WO2013162052A1 - Nouvel organopolysiloxane, additif de résine thermodurcissable comprenant ce composé et composition de résine thermodurcissable comprenant celui-ci - Google Patents

Nouvel organopolysiloxane, additif de résine thermodurcissable comprenant ce composé et composition de résine thermodurcissable comprenant celui-ci Download PDF

Info

Publication number
WO2013162052A1
WO2013162052A1 PCT/JP2013/062687 JP2013062687W WO2013162052A1 WO 2013162052 A1 WO2013162052 A1 WO 2013162052A1 JP 2013062687 W JP2013062687 W JP 2013062687W WO 2013162052 A1 WO2013162052 A1 WO 2013162052A1
Authority
WO
WIPO (PCT)
Prior art keywords
groups
thermosetting resin
group
organopolysiloxane
resin composition
Prior art date
Application number
PCT/JP2013/062687
Other languages
English (en)
Inventor
Yoshitsugu Morita
Satoshi Onodera
Toru Masatomi
Original Assignee
Dow Corning Toray Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dow Corning Toray Co., Ltd. filed Critical Dow Corning Toray Co., Ltd.
Publication of WO2013162052A1 publication Critical patent/WO2013162052A1/fr

Links

Classifications

    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins

Definitions

  • the present invention relates to a novel organopolysiloxane, a thermosetting resin additive comprising the same, and a thermosetting resin composition comprising the same.
  • a novel organopolysiloxane comprising the same
  • a thermosetting resin additive comprising the same
  • a thermosetting resin composition comprising the same.
  • thermosetting resin compositions such as epoxy resins and the like find application as sealing, adhesive, and other agents used in the manufacture of electrical and electronic parts.
  • the use of these compositions is associated with problems, such as low modulus of elasticity, and hence high rigidity, of cured products obtained from these compositions.
  • stress is prone to be generated in electrical and electronic parts due to expansion and contraction when the aforementioned compositions are used. Therefore, various additives are added to thermosetting resin compositions in order to mitigate the internal stress in the cured body.
  • Japanese Unexamined Patent Application Publication Nos. 2006-269730 and 2005-15559 disclose sealing epoxy resin molding materials comprising a silicone-containing polymer having an epoxy group as such additives.
  • compatibility of such a silicone-containing polymer having an epoxy group in the resin composition is insufficient, and reactivity with the epoxy resin is low.
  • bleeding out occurs when a large amount of the additive is added.
  • variations in the characteristics of the resin are seen if the content of the epoxy groups is increased in order to enhance compatibility and reactivity.
  • Japanese Unexamined Patent Application Publication No. 2011-152196 discloses an epoxy resin composition for sealing semiconductors comprising a reaction product of a higher fatty acid and a primary amino group-containing polysiloxane as a release agent.
  • Japanese Examined Patent Application Publication S62-27095 discloses an epoxy resin composition comprising an organopolysiloxane having a primary amino group-containing organic group.
  • organopolysiloxanes having secondary amino groups have been proposed.
  • Japanese Unexamined Patent Application Publication Nos. 2008-285552 and 2008-285553 disclose curable epoxy resin compositions comprising crosslinking silicone particles having aryl groups or aralkyi groups and secondary amino groups, and a mixture of said crosslinking silicone particles and an epoxy resin and an epoxy resin curing agent.
  • crosslinking silicone particles have fine pores and, thus, there is a problem in that the hygroscopicity of the obtained cured product is high. Additionally, there is a problem in that shrinkage ratio is high when curing the composition.
  • Patent Document 1 Japanese Unexamined Patent Application Publication No.
  • Patent Document 2 Japanese Unexamined Patent Application Publication No. 2005-015559A
  • Patent Document 3 Japanese Unexamined Patent Application Publication No. 2011-152196A
  • Patent Document 4 Japanese Examined Patent Application Publication No. S62-027095
  • Patent Document 5 Japanese Unexamined Patent Application Publication No. 2008-285552A
  • Patent Document 6 Japanese Unexamined Patent Application Publication No. 2008-285553A
  • Patent Document 7 Japanese Unexamined Patent Application Publication No. H03-157453A
  • an object of the present invention is to provide a novel organopolysiloxane having superior compatibility with thermosetting resins and superior reactivity with thermosetting resins, and a thermosetting resin additive comprising the
  • Another object is to provide a thermosetting resin composition that is free of problems such as bleeding out and the like and that has low curing shrinkage ratio.
  • the object of the present invention is achieved by an organopolysiloxane represented by the average unit formula:
  • R 1 Si03/ 2 a(R 2 R 3 Si0 2/2 ) b (R 4 R 5 R 6 SiO 1/2 ) c (Si0 4 / 2 ) d
  • R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are each identical or differing monovalent hydrocarbon groups, halogen-substituted monovalent hydrocarbon groups, or secondary amino
  • the organopolysiioxane preferably comprises aryl groups having from 6 to 20 carbons at an amount of not less than 5 mol% of the total number of moles of the R 1 to R 6 moieties.
  • the organopolysiioxane preferably comprises alkyl groups having from 1 to 20 carbons at an amount of not less than 10 mol% of the total number of moles of the R 1 to R 6 moieties.
  • the organopolysiioxane preferably comprises secondary amino group-containing organic groups having nitrogen atom-bonded aromatic rings at an amount of not less than 5 mol% of the total number of moles of the R 1 to R 6 moieties.
  • the secondary amino group-containing organic groups having nitrogen atom-bonded aromatic rings are preferably groups represented by the following formula:
  • R 7 is a divalent hydrocarbon group
  • R 8 is a hydrogen atom, a monovalent hydrocarbon group, an acyl groups, or a group represented by the formula: -CH 2 CH(OH)R 10 (wherein, R 10 is a monovalent organic group); and R 9 is a monovalent hydrocarbon group or an acyl group; provided that at least one of R 8 and R 9 is an aryl group and when "e" is 0, R 9 is an aryl group).
  • a weight average molecular weight of the organopolysiioxane is preferably in a range from 500 to 50,000.
  • the present invention is also related to a thermosetting resin additive comprising the organopolysiioxane described above.
  • thermosetting resin composition comprising a thermosetting resin, a curing agent, and the thermosetting resin additive described above.
  • thermosetting resin additive is preferably comprised at an amount of from 0.1 to 500 parts by mass per a total 100 parts by mass of the thermosetting resin and the curing agent.
  • thermosetting resin is preferably an epoxy resin.
  • the curing agent is preferably a phenolic resin.
  • thermosetting resin composition of the present invention can further comprise an inorganic filler.
  • an organopolysiioxane having superior compatibility with epoxy resins and similar thermosetting resins and superior reactivity, and a thermosetting resin additive comprising this organopolysiloxane can be provided.
  • thermosetting resin composition comprising the thermosetting resin additive of the present invention
  • internal stress in cured resin can be mitigated and formability can be improved. Furthermore, warping and similar deformations of the cured resin can be suppressed.
  • organopolysiloxane of the present invention is represented by the average unit formula:
  • R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are each identical or differing monovalent hydrocarbon groups, halogen-substituted monovalent hydrocarbon groups, or secondary amino group-containing organic groups having nitrogen atom-bonded aromatic rings; and from 0.1 to 70 mol% of the total number of moles of the R to R 6 moieties is constituted by the secondary amino group-containing organic groups; and
  • organopolysiloxane of the present invention include methyl groups, ethyl groups, propyl groups, butyl groups, pentyl groups, hexyl groups, heptyl groups, and similar alkyl groups; vinyl groups, allyl groups, butenyl groups, pentenyl groups, hexenyl groups, and similar alkenyl groups; phenyl groups, tolyl groups, xylyl groups, naphthyl groups, and similar aryl groups; benzyl groups, phenethyl groups, and similar aralkyl groups; and chloromethyl groups, 3-chloropropyl groups, 3,3,3-trifluoropropyl groups, nonafluorobutyl ethyl groups, and similar substituted alkyl groups.
  • the organopolysiloxane of the present invention preferably comprises aryl groups having from 6 to 20 carbons at an amount of not less than 5 mol% and more preferably comprises aryl groups having from 6 to 20 carbons at an amount of from 20 to 70 mol% of the total number of moles of the R 1 to R 6 moieties.
  • the aryl groups include phenyl, tolyl, xylyl, and naphthyl groups.
  • the aryl groups are preferably phenyl groups or naphthyl groups.
  • the organopolysiloxane of the present invention preferably comprises alkyl groups having from 1 to 20 carbons at an amount of not less than 0 mol% and more preferably comprises alkyl groups having from 1 to 20 carbons at an amount from 5 to 80 mol% of the total number of moles of the R 1 to R 6 moieties.
  • alkyl groups include methyl groups, ethyl groups, propyl groups, butyl groups, pentyl groups, hexyl groups, heptyl groups, octyl groups, decyl groups, and dodecyl groups.
  • the alkyl groups are preferably methyl groups or ethyl groups.
  • the organopolysiloxane of the present invention preferably comprises secondary amino group-containing organic groups having nitrogen atom-bonded aromatic rings at an amount of not less than 5 mol% and more preferably comprises secondary amino group-containing organic groups having nitrogen atom-bonded aromatic rings at an amount from 5 to 40 mol% of the total number of moles of the R to R 6 moieties. Because of including the secondary amino group-containing organic groups, the thermosetting resin additive of the present invention has superior compatibility with thermosetting resins even in cases where the R 1 to R 6 moieties do not include aryl groups.
  • the secondary amino group-containing organic groups having nitrogen atom-bonded aromatic rings are preferably groups represented by the following formula:
  • R 7 is a divalent hydrocarbon group
  • R 8 is a hydrogen atom, a monovalent hydrocarbon group, an acyl groups, or a group represented by the formula: -CH 2 CH(OH)R 10 (wherein, R 10 is a monovalent organic group)
  • R 9 is a monovalent hydrocarbon group or an acyl group; provided that at least one of R 8 and R 9 is an aryl group and when "e" is 0, R 9 is an aryl group.
  • Examples of the divalent hydrocarbon group include methylene, ethylene, propylene, butylene, hexene, and similar alkylene groups having from 1 to 10 carbons. Additionally, the monovalent hydrocarbon group is synonymous with the groups recited for the R 1 to R 6 moieties. Examples of the monovalent organic group include the monovalent hydrocarbon group and groups wherein a portion or all of the carbon-bonded hydrogen atoms in the monovalent hydrocarbon group are substituted with cyano groups, epoxy groups, or the like. Additionally, a small amount of silicon-bonded hydrogen atoms, hydroxyl groups, or alkoxy groups may be comprised.
  • a small portion of the R 1 to R 6 moieties may be hydroxyl groups or alkoxy groups having from 1 to 20 carbons. In this case, preferably less than 40 mol% and more preferably less than 10 mol% of the total number of moles of the R to R 6 moieties are hydroxyl groups or alkoxy groups.
  • a is preferably from 0.10 to 0.95 and more preferably is from 0.20 to 0.90.
  • b is preferably from 0.05 to 0.80 and more preferably from 0. 0 to 0.75.
  • b+c is preferably from 0.05 to 0.85 and more preferably from 0.10 to 0.80.
  • d 0.
  • the organopolysiloxane of the present invention preferably has a weight average molecular weight in a range from 500 to 50,000 and more preferably has a weight average molecular weight in a range from 1 ,000 to 10,000 when measured by gel permeation
  • the organopolysiloxane of the present invention preferably is soluble in toluene at 25°C.
  • soluble means that 1 mass.% or more of the organopolysiloxane dissolves in toluene
  • dissolve means that residue is not visually identifiable after adding 1 g of the organopolysiloxane to 99 g of toluene and stirring for 10 minutes at 25°C. If the organopolysiloxane has a crosslinked or gelled structure or has an excessive amount of siloxane units represented by (Si0 4 / 2 ), the organopolysiloxane will be insoluble in toluene.
  • Organopolysiloxanes that are insoluble in toluene have problems such as the effects of reducing internal stress in the cured resin being insufficient and the shrinkage ratio being high when curing.
  • contents of potassium and sodium are not greater than 0.1 ppm
  • content of chlorine is not greater than 5 ppm
  • contents of uranium and thorium are not greater than 1 ppb. This is because there is a possibility that the moisture-resistant properties in high-temperature/high-humidity environments of a sealed or bonded semiconductor will be inhibited if the content of chlorine or the contents of sodium and potassium exceed the upper limits described above.
  • organopolysiloxane of the present invention may be produced according to conventional methods, it may also be produced according to the method described below.
  • R 17 R 18 f Si(OR 19 ) (3 _ f) (wherein R 17 is a secondary amino group-containing organic group, R 18 is a monovalent hydrocarbon group, R 20 is an alkyl group, and "f is 0, 1 , or 2), or a partial hydrolysate thereof.
  • the component (I) is the main starting material and is constituted by the one type or the mixture of two or more types of siloxanes having at least one type of unit selected from the group consisting of the units described as (i) to (iv) above or, alternatively, is the one type of alkoxysilane or the mixture of two or more types of alkoxysilanes.
  • Examples of the component (I) include the siloxane consisting only of the unit described in (i), the siloxane consisting only of the unit described in (iii), the siloxane consisting only of the unit described in (iv), a siloxane consisting of the unit described in (i) and the unit described in (ii), a siloxane consisting of the unit described in (i) and the unit described in (iii), a siloxane consisting of the unit described in (i) and the unit described in (iv), a siloxane consisting of the unit described in (i), the unit described in (ii), and the unit described in (iii), a siloxane consisting of the unit described in (i), the unit described in (ii), and the unit described in (iv), and a siloxane consisting of the unit described in (i), the unit described in (ii), the unit described in (ii), and the unit described in (iv), and a siloxane consisting of
  • the R 1 , R 12 , R 13 , R 14 , R 15 , and R 16 moieties are identical or different monovalent hydrocarbon groups and examples thereof include methyl groups, ethyl groups, propyl groups, butyl groups, pentyl groups, hexyl groups, heptyl groups, and similar alkyl groups; vinyl groups, allyl groups, butenyl groups, pentenyl groups, hexenyl groups, and similar alkenyl groups; phenyl groups, tolyl groups, xylyl groups, naphthyl groups, and similar aryl groups; benzyl groups, phenethyl groups, and similar aralkyl groups; chloromethyl groups, 3-chloropropyl groups, 3,3,3-trifluoropropyl groups, nonafluorobutyl ethyl groups, and similar substituted alkyl groups.
  • preferably 10 mol% or more and more preferably 30 mol% or more of the R 1 moieties are phenyl groups.
  • examples of the silicon-bonded organic group in the alkoxysilanes are synonymous with the monovalent hydrocarbon groups described above for the R 11 , R 12 , R 13 , R 14 , R 15 , and R 16 moieties, and examples of the alkoxy groups include alkoxy groups having from 1 to 10 carbons.
  • the monovalent hydrocarbon groups in the component (II) are synonymous with the groups described for the R 11 to R 16 moeities of component (I).
  • Examples of the alkyl groups include methyl groups, ethyl groups, propyl groups, butyl groups, pentyl groups, hexyl groups, heptyl groups, octyl groups, decyl groups, and dodecyl groups.
  • Examples of the silane or the siloxane in the component (I) include methyl
  • trimethoxysilane methyl triethoxysilane, ethyl trimethoxysilane, ethyl triethoxysilane, vinyl trimethoxysilane, phenyltrimethoxysilane, 3,3,3-trifluoropropyl trimethoxysilane, dimethyl dimethoxysilane, methylphenyl dimethoxysilane, methylvinyl dimethoxysilane, diphenyl dimethoxysilane, dimethyl diethoxysilane, methylphenyl diethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, dimethoxy diethoxysilane, and hydrolysis/condensation reaction products thereof.
  • the component (I) and the component (II) are reacted using a basic catalyst.
  • the basic catalyst serves a purpose of co-hydrolyzing, co-condensing, and also equilibrating the component (I) and the component (II).
  • Examples thereof include sodium hydroxide, potassium hydroxide, cesium hydroxide, and similar hydroxides of alkali metals; sodium-t-butoxide, potassium-t-butoxide, cesium-t-butoxide, and similar alkoxides of alkali metals; and sodium silanolate compounds, potassium silanolate compounds, cesium silanolate compounds, and similar silanol compounds of alkali metals.
  • the basic catalyst is preferably a potassium or cesium basic catalyst. Additionally, as necessary, water may be added for the purpose of co-hydrolyzing or co-condensing the component (I) and the component (II). After reacting the component (I) and the component (II), the solid content concentration in the reaction system may, as necessary, be adjusted using an organic solvent, and the system may be further reacted.
  • the siloxane bonds are randomly cleaved and re-bonded through the equilibrium reaction.
  • the obtained epoxy group-containing silicone resin is in an equilibrium condition. If the reaction temperature is low, the equilibrium reaction will not progress sufficiently, and if the reaction temperature is excessively high, the silicon-bonded organic groups will pyrolyze. Therefore, the reaction temperature is preferably from 80°C to 200°C and more preferably from 100°C to 150°C.
  • the equilibrium reaction can be carried out easily at reflux temperature by selecting an organic solvent having a boiling point from 80 to 200°C. Note that, the equilibrium reaction can be stopped by neutralizing the basic catalyst. Preferably, carbonic acid gas, carboxylic acid gas, or a similar weak acid is added to neutralize the basic catalyst.
  • the salt produced as a result of the neutralization can be removed via filtration or water rinsing.
  • the present invention also relates to a thermosetting resin additive comprising an organopolysiloxane.
  • the thermosetting resin additive of the present invention is characterized by comprising the organopolysiloxane of the present invention described above as said organopolysiloxane.
  • the present invention also relates to a thermosetting resin composition
  • a thermosetting resin composition comprising a thermosetting resin, a curing agent, and a thermosetting resin additive.
  • the composition of the present invention is characterized by comprising the thermosetting resin additive of the present invention described above as said thermosetting resin additive.
  • thermosetting resin additive comprised in the thermosetting resin composition of the present invention is preferably comprised at an amount of from 0.1 to 500 parts by mass per a total 100 parts by mass of the thermosetting resin and the curing agent.
  • epoxy resin examples include biphenyl type epoxy resins, bisphenol-A epoxy resins, bisphenol-F epoxy resins, stilbene epoxy resins, biphenyl-ether epoxy resins, and
  • a crystalline epoxy resin is preferably and a biphenyl type epoxy resin is more preferable.
  • biphenyl type epoxy resin examples include 4,4'-bis(2,3-epoxypropoxy)biphenyl, 4,4'-bis(2,3-epoxypropoxy)-3,3',5,5'-tetramethyl biphenyl,
  • biphenyl type epoxy resin is available as, for example, YX4000HK, manufactured by Yuka Shell Epoxy Co., Ltd.
  • the curing agent comprised in the thermosetting resin composition of the present invention preferably is a phenolic resin.
  • the phenolic resin include phenol novolac type phenolic resins, cresol novolac type phenolic resins, resole type phenolic resins, triphenyl alkane type epoxy resins, dicyclopentadiene-modified phenolic resins, phenol aralkyl type phenolic resins, biphenol type phenolic resins, and naphthol aralkyl type phenolic resins.
  • a phenol aralkyl type phenolic resin is preferable.
  • a phenol aralkyl type phenolic resin is available as, for example, Milex XLC-3L, manufactured by Mitsui Chemicals, Inc.
  • a content of the curing agent comprised in the thermosetting resin composition of the present invention is not particularly limited, but is an amount where a molar ratio of the phenolic hydroxyl groups in the phenolic resin to the epoxy groups in the epoxy resin is preferably from 0.5 to 2.5 and more preferably from 0.5 to 1.5. This is because if the curing agent is used in an amount less than the lower limit described above, the curing of the thermosetting resin composition will tend to be insufficient; and, if the content of curing agent exceeds the upper limit described above, strength of a cured product obtained from the composition will tend to decline.
  • the thermosetting resin composition of the present invention may further comprise an inorganic filler for the purpose of imparting mechanical strength and heat resistant properties and reducing expansion due to heat in the obtained cured product of the composition.
  • a content of the inorganic filler in the thermosetting resin composition is preferably from 100 to 1 ,200 parts by mass, more preferably from 400 to 1 ,000 parts by mass, and even more preferably from 400 to 800 parts by mass per a total 100 parts by mass of the thermosetting resin and the curing agent. If the content of inorganic filler is less than the lower limit described above, the strength of the obtained cured product will tend to be insufficient.
  • Examples of the inorganic filler include fibrous fillers such as glass fiber, asbestos, alumina fiber, ceramic fiber having alumina and silica as components, boron fiber, zirconia fiber, silicon carbide fiber, and metal fiber; particulate fillers such as fused silica, crystalline silica, precipitated silica, fumed silica, baked silica, zinc oxide, baked clay, carbon black, glass beads, alumina, talc, calcium carbonate, clay, aluminum hydroxide, magnesium hydroxide, barium sulfate, titanium dioxide, aluminum nitride, boron nitride, silicon carbide, aluminium oxide, magnesium oxide, titanium oxide, beryllium oxide, kaolin, mica, zirconia, and the like; and mixtures of two or more thereof.
  • fibrous fillers such as glass fiber, asbestos, alumina fiber, ceramic fiber having alumina and silica as components, boron fiber, zirconia fiber, silicon carbide fiber, and metal fiber
  • the form of the inorganic filler is not particularly limited, and examples thereof include spherical, needle-like, flat, irregularly crushed shape, and the like. Of these, a spherical form is preferable. Particularly, from the perspective of formability and hygroscopicity, spherical fused silica having an average particle size of from 5 to 40 pm is preferable.
  • a silane coupling agent, titanate coupling agent, or similar coupling agent can be used for the purpose of enhancing dispersibility and adhesion of the inorganic filler with respect to the thermosetting resin. Examples of such silane coupling agents include
  • alkoxysilanes N-(2-aminoethyl)-3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and similar amino group-containing alkoxysilanes; and 3-mercaptopropyltrimethoxysilane and similar mercapto group-containing alkoxysilanes.
  • titanate coupling agent examples include i-propoxytitane tri(i-isostearate).
  • a combination of two or more coupling agents may be used.
  • the method of surface treating and the compounded amount of the coupling agent used in the surface treating are not limited.
  • thermosetting resin composition of the present invention preferably further comprises a curing accelerator for the purpose of accelerating the curing.
  • the curing accelerator include triphenylphosphine, tributylphosphine, tri(p-methylphenyl)phosphine, tri(nonylphenyl)phosphine, triphenylphosphine-triphenylborate,
  • An amount of the curing accelerator is not particularly limited, but is preferably within a range of 0.001 to 20 parts by mass per 100 parts by mass of the thermosetting resin. This is because if the content of the curing accelerator is less than the lower limit described above, accelerating the reaction of the thermosetting resin with the curing agent will tend to be difficult; and, if the content exceeds the upper limit described above, the strength of the obtained cured product will tend to decline.
  • thermosetting resin composition of the present invention may comprise a thermoplastic resin, a thermoplastic elastomer, an organic synthetic rubber, a silicone, or a similar stress relaxing agent; Carnauba wax, higher fatty acids, a synthetic wax, or a similar wax; carbon black or a similar coloring agent; a halogen trapping agent; and the like.
  • thermosetting resin composition of the present invention is not particularly limited, and can be prepared by uniformly mixing the thermosetting resin additive with the thermosetting resin and the curing agent.
  • an example of a preparation method is one in which the curing agent, the thermosetting resin additive component, and the other optional components are uniformly mixed after mixing the inorganic filler with the thermosetting resin.
  • methods include adding and integrally blending the coupling agent with the thermosetting resin and the inorganic filler, or surface treating the inorganic filler with the coupling agent beforehand and then mixing the surface treated inorganic filler with the thermosetting resin.
  • devices for preparing the thermosetting resin composition of the present invention include single-screw or double-screw continuous kneaders, two-roll mills, Ross mixers, and kneader-mixers.
  • the melting point of the organopolysiloxane was measured using the MEL-TEMP II,
  • the weight average molecular weight of the organopolysiloxane was measured via gel permeation chromatography (GPC), using a toluene solution having a sample concentration of 1 % and employing the use of an Rl detector; and is expressed as a value obtained by converting the molecular weight using the standard polystyrene calibration curve.
  • GPC gel permeation chromatography
  • Viscosity at 25°C was measured using a rotational viscometer VG-DA (manufactured by Shibaura System Co., Ltd.).
  • the structure of the organopolysiloxane was determined via 29 Si-nuclear magnetic resonance spectroscopy (using the JNM-ECA500, manufactured by JEOL Ltd.).
  • Burr length at the time of molding was measured with a burr measurement mold (a groove having a depth of 20 ⁇ ), using a transfer pressing apparatus under the following conditions: mold temperature: 175°C, curing time: 2 minutes, molding pressure: 70 kgf/cm 2 .
  • the evaluation was recorded as follow; Cases where the burr length was 2 mm or less were indicated by "o”, cases where the burr length was greater than 2 mm and less than or equal to 10 mm were indicated by " ⁇ ”, and cases where the burr length was greater than 10 mm were indicated by "x".
  • PC Curing shrinkage ratio
  • the shrinkage ratio prior to the post-curing is designated as “Curing shrinkage ratio (AM)” and the post-curing shrinkage ratio is designated as “Curing shrinkage ratio (PC)”.
  • a specimen was cut from the sample formed in said procedure in evaluation (3), post-cured for 5 hours at 180°C, and the weight of the specimen was precisely measured (W 0 : about 5 g).
  • the specimen was placed in a 50 cc pressure-cooker test (PCT) container along with 40 g of ion exchanged water, and was retained in a pressurized water vapor environment (121°C) for 20 hours. Then, the specimen was removed from the PCT container, water was wiped from the surface, and a weight (W ⁇ thereof was measured.
  • Moisture absorption was calculated according to the following formula:
  • phenylmethylsiloxane (710 FLUID, manufactured by Dow Corning Toray Co., Ltd.), 162.2 g of toluene, and 0.29 g of cesium hydroxide were placed in a 300 ml flask provided with a thermometer, a Dean-Stark apparatus, and a refluxing cooler and stirred. 12.2 g of water was added and then the system was co-hydrolyzed while applying heat. Then, the generated alcohol and excess water were removed by azeotropic dehydration and the system was heated to reflux for 6 hours. The system was cooled, and then 0.6 g of acetic acid was added to neutralize the system.
  • the siloxane was determined via 29 Si-nuclear magnetic resonance spectroscopic analysis to be a phenylamino group-containing siloxane compound represented by the average structural formula:
  • a crosslinkable silicone composition was prepared. 5 parts by mass of a mixture containing this composition and secondary tridecylether and secondary dodecylether of ethylene oxide (7-mol addition) (43 mass.% of dodecyl groups, 57 mass.% of tridecyl groups, and HLB equal to 12.8) was premixed with 97 parts by mass of water. Thereafter, this mixture was emulsified by a colloid mill. Then, the emulsion was diluted with 100 parts by mass of pure water. Thus, a water-based emulsion of a silicone mixture was prepared.
  • a water-based emulsion of tin octoate having an average particle size of about 1.2 pm was prepared by emulsifying 1 part by mass of tin octoate (II) with 1 part by mass of a mixture containing secondary tridecylether and secondary dodecylether of ethylene oxide (7-mol addition) (43 mass.% of dodecyl groups, 57 mass.% of tridecyl groups, and HLB equal to 12.8) and 10 parts by mass of pure water.
  • the emulsion was added to the water-based emulsions of silicone composition, respectively and uniformly mixed, and allowed to sit at rest for 1 day and the crosslinkable silicone composition emulsifying in the water was cured.
  • a uniform aqueous suspension of cross-linked silicone-rubber particles, free of gel-like substance was prepared.
  • the suspension was dried by using a hot-air dryer and the cross-linked
  • silicone-rubber particles were collected.
  • dimethylsiloxane blocks represented by the average structure formula: -[Si(CH 3 ) 2 0]i 2 - were prepared.
  • the average particle size of the cross-linked silicone-rubber particles was 1.9 Mm, the type A durometer hardness was 67, and the anilino group content was 1.56 mass.%.
  • Solubility was checked by adding 1 g of the obtained cross-linked silicone-rubber particles to 99 g of toluene and stirring at 25°C. As dissolution could not be visually confirmed even after 10 minutes of stirring, it was determined that the cross-linked silicone-rubber particles were insoluble in toluene.
  • thermosetting resin composition [0081] Preparation and evaluation of the thermosetting resin composition
  • the curable epoxy resin composition of Practical Example 8 was prepared in the same procedure as that of Practical Example 7.
  • the curable epoxy resin composition and a cured body thereof were evaluated in the same manner as described in Practical Example 7. The results are shown in Table 2.
  • the curable epoxy resin composition of Practical Example 9 was prepared in the same procedure as that of Practical Example 7.
  • the curable epoxy resin composition and a cured body thereof were evaluated in the same procedure as described in Practical Example 7. The results are shown in Table 2.
  • the curable epoxy resin composition of Comparative Example 7 was prepared in the same manner as that of Practical Example 7.
  • the curable epoxy resin composition and a cured body thereof were evaluated in the same procedure as described in Practical Example 7. The results are shown in Table 2.
  • the curable epoxy resin composition of Comparative Example 9 was prepared in the same procedure as that of Practical Example 7.
  • the curable epoxy resin composition and a cured body thereof were evaluated in the same procedure as described in Practical Example 7. The results are shown in Table 2.
  • thermosetting resin compositions of Practical Examples 7 to 10 were cured, formability was superior, and moisture absorption and cure shrinkage were superior.
  • thermosetting resin compositions of Comparative Example 5 to 10 were cured, either gelling occurred or moisture absorption and curing shrinkage ratio were inferior.
  • thermosetting resin composition of the present invention By using the thermosetting resin composition of the present invention, a cured body having excellent formability, low moisture absorption, and low curing shrinkage ratio can be formed.
  • the thermosetting resin composition of the present invention can be suitably used as a sealing agent or adhesive for electric and electronic parts that are sensitive to stress generated when curing or when exposed to thermal shock.

Abstract

L'invention concerne un organopolysiloxane représenté par la formule unitaire moyenne suivante : (R1SiO3/2)a(R2R3SiO2/2)b(R4R5R6SiO1/2)c(SiO4/2)d (dans laquelle R1, R2, R3, R4, R5 et R6 représentent chacun des groupes hydrocarbure monovalents identiques ou différents, des groupes hydrocarbure monovalents substitués par un halogène ou des groupes organiques contenant un groupe amino secondaire qui comportent des noyaux aromatiques liés par un atome d'azote ; et 0,1 à 70 % molaire du nombre total de moles des fractions R1 à R6 est constitué par les groupes organiques contenant un groupe amino secondaire) ;"a" à "d" satisfont les relations suivantes : 0<a, 0<b, 0≤c, 0≤d≤0,3, 0,01≤b/a≤10, 0≤c/a≤0,8 et a+b+c+d=1.
PCT/JP2013/062687 2012-04-26 2013-04-23 Nouvel organopolysiloxane, additif de résine thermodurcissable comprenant ce composé et composition de résine thermodurcissable comprenant celui-ci WO2013162052A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2012-101221 2012-04-26
JP2012101221A JP2013227446A (ja) 2012-04-26 2012-04-26 新規なオルガノポリシロキサン、それを含む熱硬化性樹脂用添加剤、およびそれを含む熱硬化性樹脂組成物

Publications (1)

Publication Number Publication Date
WO2013162052A1 true WO2013162052A1 (fr) 2013-10-31

Family

ID=48428585

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2013/062687 WO2013162052A1 (fr) 2012-04-26 2013-04-23 Nouvel organopolysiloxane, additif de résine thermodurcissable comprenant ce composé et composition de résine thermodurcissable comprenant celui-ci

Country Status (3)

Country Link
JP (1) JP2013227446A (fr)
TW (1) TW201348340A (fr)
WO (1) WO2013162052A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9840641B2 (en) 2014-01-24 2017-12-12 Sumitomo Chemical Company, Limited Silicone resin liquid composition

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114591598B (zh) * 2022-03-13 2023-06-02 连云港华海诚科电子材料有限公司 一种晶圆级封装用液体塑封料及其制备方法

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6227095B2 (fr) 1980-03-31 1987-06-12 Shinetsu Chem Ind Co
US5008349A (en) * 1989-10-26 1991-04-16 Dow Corning Corporation Silicone primer compositions
JP2005015559A (ja) 2003-06-24 2005-01-20 Hitachi Chem Co Ltd 封止用エポキシ樹脂成形材料及び電子部品装置
JP2006269730A (ja) 2005-03-24 2006-10-05 Hitachi Chem Co Ltd 封止用エポキシ樹脂成形材料及びそれを用いた電子部品装置
JP2008285552A (ja) 2007-05-16 2008-11-27 Dow Corning Toray Co Ltd 架橋シリコーン粒子およびその製造方法
JP2008285553A (ja) 2007-05-16 2008-11-27 Dow Corning Toray Co Ltd 硬化性エポキシ樹脂組成物およびその硬化物
JP2011152196A (ja) 2010-01-26 2011-08-11 Taiyo Elec Co Ltd 回胴式遊技機
JP2011152186A (ja) 2010-01-26 2011-08-11 Nakano Refrigerators Co Ltd リーチインショーケース

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6227095B2 (fr) 1980-03-31 1987-06-12 Shinetsu Chem Ind Co
US5008349A (en) * 1989-10-26 1991-04-16 Dow Corning Corporation Silicone primer compositions
JPH03157453A (ja) 1989-10-26 1991-07-05 Dow Corning Corp シリコーンプライマー組成物
JP2005015559A (ja) 2003-06-24 2005-01-20 Hitachi Chem Co Ltd 封止用エポキシ樹脂成形材料及び電子部品装置
JP2006269730A (ja) 2005-03-24 2006-10-05 Hitachi Chem Co Ltd 封止用エポキシ樹脂成形材料及びそれを用いた電子部品装置
JP2008285552A (ja) 2007-05-16 2008-11-27 Dow Corning Toray Co Ltd 架橋シリコーン粒子およびその製造方法
JP2008285553A (ja) 2007-05-16 2008-11-27 Dow Corning Toray Co Ltd 硬化性エポキシ樹脂組成物およびその硬化物
JP2011152196A (ja) 2010-01-26 2011-08-11 Taiyo Elec Co Ltd 回胴式遊技機
JP2011152186A (ja) 2010-01-26 2011-08-11 Nakano Refrigerators Co Ltd リーチインショーケース

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9840641B2 (en) 2014-01-24 2017-12-12 Sumitomo Chemical Company, Limited Silicone resin liquid composition

Also Published As

Publication number Publication date
TW201348340A (zh) 2013-12-01
JP2013227446A (ja) 2013-11-07

Similar Documents

Publication Publication Date Title
EP0620242B1 (fr) Résine silicone contenant des groupes époxy et composition à base de celui-ci
US5952439A (en) Epoxy group-containing silicone resin and compositions based thereon
KR100851769B1 (ko) 경화성 에폭시 수지 조성물
JP3339910B2 (ja) 硬化性樹脂組成物
KR20010111026A (ko) 열전도성 실리콘 고무 조성물
KR100591671B1 (ko) 반도체 캡슐화 에폭시 수지 조성물 및 반도체 장치
WO2008047892A1 (fr) COMPOSITION de POLYORGANOSILOXANE durcissable
JP5473195B2 (ja) 架橋シリコーン粒子およびその製造方法
JP5877163B2 (ja) 硬化性エポキシ樹脂組成物
KR101486221B1 (ko) 경화성 에폭시 수지 조성물 및 이의 경화체
US20170029571A1 (en) Hydrosilyl-containing organopolysiloxane, making method, addition curable silicone composition, and semiconductor package
JP4050070B2 (ja) シリコーンレジン組成物、硬化性樹脂組成物、および硬化物
JP2009185226A (ja) 加熱硬化性シリコーン組成物とそれを用いた光学部材用成形物
US20220363835A1 (en) Thermally conductive silicone composition and method for producing the same
KR20100058519A (ko) 경화성 에폭시 수지 조성물 및 이의 경화 생성물
KR101383128B1 (ko) 경화성 실리콘 조성물 및 이의 경화물
WO2013162052A1 (fr) Nouvel organopolysiloxane, additif de résine thermodurcissable comprenant ce composé et composition de résine thermodurcissable comprenant celui-ci
KR101496746B1 (ko) 실리콘 고무 분말 및 이의 제조 방법
US10179840B2 (en) Condensation curable resin composition and semiconductor package
JP2011132299A (ja) シリコーン樹脂組成物

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13722130

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 13722130

Country of ref document: EP

Kind code of ref document: A1