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WO2017094357A1 - Composition de gel de silicone auto-adhésive et gel de silicone - Google Patents

Composition de gel de silicone auto-adhésive et gel de silicone Download PDF

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Publication number
WO2017094357A1
WO2017094357A1 PCT/JP2016/080237 JP2016080237W WO2017094357A1 WO 2017094357 A1 WO2017094357 A1 WO 2017094357A1 JP 2016080237 W JP2016080237 W JP 2016080237W WO 2017094357 A1 WO2017094357 A1 WO 2017094357A1
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group
silicone gel
composition
component
self
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Japanese (ja)
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正 荒木
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Shin Etsu Chemical Co Ltd
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Shin Etsu Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers

Definitions

  • the present invention relates to a silicone gel composition excellent in self-adhesiveness, and a silicone gel comprising a cured product thereof, and particularly has good adhesion to a substrate such as copper and aluminum, and is free from peeling and voids after adhesion.
  • the present invention relates to a self-adhesive silicone gel composition capable of suppressing generation and a silicone gel comprising a cured product of the composition.
  • the silicone gel composition contains an organohydrogenpolysiloxane having a hydrogen atom (ie, SiH group) bonded to a silicon atom, an organopolysiloxane having an alkenyl group such as a vinyl group bonded to a silicon atom, and a platinum-based catalyst.
  • the addition reaction curable organopolysiloxane composition is obtained by obtaining a cured product by addition reaction of hydrogen atoms bonded to silicon atoms to alkenyl groups.
  • the silicone gel cured product cured by heating this silicone gel composition is excellent in heat resistance, weather resistance, oil resistance, cold resistance, electrical insulation, etc. It is used to protect electronic parts such as parts and consumer electronic parts.
  • silicone gel cured products are not found in other elastomer products.
  • high adhesiveness with a base material is required for silicone gel materials used for sealing because of demands for high reliability of in-vehicle electronic parts and consumer electronic parts.
  • Patent Literature 1 to 7 have adhesive components that exhibit high adhesiveness, that is, have hydrolyzable groups such as methoxy groups and ethoxy groups in the molecule and functional groups such as epoxy groups, isocyanate groups, and isocyanur groups. Adhesion is improved using a silane coupling agent.
  • Patent Documents 8 to 11 adhesion due to addition of an organic peroxide is disclosed. Improvement techniques have been introduced, but this also causes a problem that peeling and voids occur due to oxygen generated as a by-product.
  • Patent Documents 12 to 14 the structure of the organopolysiloxane used, the structure of hydrosilyl group (SiH group), etc. are described.
  • the technology to improve the adhesiveness by changing it has been introduced, the adhesion with the base material is certainly improved with this method, but the adhesive has not been reached yet, so the adhesiveness will deteriorate with long-term use There was a problem.
  • An object of the present invention is to provide a self-adhesive silicone gel composition having adhesiveness and capable of suppressing the occurrence of peeling and voids after adhesion, and a silicone gel comprising a cured product of the composition.
  • an addition reaction curable silicone gel composition has at least one isocyanate group in one molecule and contains a hydrolyzable group. It has been found that by adding a certain amount of a non-aliphatic organic compound, it can be a self-adhesive silicone gel composition having no adhesion to the substrate and no peeling or voiding after bonding, and has led to the present invention. .
  • the present invention provides the following self-adhesive silicone gel composition and silicone gel.
  • A The following average composition formula (1) R a R 1 b SiO (4-ab) / 2 (1) Wherein R is independently an alkenyl group, R 1 is independently an unsubstituted or substituted monovalent hydrocarbon group not containing an aliphatic unsaturated bond, and a is a positive number of 0.0001 to 0.2 And b is a positive number from 1.7 to 2.2, where a + b is 1.9 to 2.4.) An organopolysiloxane having at least one alkenyl group bonded to a silicon atom in one molecule: 100 parts by mass, (B) The following average composition formula (2) R 2 c H d SiO (4-cd) / 2 (2) (Wherein R 2 independently represents an unsubstituted or substituted monovalent hydrocarbon group that does not contain an aliphatic unsaturated bond, c is a positive number of 0.7 to 2.2,
  • (D) component is the following general formula (3) X—C n H m —NCO (3) (In the formula, n is an integer of 1 to 10, m is an integer of 2 to 20, provided that n and m are n ⁇ m, and X is a functional group other than a hydrolyzable group.)
  • [4] [1] A silicone gel comprising a cured product of the self-adhesive silicone gel composition according to any one of [3].
  • the self-adhesive silicone gel composition of the present invention provides a cured silicone gel with better adhesion than before and less occurrence of peeling and voids after adhesion.
  • the self-adhesive silicone gel composition of the present invention comprises the following components (A) to (D) as essential components.
  • a silicone gel silicone gel cured product
  • a silicone gel is a cured product having an organopolysiloxane as a main component and a low crosslinking density, and has a penetration of 10 to 10 according to JIS K2220 (1/4 cone).
  • 80 means. This is equivalent to a measured value (rubber hardness value) of 0 in rubber hardness measurement according to JIS K6253, which is so low that it does not show an effective rubber hardness value (ie, soft). It is different from a rubber cured product (rubber-like elastic body).
  • a viscosity is a value in 25 degreeC.
  • (A) component of this invention is the main ingredient (base polymer) of a silicone gel composition.
  • the component (A) is an average of alkenyl groups bonded to silicon atoms in one molecule represented by the following average composition formula (1) (referred to herein as “silicon atom-bonded alkenyl groups”).
  • An organopolysiloxane having at least one.
  • R a R 1 b SiO (4-ab) / 2 (1) Wherein R is independently an alkenyl group, R 1 is independently an unsubstituted or substituted monovalent hydrocarbon group not containing an aliphatic unsaturated bond, and a is a positive number of 0.0001 to 0.2 And b is a positive number from 1.7 to 2.2, where a + b is 1.9 to 2.4.)
  • R is independently an alkenyl group usually having 2 to 6, preferably 2 to 4, more preferably 2 to 3 carbon atoms. Specific examples thereof include a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, and an isobutenyl group, and a vinyl group is preferable.
  • R 1 independently represents an unsubstituted or substituted monovalent hydrocarbon group that does not contain an aliphatic unsaturated bond, and the number of carbon atoms is usually 1 to 10, preferably 1 to 6.
  • a needs to be a positive number from 0.0001 to 0.2, and is preferably a positive number from 0.0005 to 0.1.
  • b needs to be a positive number of 1.7 to 2.2, and is preferably a positive number of 1.9 to 2.02.
  • a + b needs to satisfy the range of 1.9 to 2.4, and preferably 1.95 to 2.05.
  • the component (A) needs to have at least one silicon atom-bonded alkenyl group on average in the molecule as the whole component (A), preferably 2 to 50, more preferably 2 to 10 Have one. What is necessary is just to select the value of said a and b so that the conditions of this silicon atom bond alkenyl group may be satisfy
  • the molecular structure of the organopolysiloxane of component (A) is not particularly limited, and even if it is linear, for example, RSiO 3/2 unit, R 1 SiO 3/2 unit (R and R 1 are the same as above) , A branched chain containing a SiO 2 unit or the like may be used.
  • R 3 independently represents an unsubstituted or substituted monovalent hydrocarbon group that does not contain an aliphatic unsaturated bond
  • R 4 independently represents an unsubstituted or substituted monovalent radical that does not contain an aliphatic unsaturated bond.
  • a hydrocarbon group or an alkenyl group provided that at least one, preferably 2 to 50, more preferably 2 to 10, R 4 is an alkenyl group, and either R 4 at both ends of the molecular chain is an alkenyl group.
  • E is an integer of 40 to 1,200
  • f is an integer of 0 to 50
  • g is an integer of 0 to 50
  • both R 4 at both ends of the molecular chain are alkenyl.
  • e is an integer of 40 to 1,200
  • f is an integer of 1 to 50
  • g is an integer of 0 to 50, provided that f + g is 1 or more.
  • the unsubstituted or substituted monovalent hydrocarbon group not containing an aliphatic unsaturated bond represented by R 3 is usually one having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms. Specific examples thereof include those exemplified for R 1 . Among them, a methyl group, a phenyl group, or a 3,3,3-trifluoropropyl group is preferable because synthesis is easy.
  • the unsubstituted or substituted monovalent hydrocarbon group not containing an aliphatic unsaturated bond is usually one having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms. Specific examples thereof include those exemplified for R 1 . Among them, a methyl group, a phenyl group, or a 3,3,3-trifluoropropyl group is preferable because synthesis is easy.
  • the alkenyl group is usually one having 2 to 6, preferably 2 to 4, more preferably 2 to 3 carbon atoms. Specific examples thereof include a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, and an isobutenyl group, and a vinyl group is preferable.
  • organopolysiloxane represented by the above formula (1a) examples include dimethylpolysiloxane having both ends dimethylvinylsiloxy group-blocked dimethylpolysiloxane, dimethylvinylsiloxy group-blocked dimethylsiloxane / methylvinylsiloxane copolymer, and both ends dimethylvinylsiloxy.
  • the viscosity of the organopolysiloxane of component (A) is not particularly limited, but the viscosity at 25 ° C. is 50 to 100,000 mPa from the point that the handling workability of the composition, the strength of the resulting cured product, and the fluidity are good. S is preferable, and 100 to 10,000 mPa ⁇ s is more preferable.
  • the viscosity can be measured with a rotational viscometer (for example, BL type, BH type, BS type, cone plate type, rheometer, etc.) (hereinafter the same).
  • the viscosity range is such that the degree of polymerization (or the number of silicon atoms in the molecule) of the organopolysiloxane (A) is usually 30 to 1,500, preferably 50 to 1,000, more preferably 100 to This is equivalent to about 600.
  • the degree of polymerization (or molecular weight) can be determined, for example, as the number average degree of polymerization (or number average molecular weight) in terms of polystyrene in gel permeation chromatography analysis using toluene or the like as a developing solvent (hereinafter the same).
  • the organopolysiloxane of component (A) can be used alone or in combination as long as it satisfies the condition that the entire component (A) has at least one silicon-bonded alkenyl group on average in one molecule.
  • a combination of the above may also be used.
  • Organopolysiloxane having one alkenyl group or organopolysiloxane having less than one for example, organopolysiloxane having the same average degree of polymerization and distribution of polymerization degree and having one alkenyl group bonded to a silicon atom at one end of the molecular chain
  • organopolysiloxane having the same average degree of polymerization and distribution of polymerization degree and having one alkenyl group bonded to a silicon atom at one end of the molecular chain And a uniform mixture of an organopolysiloxane containing no alkenyl group in the molecule, etc.
  • a mass ratio of about 100: 0 to 40:60, particularly 100: 0 to 60:40 it is preferable because the composition has good curability and can stably obtain a soft (high penetration) silicone gel cured product. .
  • the component (B) of the present invention reacts with the component (A) and acts as a crosslinking agent (curing agent).
  • the component (B) has the following average composition formula (2) R 2 c H d SiO (4-cd) / 2 (2) (Wherein R 2 independently represents an unsubstituted or substituted monovalent hydrocarbon group that does not contain an aliphatic unsaturated bond, c is a positive number of 0.7 to 2.2, and d is 0.001.
  • An organohydrogenpolysiloxane having at least two hydrogen atoms bonded to a silicon atom in one molecule has preferably 3 to 500, more preferably 5 to 100, and particularly preferably 10 to silicon-bonded hydrogen atoms (ie, a hydrosilyl group represented by SiH) in one molecule.
  • the SiH group may be bonded to the silicon atom at the end of the molecular chain or may be bonded to the silicon atom at the non-terminal end of the molecular chain (in the middle of the molecular chain). Good.
  • R 2 independently represents an unsubstituted or substituted monovalent hydrocarbon group that does not contain an aliphatic unsaturated bond, and the number of carbon atoms is usually 1 to 10, preferably 1 to 6. is there. Specific examples thereof include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, cyclohexyl group, octyl group, nonyl group, decyl group.
  • An alkyl group such as phenyl group, tolyl group, xylyl group, naphthyl group, etc .; aralkyl group such as benzyl group, phenylethyl group, phenylpropyl group, etc .; And a 3,3,3-trifluoropropyl group substituted with a halogen atom such as bromine and fluorine.
  • a halogen atom such as bromine and fluorine.
  • an alkyl group, an aryl group, and a 3,3,3-trifluoropropyl group are preferable, and a methyl group, a phenyl group, and a 3,3,3-trifluoropropyl group are more preferable.
  • c is a positive number of 0.7 to 2.2, and is preferably a positive number of 1.0 to 2.1.
  • d is a positive number of 0.001 to 0.5, and is preferably a positive number of 0.005 to 0.1.
  • c + d is 0.8 to 3.0, preferably 1.0 to 2.5, and more preferably 1.5 to 2.2.
  • the molecular structure of the organohydrogenpolysiloxane of component (B) is not particularly limited, and may be any of a linear, cyclic, branched, and three-dimensional network (resinous) structure.
  • the number of silicon atoms (that is, the degree of polymerization) is usually 10 to 1,000, but the workability of the composition and the properties of the resulting cured product (low elastic modulus, low stress) are improved. Therefore, the number is preferably 10 to 500, more preferably 15 to 100, and still more preferably 20 to 60.
  • organohydrogenpolysiloxane represented by the above formula (2) examples include 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, and methylhydrogensiloxane.
  • Cyclic polymer tris (dimethylhydrogensiloxy) methylsilane, tris (dimethylhydrogensiloxy) phenylsilane, methylhydrogensiloxane / dimethylsiloxane cyclic copolymer, both ends dimethylhydrogensiloxy group-blocked methylhydrogenpolysiloxane, both Terminal dimethylhydrogensiloxy group-blocked methylhydrogen / dimethylsiloxane copolymer, both-end dimethylhydrogensiloxy group-blocked methylhydrogen / diphenylsiloxane copolymer, both-end dimethyl Hydroxysiloxy group-blocked methylhydrogen / dimethylsiloxane / diphenylsiloxane copolymer, trimethylsiloxy group-blocked methylhydrogenpolysiloxane at both ends, trimethylsiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane cop
  • the (B) component organohydrogenpolysiloxane may be used singly or in combination of two or more.
  • organohydrogenpolysiloxane having 2 or more, particularly 3 or more hydrogen atoms bonded to silicon atoms in the middle of the molecular chain (side chain), and hydrogen atoms bonded to silicon atoms at both ends of the molecular chain It is possible to mix and use organohydrogenpolysiloxane having 2 (only) in a mass ratio of about 100: 0 to 5:95, particularly about 100: 0 to 8:92.
  • a favorable and flexible (high penetration) silicone gel cured product is preferred because it can be stably obtained.
  • Component (B) is added in an amount of 0.01 to 3 hydrogen atoms bonded to silicon atoms relative to one alkenyl group bonded to silicon atoms in the entire composition (that is, component (A) above), preferably Is in an amount of 0.05 to 2, more preferably 0.2 to 1.5.
  • component (A) a cured product cannot be obtained.
  • cured material falls.
  • the component (C) of the present invention is a catalyst (platinum group metal catalyst) for promoting the addition reaction between the silicon atom-bonded alkenyl group of the component (A) and the silicon atom-bonded hydrogen atom in the component (B). It is what is used.
  • the component (C) is a platinum-based catalyst (platinum or a platinum-based compound), and a known one can be used. Specific examples thereof include alcohol-modified products such as platinum black, chloroplatinic acid, and chloroplatinic acid; complexes of chloroplatinic acid and olefins, aldehydes, vinyl siloxanes, acetylene alcohols, and the like.
  • the compounding amount of the component (C) may be an effective amount, and can be appropriately increased or decreased depending on the desired curing rate. Usually, it is in the range of 0.1 to 1,000 ppm, preferably 1 to 300 ppm. If the amount is too large, the heat resistance of the resulting cured product may decrease.
  • Component (D) of the present invention contains at least one isocyanate group in one molecule and does not contain a hydrolyzable group, and contains an aromatic ring structure such as a benzene ring (for example, a phenylene group) in the molecule. It is an aliphatic organic compound that does not, and is an essential component for imparting excellent adhesiveness to the silicone gel composition of the present invention.
  • the component (D) is preferably an aliphatic organic compound represented by the following general formula (3).
  • n is an integer of 1 to 10
  • m is an integer of 2 to 20, provided that n and m are n ⁇ m
  • X is a functional group other than a hydrolyzable group.
  • n is an integer of 1 to 10, preferably an integer of 3 to 8
  • m is an integer of 2 to 20, preferably 6 to 16
  • n and m must always satisfy n ⁇
  • an aliphatic organic compound that satisfies the relationship of m and has one or more, preferably two, isocyanate groups in one molecule and does not contain a hydrolyzable group. It is essential for this.
  • any functional group can be used.
  • an isocyanate group is particularly effective because the same effect can be obtained even if the amount of component (D) is small.
  • aliphatic organic compound having at least one isocyanate group in one molecule of component (D) and not containing a hydrolyzable group include butyl isocyanate, tert-butyl isocyanate, hexyl isocyanate, heptyl isocyanate, X in the formula (3) such as cyclopentyl isocyanate, cyclohexyl isocyanate and other compounds having one isocyanate group in the molecule, hexamethylene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate is an isocyanate group A compound having two isocyanate groups in the molecule, an isocyanate compound having a halogen group as X in formula (3), such as 2-chloroethyl isocyanate, 2-fluoroethyl isocyanate, etc.
  • X is the isocyanate
  • the amount of component (D) added is in the range of 0.001 to 1.0 part by weight, preferably 0.005 to 0.2 part by weight, more preferably 100 parts by weight of component (A). The range is 0.01 to 0.1 parts by mass.
  • (D) When the addition amount of a component is less than 0.001 mass part, the adhesiveness expected with respect to copper or aluminum cannot be expressed. Moreover, when the addition amount of (D) component exceeds 1.0 mass part, since the platinum-type catalyst of (C) component is stabilized more by the isocyanate group of (D) component, hardening may become slow or obtained. The resulting silicone gel is too soft or in the worst case uncured.
  • an optional component can be blended in the silicone gel composition of the present invention as long as the object of the present invention is not impaired.
  • this optional component for example, reaction inhibitor, inorganic filler, organopolysiloxane containing no silicon atom-bonded hydrogen atom and silicon atom-bonded alkenyl group, heat resistance imparting agent, flame retardancy imparting agent, thixotropic property imparting agent, Examples thereof include pigments and dyes.
  • the reaction inhibitor is a component for suppressing the reaction of the composition, and specifically includes, for example, acetylene-based, amine-based, carboxylic acid ester-based, phosphite-based reaction inhibitor, and the like. It is done.
  • inorganic fillers examples include fumed silica, crystalline silica, precipitated silica, hollow filler, silsesquioxane, fumed titanium dioxide, magnesium oxide, zinc oxide, iron oxide, aluminum hydroxide, magnesium carbonate, and calcium carbonate.
  • inorganic fillers such as zinc carbonate, layered mica, carbon black, diatomaceous earth, and glass fiber; these fillers are organic silicon compounds such as organoalkoxysilane compounds, organochlorosilane compounds, organosilazane compounds, and low molecular weight siloxane compounds. Examples thereof include a surface hydrophobized filler. Silicone rubber powder, silicone resin powder, and the like may also be blended.
  • the silicone gel composition of the present invention can be prepared by mixing the above components (A) to (D) (including optional components when optional components are blended) according to a conventional method.
  • the components to be mixed may be divided into two or more parts and mixed as necessary, for example, (A) part or all of the component and (C) the part consisting of the component and It is also possible to divide and mix the remainder of the component (A) and the part composed of the components (B) and (D).
  • a part consisting of part or all of the component (A) and the component (C), the remainder of the component (A) and the part consisting of the components (B) and (D) It is more preferable to divide into
  • the silicone gel composition of the present invention is heated at room temperature (25 ° C. ⁇ 10 ° C.) or under a heating temperature according to the application (for example, about 35 to 150 ° C., particularly about 50 to 130 ° C.) for 10 to 120 minutes.
  • a cured silicone gel can be obtained by curing for about 30 to 60 minutes.
  • the silicone gel composition of the present invention is preferably used for sealing or filling electric / electronic parts.
  • the cured product (silicone gel or silicone gel cured product) of the silicone gel composition of the present invention preferably has a penetration of 10 to 80, more preferably 20 to 20 with a 1/4 cone defined by JIS K2220. 70, more preferably 30-60. If the penetration is less than 10, the silicone gel composition may not be able to withstand the stress at the time of curing, and a part of the electronic circuit may be broken or a crack may be generated inside the silicone gel. Moreover, when the penetration exceeds 80, since it is too soft, if the silicone gel cured product is largely deformed, it may be easily peeled off or the adhesion to the substrate may be reduced.
  • the cured product of the silicone gel composition of the present invention has a loss factor at 25 ° C. and a shear frequency of 1 Hz, preferably 0.1 to 1.0, more preferably 0.12 to 0.8, and still more preferably 0.
  • the loss factor at 25 ° C. and a shear frequency of 10 Hz is preferably 0.3 to 1.5, more preferably 0.35 to 1.2, and still more preferably 0.4 to 1. 0.
  • the loss factor at 25 ° C. and shear frequency of 1 Hz is less than 0.1, the silicone gel composition cannot withstand the stress at the time of curing, and part of the electronic circuit breaks or cracks are generated inside the silicone gel. Sometimes.
  • the loss coefficient at 25 ° C. and a shear frequency of 10 Hz exceeds 1.5, a cured silicone gel having sufficient shape retention ability cannot be obtained, and the adhesion to the substrate is the same as described above. May decrease.
  • the present invention will be specifically described by way of examples and comparative examples, but the following examples are not intended to limit the present invention.
  • “part” represents “part by mass”
  • “%” represents “mass%”
  • “Vi” represents “vinyl group”.
  • the penetration is a penetration with a 1 ⁇ 4 cone defined by JIS K2220, and was measured using an automatic penetration meter RPM-101 manufactured by Kouaisha.
  • Example 1 The following average molecular formula (4) 60 parts of a dimethylvinylsiloxy group-blocked dimethylsiloxane / diphenylsiloxane copolymer having a viscosity at 25 ° C. of 1,000 mPa ⁇ s represented by the following average molecular formula (5) 40 parts of a trimethylsiloxy group / vinyldimethylsiloxy group-blocked dimethylsiloxane / diphenylsiloxane copolymer having a viscosity at 25 ° C.
  • a composition 1 was obtained in which 0.05 part of the polysiloxane solution, 0.02 part of ethynylcyclohexanol, which is an optional component, and 0.01 part of hexamethylene diisocyanate, which is the component (D), were uniformly mixed.
  • a cured silicone gel having a penetration of 45 was obtained.
  • Example 2 In Example 1, composition 2 was obtained in the same manner except that 0.015 part of hexyl isocyanate was used instead of 0.01 part of hexamethylene diisocyanate. When this composition 2 was heat-cured at 80 ° C. for 60 minutes, a cured silicone gel having a penetration of 42 was obtained.
  • composition 3 was obtained in the same manner as in Example 1 except that hexamethylene diisocyanate was not used. This composition 3 was cured by heating at 80 ° C. for 60 minutes to obtain a cured silicone gel having a penetration of 40.
  • composition 5 was obtained in the same manner as in Example 1, except that 0.01 part of ⁇ -glycidoxypropyltrimethoxysilane was added instead of 0.01 part of hexamethylene diisocyanate. When this composition 5 was heat-cured at 80 ° C. for 60 minutes, a cured silicone gel having a penetration of 35 was obtained.
  • composition 6 was obtained in the same manner as in Example 1, except that 0.01 part of 3-isocyanatopropyltriethoxysilane was added instead of 0.01 part of hexamethylene diisocyanate. When this composition 6 was heat-cured at 80 ° C. for 60 minutes, a cured silicone gel having a penetration of 45 was obtained.
  • composition 7 was obtained in the same manner as in Example 1 except that the amount of hexamethylene diisocyanate was changed to 1.5 parts. When this composition 7 was heat-cured at 80 ° C. for 60 minutes, it was not cured, so a cured product could not be obtained.
  • Void test About 5 g of the composition obtained above was poured into an aluminum petri dish having a diameter of 60 mm and a depth of 10 mm, and was cured by heating at 80 ° C. for 1 hour. Then, after being left in an environment of 85 ° C. ⁇ 85% RH for 24 hours, it was immediately exposed on a hot plate at 110 ° C., and after 1 hour, it was visually confirmed whether peeling or void occurred at the interface with the aluminum petri dish. Those in which no peeling or void was confirmed were regarded as acceptable.
  • Example and Comparative Example are divided into two components, and the uncured liquid is allowed to stand for 12 months in a 25 ° C. environment, and then both are prepared and mixed so as to have the same mixing ratio as in the Example and Comparative Example. In the same manner, the penetration and adhesion were evaluated. In addition, when making it into two components, it divided
  • compositions of Examples 1 and 2 satisfy the requirements of the present invention, and the cured product of the composition has good adhesiveness, and no peeling or void has been confirmed after bonding. . Moreover, when the components were divided and the storage stability was evaluated, it was confirmed that there was no change in the penetration and adhesiveness. On the other hand, since the composition of Comparative Example 1 does not contain the component (D) of the present invention, it can be seen that the cured product of the composition has poor adhesion to oxygen-free copper or aluminum. Further, the composition of Comparative Example 2 does not satisfy the requirement of the aliphatic organic compound (specifically, n ⁇ m in the formula (3)), which is the condition of the component (D) of the present invention.
  • the cured product of the composition has poor adhesion to oxygen-free copper. This is presumed to be because when n> m, that is, since many conjugated or non-conjugated double bonds exist in the molecule, the compatibility with silicone oil decreases.
  • the cured product is free from peeling and voids by a void test. It is confirmed that the result does not reach the expected adhesiveness.
  • the silicone gel cured product obtained by curing the silicone gel composition of the present invention adheres well to a substrate used for an electronic substrate, particularly a substrate such as copper or aluminum, and peels off after bonding. It is possible to manufacture an electronic component with less generation of voids and improved long-term reliability. Therefore, improvement in reliability is expected in the protection application of electronic parts such as IC and hybrid IC.

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Abstract

L'invention concerne : une composition de gel de silicone auto-adhésive qui présente une excellente adhésivité à une base qui est présente dans une carte électronique et est formée de cuivre, d'aluminium ou analogue, tout en maintenant les caractéristiques des matériaux d'étanchéité classiques, et qui permet de supprimer l'apparition de vides ou de séparation après adhérence ; et un gel de silicone qui est composé d'un produit durci de cette composition. Selon la présente invention, un composé organique aliphatique qui contient un ou plusieurs groupes isocyanates dans chaque molécule mais ne contient pas de groupe hydrolysable est ajouté en une quantité spécifique dans une composition de gel de silicone durcissable par addition.
PCT/JP2016/080237 2015-11-30 2016-10-12 Composition de gel de silicone auto-adhésive et gel de silicone Ceased WO2017094357A1 (fr)

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WO2021210273A1 (fr) * 2020-04-14 2021-10-21 信越化学工業株式会社 Composition de caoutchouc de silicone broyable auto-adhésive
JP2023007206A (ja) * 2021-07-01 2023-01-18 信越化学工業株式会社 付加硬化型シリコーンゴム組成物及びシリコーンゴム硬化物

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WO2020203597A1 (fr) 2019-04-01 2020-10-08 信越化学工業株式会社 Composition de gel de silicone auto-adhésive et produit durci à base de gel de silicone

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JPH03223362A (ja) * 1989-12-05 1991-10-02 Shin Etsu Chem Co Ltd 自己接着型シリコーンゴム組成物及びシリコーンゴム被覆布
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WO2021210273A1 (fr) * 2020-04-14 2021-10-21 信越化学工業株式会社 Composition de caoutchouc de silicone broyable auto-adhésive
JP2021169542A (ja) * 2020-04-14 2021-10-28 信越化学工業株式会社 自己接着ミラブル型シリコーンゴム組成物
JP7285800B2 (ja) 2020-04-14 2023-06-02 信越化学工業株式会社 自己接着ミラブル型シリコーンゴム組成物
JP2023007206A (ja) * 2021-07-01 2023-01-18 信越化学工業株式会社 付加硬化型シリコーンゴム組成物及びシリコーンゴム硬化物
JP7540975B2 (ja) 2021-07-01 2024-08-27 信越化学工業株式会社 付加硬化型シリコーンゴム組成物及びシリコーンゴム硬化物

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