断面を透過型電子顕微鏡で得た写真から、任意の100個のポリシロキサンドメインの直径を測長し、下式に従い、算出した。
ブロック共重合体が分散したエポキシ樹脂硬化物3gをクロロホルム5gに1日浸漬した後に、クロロホルムを分離し、溶媒を蒸発除去することで、クロロホルム中に溶解したブロック共重合体の質量を測定した。組成から計算したエポキシ樹脂硬化物中のブロック共重合体の質量に対して、クロロホルム中に溶解したブロック共重合体の質量が5質量%以上の場合、ブリードアウト有り、5質量%未満の場合はブリードアウト無しと評価した。
100mLの2つ口フラスコ中に、両末端無水マレイン酸変性シリコーンオイル(信越化学工業株式会社製、X-22-168AS、重量平均分子量1300、5%重量減少温度299℃)を5.0g、ポリテトラメチレングリコール(和光純薬工業株式会社製、ポリテトラメチレンオキシド1,000、重量平均分子量2700、5%重量減少温度275℃)を5.0g、およびトルエン40gを加え、窒素置換を行った。その後、120℃に加熱し8時間反応させ、無色透明液体を得た。エバポレータにて、トルエンを除去後、80℃の真空乾燥機にて18時間乾燥し、トルエンを完全に除去した。得られたブロック共重合体は無色透明な液体であり、ポリシロキサン(A)由来の構造の含有量は50質量%、重量平均分子量は46,000、5%重量減少温度は309℃、カルボン酸含有量は1.01mmol/gであった。
100mLの2つ口フラスコ中に、両末端無水マレイン酸変性シリコーンオイル(信越化学工業株式会社製、X-22-168AS、重量平均分子量1300、5%重量減少温度299℃)を10.0g、およびポリテトラメチレングリコール(和光純薬工業株式会社製、ポリテトラメチレンオキシド1,000、重量平均分子量2700、5%重量減少温度275℃)を10.0g加え、窒素置換を行った。その後、120℃に加熱し8時間反応させ、無色透明液体を得た。得られたブロック共重合体のポリシロキサン(A)由来の構造の含有量は50質量%、重量平均分子量は49,000、5%重量減少温度は313℃、カルボン酸含有量は1.01mmol/gであった。
100mLの2つ口フラスコ中に、両末端無水マレイン酸変性シリコーンオイル(信越化学工業株式会社製、X-22-168AS、重量平均分子量1300、5%重量減少温度299℃)を2.5g、およびポリテトラメチレングリコール(和光純薬工業株式会社製、ポリテトラメチレンオキシド2,900、重量平均分子量12500、5%重量減少温度299℃)を7.5g加え、窒素置換を行った。その後、160℃に加熱し8時間反応させ、無色透明液体を得た。得られたブロック共重合体のポリシロキサン(A)由来の構造の含有量は25質量%、重量平均分子量は30,000、5%重量減少温度は325℃、カルボン酸含有量は0.51mmol/gであった。
100mLの2つ口フラスコ中に、両末端無水マレイン酸変性シリコーンオイル(信越化学工業株式会社製、X-22-168AS、重量平均分子量1300、5%重量減少温度299℃)を5.0g、ポリテトラメチレングリコール(和光純薬工業株式会社製、ポリテトラメチレンオキシド2,000、重量平均分子量7300、5%重量減少温度293℃)を10.0g、およびトルエン60gを加え、窒素置換を行った。その後、120℃に加熱し8時間反応させ、無色透明液体を得た。エバポレータにて、トルエンを除去後、80℃の真空乾燥機にて18時間乾燥し、トルエンを完全に除去した。得られたブロック共重合体は無色透明な液体であり、ポリシロキサン(A)由来の構造の含有量は33質量%、重量平均分子量は53,000、5%重量減少温度は311℃、カルボン酸含有量は0.71mmol/gであった。
100mLの2つ口フラスコ中に、両末端無水マレイン酸変性シリコーンオイル(信越化学工業株式会社製、X-22-168AS、重量平均分子量1300、5%重量減少温度299℃)を10.0g、ポリテトラメチレングリコール(和光純薬工業株式会社製、ポリテトラメチレンオキシド650、重量平均分子量1600、5%重量減少温度263℃)を6.5g、およびトルエン66gを加え、窒素置換を行った。その後、120℃に加熱し8時間反応させ、無色透明液体を得た。エバポレータにて、トルエンを除去後、80℃の真空乾燥機にて18時間乾燥し、トルエンを完全に除去した。得られたブロック共重合体は無色透明な液体であり、ポリシロキサン(A)由来の構造の含有量は61質量%、重量平均分子量は49,000、5%重量減少温度は312℃、カルボン酸含有量は0.68mmol/gであった。
100mLの2つ口フラスコ中に、両末端無水マレイン酸変性シリコーンオイル(信越化学工業株式会社製、X-22-168AS、重量平均分子量1300、5%重量減少温度299℃)を2.0g、ポリテトラメチレングリコール(和光純薬工業株式会社製、ポリテトラメチレンオキシド1000、重量平均分子量2700、5%重量減少温度275℃)を6.93g、およびピロメリット酸二無水物(東京化成工業株式会社製)1.07gを加え、窒素置換を行った。その後、120℃に加熱し8時間反応させ、ブロック共重合体を得た。ポリシロキサン(A)由来の構造の含有量は20質量%、重量平均分子量は106,000、5%重量減少温度は285℃、カルボン酸含有量は0.98mmol/gであった。
100mLの2つ口フラスコ中に、両末端無水マレイン酸変性シリコーンオイル(信越化学工業株式会社製、X-22-168AS、重量平均分子量1300、5%重量減少温度299℃)を2.0g、ポリテトラメチレングリコール(和光純薬工業株式会社製、ポリテトラメチレンオキシド1000、重量平均分子量2700、5%重量減少温度275℃)を6.93g、およびピロメリット酸二無水物(東京化成工業株式会社製)1.07gを加え、窒素置換を行った。その後、160℃に加熱し3時間反応させ、ブロック共重合体を得た。ポリシロキサン(A)由来の構造の含有量は20質量%、重量平均分子量は182,000、5%重量減少温度は289℃、カルボン酸含有量は0.98mmol/gであった。
100mLの2つ口フラスコ中に、両末端無水マレイン酸変性シリコーンオイル(信越化学工業株式会社製、X-22-168AS、重量平均分子量1300、5%重量減少温度299℃)を10.0g、ポリテトラメチレングリコール(和光純薬工業株式会社製、ポリテトラメチレンオキシド1000、重量平均分子量2700、5%重量減少温度275℃)を10.0g、および無水コハク酸(東京化成工業株式会社製)0.2gを加え、窒素置換を行った。その後、120℃に加熱し8時間反応させ、ブロック共重合体を得た。ポリシロキサン(A)由来の構造の含有量は50質量%、重量平均分子量は33,000、5%重量減少温度は312℃、カルボン酸含有量は1.11mmol/gであった。
100mLのセパラブルフラスコ中に、両末端水酸基変性シリコーンオイル(信越化学工業株式会社製、KF-6001、重量平均分子量3000、5%重量減少温度298℃)を7.5g、およびポリプロピレングリコール(和光純薬工業株式会社製、ポリプロピレングリコール、ジオール型、2000、重量平均分子量3350、5%重量減少温度296℃)を6.0gを加え、均一溶液を得た。次に、ピロメリット酸二無水物(東京化成工業株式会社製)1.5gを加え、窒素置換を行った。その後、160℃に加熱し8時間反応させ、ブロック共重合体を得た。ポリシロキサン(A)由来の構造の含有量は50質量%、重量平均分子量は37,000、5%重量減少温度は289℃、カルボン酸含有量は0.95mmol/gであった。
100mLのセパラブルフラスコ中に、両末端水酸基変性シリコーンオイル(信越化学工業株式会社製、KF-6001、重量平均分子量3000、5%重量減少温度298℃)を7.5g、およびポリプロピレングリコール(和光純薬工業株式会社製、ポリプロピレングリコール、ジオール型、2000、重量平均分子量3350、5%重量減少温度296℃)を6.0gを加え、均一溶液を得た。次に、ピロメリット酸二無水物(東京化成工業社製)1.5g、n-オクタノール(和光純薬工業株式会社製)0.5gを加え、窒素置換を行った。その後、160℃に加熱し6時間反応させ、ブロック共重合体を得た。ポリシロキサン(A)由来の構造の含有量は48質量%、重量平均分子量は18,000、5%重量減少温度は274℃、カルボン酸含有量は0.80mmol/gであった。
100mLのセパラブルフラスコ中に、両末端水酸基変性シリコーンオイル(信越化学工業株式会社製、KF-6001、重量平均分子量3000、5%重量減少温度298℃)を6.0g、およびポリプロピレングリコール(和光純薬工業株式会社製、ポリプロピレングリコール、ジオール型、2000、重量平均分子量3350、5%重量減少温度296℃)を7.5g加え、均一溶液を得た。次に、ピロメリット酸二無水物(東京化成工業社製)を1.5g加え、窒素置換を行った。その後、160℃に加熱し8時間反応させ、ブロック共重合体を得た。ポリシロキサン(A)由来の構造の含有量は40質量%、重量平均分子量は28,000、5%重量減少温度は286℃、カルボン酸含有量は0.93mmol/gであった。
100mLのセパラブルフラスコ中に、両末端水酸基変性シリコーンオイル(信越化学工業株式会社製、KF-6001、重量平均分子量3000、5%重量減少温度298℃)を10.5g、およびポリプロピレングリコール(和光純薬工業株式会社製、ポリプロピレングリコール、ジオール型、2000、重量平均分子量3350、5%重量減少温度296℃)を2.9g加え、均一溶液を得た。次に、ピロメリット酸二無水物(東京化成工業社製)1.6gを加え、窒素置換を行った。その後、160℃に加熱し8時間反応させ、ブロック共重合体を得た。ポリシロキサン(A)由来の構造の含有量は70質量%、重量平均分子量は41,000、5%重量減少温度は276℃、カルボン酸含有量は1.01mmol/gであった。
製造例1で得られたブロック共重合体9.0g、エポキシ樹脂としてビフェニル型エポキシ樹脂(三菱ケミカル株式会社製、“jER”(登録商標)YX4000H)38.25g、および硬化剤としてフェノールノボラック型硬化剤(明和化成株式会社製、H-1)21.75gを150ccのステンレス製ビーカーに秤量し、120℃のオーブンにて溶解し、均一にした。その後、硬化促進剤としてテトラフェニルホスホニウム テトラ-p-トリルボレート0.3gを加え、撹拌棒により簡単に混ぜた後、自公転ミキサー「あわとり練太郎」(株式会社シンキー製)を用いて、2000rpm、80kPa、1.5分間の混合を1回、2000rpm、50kPa、1.5分間の撹拌を1回、2000rpm、0.2kPa、1.5分間の撹拌を2回行い、未硬化のエポキシ樹脂組成物を得た。
ブロック共重合体を、製造例2で得られたブロック共重合体9.0gに代えたこと以外は実施例1と同様にして、エポキシ樹脂硬化物を得た。ブリードアウトは発生しておらず、得られたエポキシ樹脂硬化物の曲げ弾性率および破断点歪みを測定したところ、曲げ弾性率2.5GPa、破断点歪み11%であった。また未硬化のエポキシ樹脂組成物は微分散しており、その粘度は0.139Pa・s、粘度の上昇割合は5.8倍であり、硬化物におけるポリシロキサンの平均ドメイン径は53nm(図1)、可溶分は0.2%でブリードアウトは発生していなかった。結果を表1に示す。
ブロック共重合体を、製造例4で得られたブロック共重合体9.0gに代えたこと以外は実施例1と同様にして、エポキシ樹脂硬化物を得た。ブリードアウトは発生しておらず、得られたエポキシ樹脂硬化物の曲げ弾性率および破断点歪みを測定したところ、曲げ弾性率2.4GPa、破断点歪み15%であった。また未硬化のエポキシ樹脂組成物は微分散しており、その粘度は0.106Pa・s、粘度の上昇割合は4.4倍であり、硬化物におけるポリシロキサンの平均ドメイン径は40nm、可溶分は0.5%でブリードアウトは発生していなかった。結果を表1に示す。
ブロック共重合体を、製造例5で得られたブロック共重合体9.0gに代えたこと以外は実施例1と同様にして、エポキシ樹脂硬化物を得た。ブリードアウトは発生しておらず、得られたエポキシ樹脂硬化物の曲げ弾性率および破断点歪みを測定したところ、曲げ弾性率2.4GPa、破断点歪み11%であった。また未硬化のエポキシ樹脂組成物は微分散しており、その粘度は0.064Pa・s、粘度の上昇割合は2.7倍であり、硬化物におけるポリシロキサンの平均ドメイン径は65nm、可溶分は1.2%でブリードアウトは発生していなかった。結果を表1に示す。
ブロック共重合体を、製造例6で得られたブロック共重合体9.0gに代えたこと以外は実施例1と同様にして、エポキシ樹脂硬化物を得た。ブリードアウトは発生しておらず、得られたエポキシ樹脂硬化物の曲げ弾性率および破断点歪みを測定したところ、曲げ弾性率3.0GPa、破断点歪み12%であった。また未硬化のエポキシ樹脂組成物は微分散しており、その粘度は0.356Pa・s、粘度の上昇割合は14.8倍であり、硬化物におけるポリシロキサンの平均ドメイン径は60nm、可溶分は0.2%でブリードアウトは発生していなかった。結果を表1に示す。
ブロック共重合体を、製造例8で得られたブロック共重合体9.0gに代えたこと以外は実施例1と同様にして、エポキシ樹脂硬化物を得た。ブリードアウトは発生しておらず、得られたエポキシ樹脂硬化物の曲げ弾性率および破断点歪みを測定したところ、曲げ弾性率2.6GPa、破断点歪み15%であった。また未硬化のエポキシ樹脂組成物は微分散しており、その粘度は0.06Pa・s、粘度の上昇割合は2.5倍であり、硬化物におけるポリシロキサンの平均ドメイン径は63nm、可溶分は0.5%でブリードアウトは発生していなかった。結果を表1に示す。
ブロック共重合体を、製造例9で得られたブロック共重合体9.0gに代えたこと以外は実施例1と同様にして、エポキシ樹脂硬化物を得た。ブリードアウトは発生しておらず、得られたエポキシ樹脂硬化物の曲げ弾性率および破断点歪みを測定したところ、曲げ弾性率2.3GPa、破断点歪み10%であった。また未硬化のエポキシ樹脂組成物は微分散しており、その粘度は0.104Pa・s、粘度の上昇割合は4.3倍であり、硬化物におけるポリシロキサンの平均ドメイン径は51nm(図2)、可溶分は0.2%でブリードアウトは発生していなかった。結果を表1に示す。
ブロック共重合体を、製造例10で得られたブロック共重合体9.0gに代えたこと以外は実施例1と同様にして、エポキシ樹脂硬化物を得た。ブリードアウトは発生しておらず、得られたエポキシ樹脂硬化物の曲げ弾性率および破断点歪みを測定したところ、曲げ弾性率2.5GPa、破断点歪み12%であった。また未硬化のエポキシ樹脂組成物は微分散しており、その粘度は0.072Pa・s、粘度の上昇割合は3.0倍であり、硬化物におけるポリシロキサンの平均ドメイン径は80nm、可溶分は0.8%でブリードアウトは発生していなかった。結果を表1に示す。
ブロック共重合体を、製造例11で得られたブロック共重合体9.0gに代えたこと以外は実施例1と同様にして、エポキシ樹脂硬化物を得た。ブリードアウトは発生しておらず、得られたエポキシ樹脂硬化物の曲げ弾性率および破断点歪みを測定したところ、曲げ弾性率2.4GPa、破断点歪み10%であった。また未硬化のエポキシ樹脂組成物は微分散しており、その粘度は0.087Pa・s、粘度の上昇割合は3.6倍であり、硬化物におけるポリシロキサンの平均ドメイン径は60nm、可溶分は1.0%でブリードアウトは発生していなかった。結果を表1に示す。
ブロック共重合体を、製造例12で得られたブロック共重合体9.0gに代えたこと以外は実施例1と同様にして、エポキシ樹脂硬化物を得た。ブリードアウトは発生しておらず、得られたエポキシ樹脂硬化物の曲げ弾性率および破断点歪みを測定したところ、曲げ弾性率2.0GPa、破断点歪み13%であった。また未硬化のエポキシ樹脂組成物は微分散しており、その粘度は0.075Pa・s、粘度の上昇割合は3.1倍であり、硬化物におけるポリシロキサンの平均ドメイン径は163nm、可溶分は0.8%でブリードアウトは発生していなかった。結果を表1に示す。
ブロック共重合体を、両末端無水マレイン酸変性シリコーンオイル(信越化学工業株式会社製、X-22-168AS、重量平均分子量1300、5%重量減少温度299℃)9.0gに代えたこと以外は実施例1と同様にエポキシ樹脂硬化物を作製した。得られたエポキシ樹脂硬化物を用いて、3点曲げ試験を実施したところ、曲げ弾性率は2.6GPa、破断点歪みは5.7%であった。また未硬化のエポキシ樹脂組成物は2相に分離しており、その粘度は0.032Pa・s、粘度の上昇割合は1.3倍であり、硬化物におけるポリシロキサンの平均ドメイン径は100μmと粗大であり、可溶分は0.3%でブリードアウトは発生していなかった。結果を表1に示す。
ブロック共重合体を、ポリテトラメチレングリコール(和光純薬工業株式会社製、ポリテトラメチレンオキシド1,000、重量平均分子量2700、5%重量減少温度275℃)9.0gに代えたこと以外は実施例1と同様にエポキシ樹脂硬化物を作製した。ブリードアウト発生の有無を確認した結果、可溶分は7%でブリードアウトは発生しており、得られたエポキシ樹脂硬化物を用いて、3点曲げ試験を実施したところ、曲げ弾性率は3.4GPa、破断点歪みは8.3%であった。また未硬化のエポキシ樹脂組成物は微分散しており、その粘度は0.021Pa・s、粘度の上昇割合は0.9倍であり、硬化物における可溶分は11.0%でブリードアウトが発生した。結果を表1に示す。
ブロック共重合体を、ポリジメチルシロキサン(信越化学工業株式会社製、KF-96-200cs、重量平均分子量18000、カルボン酸含有量0mmol/g)9.0gに代えたこと以外は実施例1と同様にエポキシ樹脂硬化物を作製した。ブリードアウト発生の有無を確認した結果、真球状の凹凸が多数見られ、可溶分は46%でブリードアウトしていたため、曲げ試験は実施できなかった。また未硬化のエポキシ樹脂組成物は2相に分離しており、その粘度は0.029Pa・s、粘度の上昇割合は1.2倍であった。結果を表1に示す。
ブロック共重合体を、シリコーン粒子(東レ・ダウコーニング株式会社製 “トレフィル”(登録商標)EP2601)9.0gに代えたこと以外は実施例1と同様にエポキシ樹脂硬化物を作製した。得られたエポキシ樹脂硬化物を用いて、3点曲げ試験を実施したところ、曲げ弾性率は2.3GPa、破断点歪みは7.2%であった。また未硬化のエポキシ樹脂組成物は、シリコーン粒子とエポキシ組成物に分離しており、その粘度は0.49Pa・s、粘度の上昇割合は20.4倍であり、硬化物におけるシリコーン粒子の平均ドメイン径は10μmであった。結果を表1に示す。
ブロック共重合体を配合しないこと以外は実施例1と同様にエポキシ樹脂硬化物を作製した。得られたエポキシ樹脂硬化物を用いて、3点曲げ試験を実施したところ、曲げ弾性率は2.9GPa、破断点歪みは9.5%であった。また未硬化のエポキシ樹脂組成物の粘度は0.024Pa・sであった。結果を表1に示す。
Claims (15)
- カルボン酸無水物基、水酸基、エポキシ基、カルボキシル基、およびアミノ基から選ばれるいずれかの官能基を有するポリシロキサン(A)、ならびに、カルボン酸無水物基、水酸基、カルボキシル基、アミノ基、エポキシ基、チオール基、およびイソシアネート基から選ばれるいずれかの官能基を有するポリアルキレングリコール(B)を反応させて得られるポリシロキサン-ポリアルキレングリコールブロック共重合体であって、ブロック共重合体を100質量%として、ポリシロキサン(A)由来の構造の含有量が20質量%以上90質量%以下であるポリシロキサン-ポリアルキレングリコールブロック共重合体。
- ポリシロキサン-ポリアルキレングリコールブロック共重合体の官能基含有量が0.1mmol/g~3.0mmol/gである請求項1~3のいずれかに記載のポリシロキサン-ポリアルキレングリコールブロック共重合体。
- ポリシロキサン-ポリアルキレングリコールブロック共重合体の重量平均分子量が5,000~500,000である請求項1~4のいずれかに記載のポリシロキサン-ポリアルキレングリコールブロック共重合体。
- ポリシロキサン-ポリアルキレングリコールブロック共重合体がカルボキシル基および/または水酸基を有する請求項1~5に記載のポリシロキサン-ポリアルキレングリコールブロック共重合体。
- 前記ポリシロキサン(A)の官能基および/または前記ポリアルキレングリコール(B)の官能基に反応すると反応する官能基を1以上有する共重合成分(C)由来の構造を含む請求項1~6のいずれかに記載のポリシロキサン-ポリアルキレングリコールブロック共重合体。
- 前記ポリアルキレングリコール(B)がポリテトラメチレングリコールおよび/またはポリプロピレングリコールである請求項1~7のいずれかに記載のポリシロキサン-ポリアルキレングリコールブロック共重合体。
- 前記ポリシロキサン(A)がカルボン酸無水物基および/または水酸基を有する請求項1~8のいずれかに記載のポリシロキサン-ポリアルキレングリコールブロック共重合体。
- カルボン酸無水物基、水酸基、エポキシ基、カルボキシル基、およびアミノ基から選ばれるいずれかの官能基を有するポリシロキサン(A)、ならびに、カルボン酸無水物基、水酸基、カルボキシル基、アミノ基、エポキシ基、チオール基、およびイソシアネート基から選ばれるいずれかの官能基を有するポリアルキレングリコール(B)、ならびに必要に応じて前記ポリシロキサン(A)の官能基および/または前記ポリアルキレングリコール(B)の官能基に反応する共重合成分(C)を反応させてポリシロキサン-ポリアルキレングリコールブロック共重合体を製造する方法であって、前記ポリシロキサン(A)、前記ポリアルキレングリコール(B)および前記共重合成分(C)の合計を100質量%として、前記ポリシロキサン(A)の量が20質量%以上90質量%以下であるポリシロキサン-ポリアルキレングリコールブロック共重合体の製造方法。
- 前記ポリシロキサン(A)、前記ポリアルキレングリコール(B)および前記ポリシロキサン(A)の官能基および前記ポリアルキレングリコール(B)の官能基の両方に反応する共重合成分(C’)を反応させる請求項10記載のポリシロキサン-ポリアルキレングリコールブロック共重合体の製造方法。
- 反応促進剤である金属触媒を用いずに反応させる請求項10または11記載のポリシロキサン-ポリアルキレングリコールブロック共重合体の製造方法。
- 請求項1~9のいずれかに記載のポリシロキサン-ポリアルキレングリコールブロック共重合体およびエポキシ樹脂を含むエポキシ樹脂組成物。
- 請求項13記載のエポキシ樹脂組成物を硬化させてなるエポキシ樹脂硬化物。
- 請求項14記載のエポキシ樹脂硬化物からなる半導体封止材。
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WO2020255749A1 (ja) * | 2019-06-21 | 2020-12-24 | パナソニックIpマネジメント株式会社 | 封止用組成物、半導体装置及び半導体装置の製造方法 |
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JP7465790B2 (ja) * | 2020-11-18 | 2024-04-11 | 信越化学工業株式会社 | シリコーンハイブリッド樹脂組成物、及び半導体装置 |
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