Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
  • C09J11/02—Non-macromolecular additives
  • C09J11/06—Non-macromolecular additives organic
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
  • C09J183/04—Polysiloxanes
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W72/00—Interconnections or connectors in packages
  • H10W72/071—Connecting or disconnecting

Definitions

• a semiconductor element can be satisfactorily mounted even after being left for a long time after being applied to an object to be coated, and under both high-temperature heating and low-temperature heating conditions. Also, an adhesive paste whose cured product has excellent adhesiveness, a method of using this adhesive paste as an adhesive for a semiconductor element fixing material, and a method for manufacturing a semiconductor device using this adhesive paste as an adhesive for a semiconductor element fixing material Regarding.
• Adhesive pastes have heretofore been improved in various ways according to their intended use, and have been widely used industrially as raw materials for optical parts and moldings, adhesives, coating agents, and the like. Adhesive pastes are also attracting attention as pastes for semiconductor element fixing materials such as adhesives for semiconductor element fixing materials.
• Semiconductor elements include light-emitting elements such as lasers and light-emitting diodes (LEDs), optical semiconductor elements such as light-receiving elements such as solar cells, transistors, sensors such as temperature sensors and pressure sensors, and integrated circuits.
• LEDs light-emitting elements
• LEDs light-emitting diodes
• optical semiconductor elements such as light-receiving elements such as solar cells
• transistors transistors
• sensors such as temperature sensors and pressure sensors, and integrated circuits.
• a semiconductor element adhesive paste for fixing a semiconductor element is usually applied to an object to be applied, for example, a substrate such as a lead frame using a coating device having a discharge pipe (needle) as described in Patent Document 1.
• a coating apparatus having such a discharge pipe for example, the discharge pipe descends vertically to approach the object to be coated, and after discharging a predetermined amount of adhesive paste from the tip of the discharge pipe, the discharge pipe rises to the object to be coated. As the object is separated from the object, the object to be coated moves laterally. By repeating this operation, the semiconductor element adhesive paste is continuously applied to the object to be applied. After that, a semiconductor element is mounted (mounted) on the applied adhesive paste and adhered to the object to be applied.
• the semiconductor element is mounted on the applied adhesive paste immediately and adhered to the object to be applied.
• the applied adhesive paste may be left as it is for a long time without mounting the semiconductor element. In such a case, if the applied adhesive paste is left for a long time, the viscosity of the adhesive paste may change and the semiconductor element may not be mounted in a preferable state.
• the semiconductor element can be satisfactorily mounted on the adhesive paste, and the cured product obtained by heating at a high temperature can be obtained.
• Adhesive pastes with excellent adhesiveness are desired.
• optical parts and sensor chips used in semiconductor devices are susceptible to heat. Therefore, when the heat curing method is used as a method for curing the adhesive, it may be preferable to cure the adhesive at the lowest possible temperature from the viewpoint of avoiding the influence of heating on the optical parts and sensor chips.
• the present invention has been made in view of such circumstances, (i) Even after a long period of time after application to the object, it is possible to mount the semiconductor element satisfactorily (excellent chip mountability), and curing obtained by heating at a high temperature To provide an adhesive paste with excellent adhesion to objects, (ii) to provide an adhesive paste having excellent balance between chip mountability and adhesiveness of the resulting cured product under both high-temperature heating and low-temperature heating conditions; (iii) To provide a method of using these adhesive pastes as adhesives for semiconductor element fixing materials, and a method of manufacturing a semiconductor device using these adhesive pastes as adhesives for semiconductor element fixing materials. .
• heating at high temperature means “heating at 150 ° C. to 190 ° C.”
• heating at low temperature means “to heat at 80°C to 120°C”.
• excellent adhesiveness means “high adhesive strength”.
• the inventors have made extensive studies to solve the above problems. As a result, even after 20 minutes or more have passed since the adhesive paste was applied to the object to be coated, It was found that a semiconductor element can be satisfactorily mounted, and that the resulting cured product has excellent adhesiveness under both high-temperature heating and low-temperature heating conditions, and the present invention has been completed. rice field.
• the following adhesive pastes [1] to [12], the method of using the adhesive paste of [13], and the method of manufacturing a semiconductor device using the adhesive paste of [14] are provided.
• the viscosity at 25°C is 20,000 mPa ⁇ s or less.
• Requirement 2 It is a silane compound.
• thermosetting organopolysiloxane compound (A) is a polysilsesquioxane compound.
• the liquid component (L) is at least one selected from the group consisting of bifunctional silane compounds, trifunctional silane compounds and silicone oils.
• the solvent (S) contains an organic solvent (SL) having a boiling point of 100 ° C. or more and less than 254 ° C. of [1] to [3] Adhesive paste according to any one of the preceding claims.
• the mass reduction rate 170 ° C. 2h of the adhesive paste before and after heating is less than 55%. adhesive paste.
• the mass loss rate of the adhesive paste before and after heating is set to 170 ° C. for 2 hours, and the adhesive paste is heated at 100 ° C. for 2 hours.
• a method of using the adhesive paste according to any one of [1] to [12] as an adhesive for a semiconductor element fixing material comprising the steps (BI) and (BII) below.
• the chip mountability that enables good mounting of a semiconductor element and the adhesion of a cured product obtained by heating at a high temperature
• Adhesive pastes are provided that are compatible with the properties.
• an adhesive paste having excellent balance between chip mountability and adhesiveness of the obtained cured product under both high temperature heating and low temperature heating conditions.
• a method of using these adhesive pastes as adhesives for semiconductor element fixing materials and a method of manufacturing a semiconductor device using these adhesive pastes as adhesives for semiconductor element fixing materials. .
• the present invention will be described in detail below by dividing it into 1) adhesive paste, 2) method of using the adhesive paste, and method of manufacturing a semiconductor device using the adhesive paste.
• Adhesive paste is an adhesive paste containing a thermosetting organopolysiloxane compound (A) and a liquid component (L) that satisfies the following requirements 1 and 2, wherein the liquid component The content of (L) is 15% by mass or more relative to the total mass of the adhesive paste, and the tack-free time of the adhesive paste is 20 minutes or longer.
• the viscosity at 25°C is 20,000 mPa ⁇ s or less.
• Requirement 2 It is a silane compound.
• the "adhesive paste” means "a viscous liquid at room temperature (23°C) and in a fluid state”. Since the adhesive paste of the present invention has the properties described above, it is excellent in workability in the coating process.
• excellent workability in the coating process means “in the coating process, when the adhesive paste is discharged from the discharge pipe and then the discharge pipe is pulled up, the amount of stringiness is small or is interrupted immediately, and the resin It must not contaminate the surroundings due to splashing or spread of droplets after application.”
• the adhesive paste of the present invention has a tack-free time of 20 minutes or longer, preferably 30 minutes or longer, more preferably 50 minutes or longer, and particularly preferably 70 minutes or longer.
• the tack-free time is 20 minutes or longer, the adhesive paste has excellent chip mountability.
• the tack-free time can be measured by the method described in Examples.
• the adhesive paste of the present invention contains a thermosetting organopolysiloxane compound (A) (hereinafter sometimes referred to as "component (A)"). Since the adhesive paste of the present invention contains the component (A), it becomes easy to obtain a cured product with excellent adhesiveness under both high-temperature heating and low-temperature heating conditions.
• component (A) thermosetting organopolysiloxane compound
• thermosetting organopolysiloxane compound (A) of the present invention is a compound having a carbon-silicon bond and a siloxane bond (--Si--O--Si--) in its molecule.
• the component (A) is preferably solid at 25° C. from the viewpoint of easily obtaining an adhesive paste that easily exhibits excellent adhesive performance.
• component (A) is a thermosetting compound, at least one functional group selected from the group consisting of functional groups capable of condensation reaction by heating and functional groups capable of condensation reaction through hydrolysis It is preferred to have a group.
• thermosetting organopolysiloxane compound (A) is not particularly limited, and may be linear, ladder-like, or cage-like.
• the structure represented by the following formula (a-1) is used as the linear main chain structure
• the structure represented by the following formula (a-2) is used as the ladder-like main chain structure.
• the main chain structure include structures represented by the following formula (a-3).
• Rx, Ry, and Rz each independently represent a hydrogen atom or an organic group, and the organic group includes an unsubstituted or substituted alkyl group, an unsubstituted A substituted or substituted cycloalkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted aryl group, or an alkylsilyl group is preferred.
• the plurality of Rx in formula (a-1), the plurality of Ry in formula (a-2), and the plurality of Rz in formula (a-3) may be the same or different. However, both Rx in formula (a-1) are not hydrogen atoms.
• alkyl group of the unsubstituted or substituted alkyl group examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, C1-C10 alkyl groups such as n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, n-heptyl group and n-octyl group can be mentioned.
• cycloalkyl groups of unsubstituted or substituted cycloalkyl groups include cycloalkyl groups having 3 to 10 carbon atoms such as cyclobutyl group, cyclopentyl group, cyclohexyl group and cycloheptyl group.
• Alkenyl groups of unsubstituted or substituted alkenyl groups include, for example, vinyl group, 1-propenyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, and the like. Ten alkenyl groups are mentioned.
• substituents of the alkyl group, cycloalkyl group and alkenyl group include halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; a hydroxyl group; a thiol group; an epoxy group; a glycidoxy group; unsubstituted or substituted aryl groups such as phenyl group, 4-methylphenyl group and 4-chlorophenyl group; and the like.
• aryl groups of unsubstituted or substituted aryl groups include aryl groups having 6 to 10 carbon atoms such as phenyl group, 1-naphthyl group and 2-naphthyl group.
• the substituents of the aryl group include halogen atoms such as fluorine, chlorine, bromine and iodine atoms; alkyl groups having 1 to 6 carbon atoms such as methyl and ethyl groups; 1 to 6 alkoxy groups; nitro group; cyano group; hydroxyl group; thiol group; epoxy group; glycidoxy group; (meth) acryloyloxy group; an aryl group having a substituent; and the like.
• the alkylsilyl group includes trimethylsilyl group, triethylsilyl group, triisopropylsilyl group, tri-t-butylsilyl group, methyldiethylsilyl group, dimethylsilyl group, diethylsilyl group, methylsilyl group, ethylsilyl group and the like.
• Rx, Ry, and Rz are preferably a hydrogen atom, an unsubstituted or substituted C 1-6 alkyl group, or a phenyl group, and an unsubstituted or substituted C 1-6 Alkyl groups are particularly preferred.
• thermosetting organopolysiloxane compound (A) can be obtained, for example, by a known production method of polycondensing a silane compound having a hydrolyzable functional group (alkoxy group, halogen atom, etc.).
• the silane compound to be used may be appropriately selected according to the desired structure of the thermosetting organopolysiloxane compound (A).
• Preferred specific examples include bifunctional silane compounds such as dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, and diethyldiethoxysilane; methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-butyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyldiethoxymethoxysilane, etc.
• a trifunctional silane compound of Tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetra-t-butoxysilane, tetra-s-butoxysilane, methoxytriethoxysilane, dimethoxydiethoxysilane, trimethoxyethoxysilane tetrafunctional silane compounds such as silane; and the like.
• the mass average molecular weight (Mw) of the thermosetting organopolysiloxane compound (A) is usually 800 or more and 30,000 or less, preferably 1,000 or more and 20,000 or less, more preferably 1,200 or more and 15,000 or less. , particularly preferably 3,000 or more and 10,000 or less.
• the molecular weight distribution (Mw/Mn) of the thermosetting organopolysiloxane compound (A) is not particularly limited, it is usually 1.0 or more and 10.0 or less, preferably 1.1 or more and 6.0 or less.
• Mw/Mn molecular weight distribution
• the mass average molecular weight (Mw) and number average molecular weight (Mn) of the thermosetting organopolysiloxane compound (A) are, for example, gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent, in terms of standard polystyrene. can be obtained as a value.
• GPC gel permeation chromatography
• THF tetrahydrofuran
• thermosetting organopolysiloxane compound (A) of the present invention is preferably a polysilsesquioxane compound obtained by polycondensation of a trifunctional organosilane compound. Since the adhesive paste of the present invention contains a polysilsesquioxane compound as the component (A), it becomes easy to obtain a cured product with excellent adhesiveness under both high-temperature heating and low-temperature heating conditions. .
• the polysilsesquioxane compound of the present invention is a compound having a repeating unit represented by the following formula (a-4).
• the adhesive paste of the present invention contains, as the component (A), a polysilsesquioxane compound having a repeating unit represented by the following formula (a-4), so that the adhesive paste can be heated under either high temperature heating or low temperature heating conditions. Also in, it becomes easy to obtain a cured product having excellent adhesiveness.
• R 1 represents an organic group.
• organic groups include unsubstituted alkyl groups, substituted alkyl groups, unsubstituted cycloalkyl groups, substituted cycloalkyl groups, unsubstituted alkenyl groups, substituted alkenyl groups, and unsubstituted aryl groups.
• aryl groups having substituents and groups selected from the group consisting of alkylsilyl groups, unsubstituted alkyl groups having 1 to 10 carbon atoms, substituted alkyl groups having 1 to 10 carbon atoms, unsubstituted
• a group selected from the group consisting of a substituted C6-C12 aryl group and a C6-C12 aryl group having a substituent is more preferred.
• the "unsubstituted alkyl group having 1 to 10 carbon atoms” includes methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, n- pentyl group, n-hexyl group, n-octyl group, n-nonyl group, n-decyl group and the like.
• the number of carbon atoms in the “unsubstituted alkyl group having 1 to 10 carbon atoms” represented by R 1 is preferably 1 to 6, more preferably 1 to 3.
• the number of carbon atoms in the “substituted alkyl group having 1 to 10 carbon atoms” represented by R 1 is preferably 1 to 6, more preferably 1 to 3. In addition, this number of carbon atoms means the number of carbon atoms in the portion (alkyl group portion) excluding the substituents. Therefore, when R 1 is a “substituted alkyl group having 1 to 10 carbon atoms”, the number of carbon atoms in R 1 may exceed 10 in some cases. Examples of the alkyl group of the "substituted alkyl group having 1 to 10 carbon atoms" include the same groups as the "unsubstituted alkyl group having 1 to 10 carbon atoms".
• substituents of the "substituted alkyl group having 1 to 10 carbon atoms” include halogen atoms such as fluorine, chlorine and bromine atoms; cyano groups; groups represented by the formula: OG;
• the number of substituent atoms in the "substituted alkyl group having 1 to 10 carbon atoms" (excluding the number of hydrogen atoms) is generally 1 to 30, preferably 1 to 20.
• G represents a hydroxyl-protecting group.
• the hydroxyl-protecting group is not particularly limited, and includes known protecting groups known as hydroxyl-protecting groups.
• acyl group silyl group such as trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, t-butyldiphenylsilyl group; methoxymethyl group, methoxyethoxymethyl group, 1-ethoxyethyl group, tetrahydropyran-2- acetal group such as yl group and tetrahydrofuran-2-yl group; alkoxycarbonyl group such as t-butoxycarbonyl group; methyl group, ethyl group, t-butyl group, octyl group, allyl group, triphenylmethyl group, benzyl group, ethers such as p-methoxybenzyl group, fluorenyl group, trityl group and benzhydryl group;
• Examples of the “unsubstituted aryl group having 6 to 12 carbon atoms” include phenyl group, 1-naphthyl group, 2-naphthyl group and the like.
• the number of carbon atoms in the “unsubstituted aryl group having 6 to 12 carbon atoms” represented by R 1 is preferably 6.
• the number of carbon atoms in the "substituted aryl group having 6 to 12 carbon atoms" represented by R 1 is preferably 6.
• the number of carbon atoms means the number of carbon atoms in the portion (aryl group portion) excluding the substituents. Therefore, when R 1 is a “substituted aryl group having 6 to 12 carbon atoms”, the number of carbon atoms in R 1 may exceed 12 in some cases.
• Examples of the aryl group of the "substituted aryl group having 6 to 12 carbon atoms” include the same aryl groups as the "unsubstituted aryl group having 6 to 12 carbon atoms".
• substituents of the "substituted aryl group having 6 to 12 carbon atoms” include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group and t-butyl.
• Alkyl groups such as group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group; halogen atoms such as fluorine atom, chlorine atom and bromine atom; alkoxy such as methoxy group and ethoxy group group; and the like.
• the number of substituent atoms (excluding the number of hydrogen atoms) of the "substituted C6-C12 aryl group” is usually 1-30, preferably 1-20.
• R 1 is an unsubstituted alkyl group having 1 to 10 carbon atoms, a fluorine atom, from the viewpoint of easily obtaining a polysilsesquioxane compound with a stable structure and more stable performance as an adhesive paste. and an unsubstituted aryl group having 6 to 12 carbon atoms.
• R 1 is an alkyl group having 1 to 10 carbon atoms and having a fluorine atom
• an adhesive paste or cured product having a long tack-free time and a low refractive index can be easily obtained. It becomes easy to be suitably used for an optical semiconductor device that requires a low refractive index.
• the alkyl group having 1 to 10 carbon atoms and having a fluorine atom a group represented by the composition formula: C m H (2m ⁇ n+1) F n (m is an integer of 1 to 10, n is 1 or more, (2m+1) are the following integers).
• a 3,3,3-trifluoropropyl group is preferred.
• the content ratio of the repeating unit represented by the formula (a-4) (that is, the T site described later) in the polysilsesquioxane compound is usually 50 to 100 mol% of the total repeating units, and 70 It is more preferably up to 100 mol %, still more preferably 90 to 100 mol %, and particularly preferably 100 mol %.
• the content ratio of the repeating unit (T site) represented by the formula (a-4) in the polysilsesquioxane compound is, for example, 29 Si- when NMR peak assignment and area integration are possible. It can be determined by measuring NMR and 1 H-NMR.
• Polysilsesquioxane compounds include ketone solvents such as acetone; aromatic hydrocarbon solvents such as benzene; sulfur-containing solvents such as dimethylsulfoxide; ether solvents such as tetrahydrofuran; ester solvents such as ethyl acetate; soluble in various organic solvents such as halogen-containing solvents such as; and mixed solvents comprising two or more of these. Therefore, these solvents can be used to measure the 29 Si-NMR of the polysilsesquioxane compound in solution.
• the repeating unit represented by the formula (a-4) is preferably represented by the following formula (a-5).
• the polysilsesquioxane compound has three oxygen atoms bonded to a silicon atom, generally collectively referred to as the T site, and one other group (R 1 ). It has a partial structure formed by bonding.
• R 1 has the same meaning as R 1 in formula (a-4).
• * represents a Si atom, a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and at least one of the three * is a Si atom.
• the alkyl group having 1 to 10 carbon atoms of * include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group and t-butyl group.
• a plurality of * may all be the same or different.
• the polysilsesquioxane compound is a thermosetting compound, and is a compound capable of undergoing condensation reaction and/or hydrolysis by heating. Therefore, at least one of * in the above formula (a-5) of the plurality of repeating units (T sites) possessed by the polysilsesquioxane compound is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. is preferred, and a hydrogen atom is more preferred.
• the hydrogen atom or the number of carbon atoms in * in the above formula (a-5) is 1 to 1 It is possible to confirm the presence of 10 alkyl groups and whether or not the three * in the above formula (a-5) are all Si atoms in the repeating unit. Furthermore, when assignment of 29 Si-NMR peaks and integration of areas are possible, with respect to the total number of repeating units (T sites) represented by the formula (a-4) in the polysilsesquioxane compound, The total number of repeating units in which all three * in the formula (a-5) are Si atoms can be roughly calculated.
• the total number is preferably 30 to 95 mol %, more preferably 40 to 90 mol %, from the viewpoint of easily obtaining an adhesive paste that gives a cured product with excellent heat resistance.
• the polysilsesquioxane compound may have one type of R 1 (homopolymer) or may have two or more types of R 1 (copolymer).
• the polysilsesquioxane compound when the polysilsesquioxane compound is a copolymer, the polysilsesquioxane compound may be any of random copolymers, block copolymers, graft copolymers, alternating copolymers, and the like. , random copolymers are preferred from the viewpoint of ease of production.
• the structure of the polysilsesquioxane compound may be any one of a ladder structure, a double decker structure, a cage structure, a partially cleaved cage structure, a cyclic structure, and a random structure.
• polysilsesquioxane compounds can be used singly or in combination of two or more.
• the method for producing the polysilsesquioxane compound is not particularly limited.
• the following formula (a-6) is not particularly limited.
• the following formula (a-6) is not particularly limited.
• the following formula (a-6) is not particularly limited.
• R 1 has the same meaning as R 1 in the formula (a-4), R 2 represents an alkyl group having 1 to 10 carbon atoms, X 1 represents a halogen atom, p is 0 to represents an integer of 3. Multiple R 2 and multiple X 1 may be the same or different.
• a polysilsesquioxane compound can be produced by polycondensing at least one of the silane compounds (1) represented by. Examples of the alkyl group having 1 to 10 carbon atoms for R 2 include the same groups as the alkyl group having 1 to 10 carbon atoms represented by * in the above formula (a-5). A chlorine atom, a bromine atom, etc. are mentioned as a halogen atom of X1.
• silane compound (1) examples include alkyltrialkoxysilane compounds such as methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, and ethyltripropoxysilane; alkylhalogenoalkoxysilane compounds such as methylchlorodimethoxysilane, methylchlorodiethoxysilane, methyldichloromethoxysilane, methylbromodimethoxysilane, ethylchlorodimethoxysilane, ethylchlorodiethoxysilane, ethyldichloromethoxysilane, ethylbromodimethoxysilane; Alkyltrihalogenosilane compounds such as methyltrichlorosilane, methyltribromosilane, ethyltrichlorosilane, ethyltribromodime
• substituted alkyltrialkoxysilane compounds such as 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 2-cyanoethyltrimethoxysilane, 2-cyanoethyltriethoxysilane; 3,3,3-trifluoropropylchlorodimethoxysilane, 3,3,3-trifluoropropylchlorodiethoxysilane, 3,3,3-trifluoropropyldichloromethoxysilane, 3,3,3-trifluoropropyldichloro substituted alkylhalogenoalkoxysilane compounds such as ethoxysilane, 2-cyanoethylchlorodimethoxysilane, 2-cyanoethylchlorodiethoxysilane, 2-cyanoethyldichloromethoxysilane, 2-cyanoethyldichloroethoxys
• Phenyltrialkoxysilane compounds with or without substituents such as phenyltrimethoxysilane, 4-methoxyphenyltrimethoxysilane; phenylhalogenoalkoxysilane compounds with or without substituents, such as phenylchlorodimethoxysilane, phenyldichloromethoxysilane, 4-methoxyphenylchlorodimethoxysilane, 4-methoxyphenyldichloromethoxysilane; phenyltrihalogenosilane compounds with or without substituents, such as phenyltrichlorosilane and 4-methoxyphenyltrichlorosilane; and the like.
• These silane compounds (1) can be used singly or in combination of two or more.
• the method of polycondensing the silane compound (1) is not particularly limited.
• a method of adding a predetermined amount of a polycondensation catalyst to the silane compound (1) in a solvent or without a solvent and stirring the mixture at a predetermined temperature can be used. More specifically, (a) a method of adding a predetermined amount of an acid catalyst to the silane compound (1) and stirring at a predetermined temperature; (b) adding a predetermined amount of a base catalyst to the silane compound (1); (c) adding a predetermined amount of an acid catalyst to the silane compound (1) and stirring at a predetermined temperature; and then adding an excess amount of a base catalyst to make the reaction system basic. , a method of stirring at a predetermined temperature, and the like. Among these, the method (a) or (c) is preferable because the desired polysilsesquioxane compound can be obtained efficiently.
• the polycondensation catalyst to be used may be either an acid catalyst or a base catalyst. Two or more polycondensation catalysts may be used in combination, but at least an acid catalyst is preferably used.
• Acid catalysts include inorganic acids such as phosphoric acid, hydrochloric acid, boric acid, sulfuric acid and nitric acid; organic acids such as citric acid, acetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid and p-toluenesulfonic acid; is mentioned. Among these, at least one selected from phosphoric acid, hydrochloric acid, boric acid, sulfuric acid, citric acid, acetic acid, and methanesulfonic acid is preferred.
• Base catalysts include aqueous ammonia; trimethylamine, triethylamine, lithium diisopropylamide, lithium bis(trimethylsilyl)amide, pyridine, 1,8-diazabicyclo[5.4.0]-7-undecene, aniline, picoline, 1,4- Organic bases such as diazabicyclo[2.2.2]octane and imidazole; Organic salt hydroxides such as tetramethylammonium hydroxide and tetraethylammonium hydroxide; sodium methoxide, sodium ethoxide, sodium t-butoxide, potassium t-butoxide Metal alkoxides such as; Metal hydrides such as sodium hydride and calcium hydride; Metal hydroxides such as sodium hydroxide, potassium hydroxide and calcium hydroxide; Metal carbonates such as sodium carbonate, potassium carbonate and magnesium carbonate; metal hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate;
• the amount of the polycondensation catalyst used is usually in the range of 0.05 to 10 mol%, preferably 0.1 to 5 mol%, relative to the total mol amount of the silane compound (1).
• the solvent to be used can be appropriately selected according to the type of silane compound (1).
• the solvent to be used can be appropriately selected according to the type of silane compound (1).
• water aromatic hydrocarbons such as benzene, toluene and xylene; esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate and methyl propionate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone.
• alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, s-butyl alcohol and t-butyl alcohol; These solvents can be used singly or in combination of two or more. Further, when the above method (c) is employed, after the polycondensation reaction is carried out in an aqueous system in the presence of an acid catalyst, an organic solvent and a base catalyst (such as aqueous ammonia) are added to the reaction solution, and neutral conditions are obtained. Alternatively, a polycondensation reaction may be further performed under basic conditions.
• the amount of the solvent used is usually 0.001 liters or more and 10 liters or less, preferably 0.01 liters or more and 0.9 liters or less per 1 mol of the total molar amount of the silane compound (1).
• the temperature at which the silane compound (1) is polycondensed is usually in the range of 0°C to the boiling point of the solvent used, preferably 20°C or higher and 100°C or lower, more preferably 30°C or higher and 95°C or lower. If the reaction temperature is too low, the polycondensation reaction may proceed insufficiently. On the other hand, if the reaction temperature is too high, it becomes difficult to suppress gelation. The reaction is usually completed in 30 minutes to 30 hours.
• a monomer in which R 1 is an alkyl group having a fluorine atom tends to be less reactive than a monomer in which R 1 is a normal alkyl group.
• a polysilsesquioxane compound having a desired molecular weight can be easily obtained by reducing the amount of catalyst and conducting the reaction under mild conditions for a long time.
• an aqueous alkali solution such as sodium hydrogen carbonate is added to the reaction solution
• an acid such as hydrochloric acid is added to the reaction solution.
• the resulting salt is removed by filtration or washing with water to obtain the intended polysilsesquioxane compound.
• the portion of OR 2 or X 1 of the silane compound (1) that did not undergo hydrolysis and the subsequent condensation reaction is the polysilsesquioxane compound remain inside.
• the curing proceeds by the condensation reaction.
• the adhesive paste containing the polysilsesquioxane compound of the present invention contains substantially no noble metal catalyst or contains only a small amount of noble metal catalyst.
• substantially contains no noble metal catalyst or has a low noble metal catalyst content means that "a component that can be interpreted as a noble metal catalyst is not intentionally added, and an effective It means that the content of the noble metal catalyst is, for example, less than 1 ppm by mass in terms of the mass of the catalytic metal element with respect to the amount of the components.
• active ingredient refers to "a component excluding the solvent (S) (described later) contained in the adhesive paste”.
• the adhesive paste does not substantially contain a noble metal catalyst, or contains a noble metal catalyst, from the viewpoint of stable production in consideration of formulation variations, etc., storage stability, and the viewpoint that noble metal catalysts are expensive. is preferably less.
• liquid component (L) The liquid component (L) (hereinafter sometimes referred to as "(L) component") that constitutes the adhesive paste of the present invention satisfies requirements 1 and 2 below.
• (L) component The viscosity at 25°C is 20,000 mPa ⁇ s or less.
• (L) component It is a silane compound. Being a silane-based compound, the liquid component (L) is easily mixed well with the component (A), making it easy to obtain an adhesive paste with stable performance.
• Examples of the liquid component (L) satisfying Requirement 1 and Requirement 2 above include bifunctional silane-based compounds, trifunctional silane-based compounds, polyfunctional silane-based compounds, and silicone oils.
• the viscosity of the liquid component (L) at 25° C. is 20,000 mPa ⁇ s or less, preferably 10,000 mPa ⁇ s or less, more preferably 7,000 mPa ⁇ s or less, and particularly preferably 5,000 mPa ⁇ s. It is below.
• An adhesive paste containing a liquid component (L) having a viscosity at 25° C. equal to or lower than the above upper limit value is less likely to volatilize at room temperature (20° C. ⁇ 15° C.), making it easier to obtain an adhesive paste with a long tack-free time.
• an adhesive paste containing a high-viscosity liquid component (L) whose viscosity at 25° C.
• the above upper limit has a high viscosity, so that the tack-free time of the adhesive paste may be shortened. By being below, the possibility can be reduced. Further, by containing the liquid component (L) having a viscosity at 25° C. of not more than the above upper limit value, workability in the coating process is excellent, and adhesiveness, It becomes easy to obtain an adhesive paste that gives an excellent cured product due to heat resistance and crack suppression of the cured product.
• the phrase "excellent crack suppression of the cured product” means that "when the adhesive paste is heated to obtain a cured product, cracking does not occur in the cured product due to temperature changes".
• Bifunctional silane compounds include dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxymethylphenylsilane, diethoxymethylphenylsilane, and 3-glycide.
• xypropylmethyldimethoxysilane 3-glycidoxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyl dimethoxysilane, 3-mercaptopropylmethyldimethoxysilane and the like.
• a commercial item can also be used as a bifunctional silane-type compound.
• Examples of commercially available products include KBM series such as KBM-22, KBM-202SS and KBM-402, and KBE series such as KBE-22, KBE-402 and KBE-502 (manufactured by Shin-Etsu Chemical Co., Ltd.). be done.
• KBM-202SS can be preferably used from the viewpoint of being easily mixed well with other active ingredients and easily obtaining an adhesive paste with stable performance.
• Trifunctional silane compounds include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyltrimethoxysilane, n -butyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyldiethoxymethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane Silane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyl
• a commercial item can also be used as a trifunctional silane-type compound.
• Commercial products include, for example, KBM series such as KBM-103, KBM-303, KBM-503, KBM-5103; KBE series such as KBE-13, KBE-103, KBE-9007N; and X-12-967C ( (manufactured by Shin-Etsu Chemical Co., Ltd.).
• KBM series such as KBM-103, KBM-303, KBM-503, KBM-5103
• KBE series such as KBE-13, KBE-103, KBE-9007N
• X-12-967C, KBM-103, KBM-503, KBM-5103, and KBE-9007N are selected from the viewpoint of being easily mixed with other active ingredients and easily obtaining an adhesive paste with stable performance.
• X-12-967C, KBM-5103 and KBE-9007N are particularly preferably used.
• polyfunctional silane-based compounds include compounds having nitrogen atoms in the molecule and having 4 or more alkoxy groups bonded to silicon atoms in the molecule, and compounds having an organic main chain with an organic functional group and silicon Examples thereof include compounds having 4 or more alkoxy groups bonded to atoms. Having 4 or more silicon-bonded alkoxy groups means that the total number of alkoxy groups bonded to the same silicon atom and alkoxy groups bonded to different silicon atoms is 4 or more.
• polyfunctional silane-based compounds having nitrogen atoms in the molecule and having 4 or more alkoxy groups bonded to silicon atoms in the molecule include isocyanurate-based compounds and urea-based compounds.
• isocyanurate-based compounds examples include compounds represented by the following formula (l-1), and examples of urea-based compounds include compounds represented by the following formula (l-2).
• R a represents an alkoxy group having 1 to 6 carbon atoms such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy and t-butoxy.
• a plurality of R a may be the same or different.
• Each of t1 to t5 independently represents an integer of 1 to 10, preferably an integer of 1 to 6, and particularly preferably 3.
• Specific examples of the compound represented by formula (l-1) include 1,3,5-N-tris(3-trimethoxysilylpropyl) isocyanurate, 1,3,5-N-tris(3-tri ethoxysilylpropyl) isocyanurate, 1,3,5-N-tris(3-tri-i-propoxysilylpropyl) isocyanurate, 1,3,5-N-tris(3-tributoxysilylpropyl) isocyanurate, etc.
• Specific examples of the compound represented by formula (l-2) include N,N'-bis(3-trimethoxysilylpropyl)urea, N,N'-bis(3-triethoxysilylpropyl)urea, N , N'-bis(3-tripropoxysilylpropyl)urea, N,N'-bis(3-tributoxysilylpropyl)urea, N,N'-bis(2-trimethoxysilylethyl)urea, etc.
• N'-bis[(tri(C1-C6)alkoxysilyl)(C1-C10)alkyl]urea N,N'-bis(3-dimethoxymethylsilylpropyl)urea, N,N'-bis(3-dimethoxyethylsilylpropyl)urea, N,N'-bis(3-diethoxymethylsilylpropyl)urea, etc.
• KBM-9659 manufactured by Shin-Etsu Chemical Co., Ltd.
• KBM-9659 can be preferably used from the viewpoint that it is easily mixed with other active ingredients and an adhesive paste with stable performance is easily obtained.
• X-12-1048 can be used as the compound having an organic main chain and having 4 or more organic functional groups and silicon-bonded alkoxy groups.
• Commercially available products include, for example, X-12-1048, X-12-981S, X-12-1159L (manufactured by Shin-Etsu Chemical Co., Ltd.).
• X-12-1159L can be preferably used from the viewpoint that it is easily mixed with other active ingredients and an adhesive paste with stable performance is easily obtained.
• Silicone oil includes straight silicone oil and modified silicone oil.
• a straight silicone oil is a straight-chain polymer compound composed of siloxane bonds, and includes dimethylsilicone oil, methylphenylsilicone oil, and methylhydrogensilicone oil.
• Modified silicone oil is obtained by introducing an organic group to the side chain or end of polysiloxane.
• Modified silicone oils are classified into side-chain type, double-end type, single-end type, and side-chain double-end type according to the bonding position of the introduced organic group.
• organic groups include amino groups, epoxy groups, methacryl groups, acryl groups, silanol groups, and carboxyl groups.
• a commercial item can also be used as silicone oil.
• examples of commercially available straight silicone oils include KF-96L series, KF-50 series, and KF-99 series (manufactured by Shin-Etsu Chemical Co., Ltd.).
• commercially available modified silicone oils include, for example, the KF series such as KF-868 in which a monoamine is introduced in the side chain, X-22-2445 in which an acrylic group is introduced at both ends, and an epoxy group at one end.
• X-22-173 series such as the introduced X-22-173BX (manufactured by Shin-Etsu Chemical Co., Ltd.), XF42-334 (manufactured by Momentive Performance Materials Japan), and the like.
• modified silicone oils can be preferably used, and X-22-2445 and XF42-334 are particularly preferable, from the viewpoint of being easily mixed well with other active ingredients and easily obtaining an adhesive paste with stable performance. can be used.
• liquid component (L) bifunctional silane compounds, trifunctional silane compounds, and silicone oils are more preferable, and bifunctional silane compounds, silicone Oils are particularly preferred, and trifunctional silane-based compounds and silicone oils are particularly preferred from the standpoint of easily obtaining an adhesive paste having excellent adhesive strength when cured by heating at a low temperature.
• the liquid component (L) may be used singly or in combination of two or more.
• the content of the liquid component (L) is 15% by mass or more, preferably 17% by mass or more and less than 50% by mass, and 19% by mass or more and less than 40% by mass, relative to the total mass of the adhesive paste. is more preferable, and 21% by mass or more and less than 35% by mass is particularly preferable.
• the adhesive paste of the present invention contains a thermosetting organopolysiloxane compound (A) and a liquid component (L), but may contain the following components.
• Solvent (S) The solvent (S) contained in the adhesive paste of the present invention is not particularly limited as long as it can dissolve or disperse the components of the adhesive paste of the present invention.
• the solvent (S) preferably contains an organic solvent (SL) having a boiling point of 100°C or higher and lower than 254°C.
• “boiling point” refers to "boiling point at 1013 hPa" (same in this specification).
• the boiling point of the organic solvent (SL) is 100°C or higher and lower than 254°C, preferably 100°C or higher and lower than 200°C, more preferably 105°C or higher and lower than 185°C, and 110°C or higher and lower than 170°C. It is particularly preferred to have
• Such an organic solvent (SL) evaporates efficiently when heated at a low temperature compared to a high boiling point organic solvent having a boiling point of 254° C. or more and 300° C. or less. Therefore, by including the organic solvent (SL) as the solvent (S), it becomes easier to obtain an adhesive paste having a mass reduction rate of 170° C. 2h ⁇ mass reduction rate of 100° C. 2h (described later) of less than 14%.
• such an organic solvent (SL) has a relatively slow volatilization rate compared to low boiling point organic solvents having a boiling point of less than 100°C.
• organic solvent examples include diethylene glycol monobutyl ether acetate (boiling point 247° C.), dipropylene glycol-n-butyl ether (boiling point 229° C.), dipropylene glycol methyl ether acetate (boiling point 209° C.), and diethylene glycol butyl methyl ether.
• organic solvent (SL) diethylene glycol monoethyl ether acetate and cyclohexanone are used as the organic solvent (SL) from the viewpoint that the effect of using the organic solvent (SL) can be further exhibited and the active ingredient can be easily mixed well.
• Preferred is cyclohexanone.
• the organic solvent (SL) may be used singly or in combination of two or more.
• the content of the organic solvent (SL) in the adhesive paste of the present invention is preferably 10% by mass or more and 50% by mass or less, and 13% by mass or more and 40% by mass or less, relative to the total mass of the adhesive paste. is more preferable, and it is particularly preferable to be 15% by mass or more and 30% by mass or less.
• excellent workability in the step of filling the syringe with the adhesive paste means “capable of filling an appropriate amount into the syringe without air bubbles”.
• the adhesive paste of the present invention may contain solvents other than the organic solvent (SL).
• a solvent other than the organic solvent (SL) an organic solvent having a boiling point of 254° C. or more and 300° C. or less (hereinafter sometimes referred to as “organic solvent (SH)”) is preferable.
• the organic solvent (SH) is not particularly limited as long as it has a boiling point of 254° C. or more and 300° C. or less and can dissolve or disperse the components of the adhesive paste of the present invention.
• the temperature range for heating the adhesive paste to obtain a cured product can be adjusted more precisely. It is possible to reduce the influence of heating on parts and sensor chips.
• organic solvent examples include tripropylene glycol-n-butyl ether (boiling point 274° C.), 1,6-hexanediol diacrylate (boiling point 260° C.), diethylene glycol dibutyl ether (boiling point 256° C.), triethylene glycol butyl methyl ether (boiling point 261° C.), polyethylene glycol dimethyl ether (boiling point 264-294° C.), tetraethylene glycol dimethyl ether (boiling point 275° C.), polyethylene glycol monomethyl ether (boiling point 290-310° C.) and the like.
• organic solvent (SH) tripropylene glycol-n-butyl ether, 1,6-hexanediol diol diol, from the viewpoint of more easily obtaining the effect of using the organic solvent (SL) and the organic solvent (SH) in combination.
• Acrylates are preferred.
• organic solvent (SL) and an organic solvent (SH) When using an organic solvent (SL) and an organic solvent (SH) together, specifically, a combination of diethylene glycol monoethyl ether acetate (organic solvent (SL)) and tripropylene glycol-n-butyl ether (organic solvent (SH)) , a combination of cyclohexanone (organic solvent (SL)) and tripropylene glycol-n-butyl ether (organic solvent (SH)), diethylene glycol monoethyl ether acetate (organic solvent (SL)) and 1,6-hexanediol diacrylate (organic A combination of cyclohexanone (organic solvent (SL)) and 1,6-hexanediol diacrylate (organic solvent (SH)) is preferred.
• the organic solvent (SL) accounts for preferably 60% by mass or more, more preferably 65% by mass or more, and particularly preferably 70% by mass or more, of the entire solvent (S). By using the organic solvent (SL) in the entire solvent (S) within the above range, the effect of using the organic solvent (SL) can be further expressed.
• the adhesive paste of the present invention preferably contains the solvent (S) in such an amount that the solid content concentration is preferably 50% by mass or more and 90% by mass or less, more preferably 70% by mass or more and 90% by mass or less.
• the solid content concentration is within this range, it is easy to mix the active ingredient well, the workability in the process of filling the adhesive paste into the syringe and the coating process is excellent, and the effect of using the organic solvent (SL) is more expressed. can be made.
• the solvent (S) in such an amount that the solid content concentration is preferably 50% by mass or more and 90% by mass or less, more preferably 70% by mass or more and 90% by mass or less.
• the adhesive paste of the present invention may contain fine particles as the component (B).
• the fine particles include fine particles (B1) having an average primary particle diameter of 5 nm or more and 40 nm or less (hereinafter sometimes referred to as “component (B1)”) and fine particles (B2) having an average primary particle diameter of more than 0.04 ⁇ m and not more than 8 ⁇ m. (hereinafter sometimes referred to as "(B2) component").
• the average primary particle size of the fine particles (B1) is preferably 5 nm or more and 30 nm or less, more preferably 5 nm or more and 20 nm or less.
• the average primary particle size of fine particles (B1) can be obtained by observing the shape of fine particles using a transmission electron microscope.
• the specific surface area of the fine particles (B1) is preferably 10 m 2 /g or more and 500 m 2 /g or less, more preferably 20 m 2 /g or more and 300 m 2 /g or less. When the specific surface area is within the above range, it becomes easier to obtain an adhesive paste with superior workability in the coating process.
• the specific surface area can be determined by the BET multipoint method.
• the shape of the fine particles (B1) may be spherical, chain-like, needle-like, plate-like, flake-like, rod-like, fiber-like, etc., but is preferably spherical.
• spherical means “generally spherical, as well as nearly spherical, including polyhedral shapes that can be approximated to spheres such as spheroids, ovoids, confetti-like, and cocoon-like".
• the components of the fine particles (B1) are not particularly limited, and include metals, metal oxides, minerals, metal carbonates, metal sulfates, metal hydroxides, metal silicates, inorganic components, organic components, silicones, and the like. mentioned. Further, the fine particles (B1) to be used may have a modified surface.
• Metals are group 1 (excluding H), groups 2 to 11, group 12 (excluding Hg), group 13 (excluding B), group 14 (excluding C and Si), group 15 (excluding C and Si) in the periodic table.
• metal oxides examples include titanium oxide, alumina, boehmite, chromium oxide, nickel oxide, copper oxide, zirconium oxide, indium oxide, zinc oxide, and composite oxides thereof.
• the fine particles of metal oxides also include sol particles composed of these metal oxides.
• Minerals include smectite, bentonite, and the like.
• smectites include montmorillonite, beidellite, hectorite, saponite, stevensite, nontronite, and sauconite.
• metal carbonates include calcium carbonate, magnesium carbonate, etc.
• metal sulfates include calcium sulfate, barium sulfate, etc.
• metal hydroxides include aluminum hydroxide, etc.
• metal silicates include aluminum silicate, Examples include calcium silicate and magnesium silicate.
• silica etc. are mentioned as an inorganic component. Examples of silica include dry silica, wet silica, surface-modified silica (surface-modified silica), and the like. Organic components include acrylic polymers and the like.
• Silicone means an artificial polymer compound with a main skeleton made up of siloxane bonds. Examples include dimethylpolysiloxane, diphenylpolysiloxane, and methylphenylpolysiloxane.
• Fine particles (B1) can be used singly or in combination of two or more.
• silica, metal oxides, and minerals are preferable, and silica is more preferable, because an adhesive paste having excellent transparency can be easily obtained.
• hydrophobic surface-modified silica includes, on the surface, a trialkylsilyl group having 1 to 20 tricarbon atoms such as a trimethylsilyl group; an alkylsilyl group having 1 to 20 dicarbon atoms such as a dimethylsilyl group; Silica bound with alkylsilyl groups of number 1 to 20; Silica surface-treated with silicone oil; and the like.
• Hydrophobic surface-modified silica is, for example, a silica particle having a trialkylsilyl group having 1 to 20 carbon atoms, an alkylsilyl group having 1 to 20 dicarbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, or the like. It can be obtained by surface modification using a coupling agent, or by treating silica particles with silicone oil.
• the content of component (B1) is not particularly limited, but the amount is determined by the mass ratio of component (A) to component (B1).
• Component (A): Component (B1) preferably 100:0.1 to 100:90, more preferably 100:0.2 to 100:60, more preferably 100:0.3 to 100:50 , more preferably 100:0.5 to 100:40, more preferably 100:0.8 to 100:30.
• the average primary particle size of the fine particles (B2) is preferably more than 0.06 ⁇ m and 7 ⁇ m or less, more preferably more than 0.3 ⁇ m and 6 ⁇ m or less, still more preferably more than 1 ⁇ m and 4 ⁇ m or less.
• the average primary particle diameter of the fine particles (B2) is measured by a laser scattering method using a laser diffraction/scattering particle size distribution analyzer (for example, product name “LA-920” manufactured by Horiba, Ltd.). can be obtained by performing
• the shape of the fine particles (B2) may be the same as those exemplified as the shape of the fine particles (B1), but a spherical shape is preferred.
• the component of the fine particles (B2) the same components as those exemplified as the components of the fine particles (B1) can be mentioned.
• the fine particles (B2) can be used singly or in combination of two or more.
• the fine particles (B2) from the viewpoint of being relatively easy to mix as an adhesive paste, and from the fact that a cured product having excellent adhesiveness and heat resistance can be easily obtained, a metal oxide whose surface is coated with silicone At least one kind of fine particles selected from the group consisting of silica, silica and silicone are preferred, and silica and silicone are more preferred.
• the content of component (B2) is not particularly limited, but the amount is determined by the mass ratio of component (A) to component (B2).
• Component (A): Component (B2) preferably 100:0.1 to 100:40, more preferably 100:0.2 to 100:30, more preferably 100:0.3 to 100:20 , more preferably 100:0.5 to 100:15, and particularly preferably 100:0.8 to 100:12.
• the adhesive paste of the present invention contains other components [(C) component] other than the above components (A), (L) and (B) within a range that does not impede the purpose of the present invention.
• the antioxidant is added for the purpose of preventing oxidative deterioration during heating.
• Antioxidants include phosphorus antioxidants, phenolic antioxidants, sulfur antioxidants, and the like.
• Phosphorus antioxidants include phosphites, oxaphosphaphenanthrene oxides and the like.
• Phenolic antioxidants include monophenols, bisphenols, polymeric phenols, and the like.
• sulfur-based antioxidants include dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate and the like.
• antioxidants can be used singly or in combination of two or more.
• the amount of antioxidant to be used is generally 10% by mass or less relative to the component (A).
• a UV absorber is added for the purpose of improving the light resistance of the resulting adhesive paste.
• UV absorbers include salicylic acids, benzophenones, benzotriazoles, hindered amines and the like. These ultraviolet absorbers can be used singly or in combination of two or more. The amount of the ultraviolet absorber to be used is usually 10% by mass or less relative to the component (A).
• Light stabilizers include, for example, poly[ ⁇ 6-(1,1,3,3,-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl ⁇ (2,2,6 ,6-tetramethyl-4-piperidine)imino ⁇ hexamethylene ⁇ (2,2,6,6-tetramethyl-4-piperidine)imino ⁇ ] and other hindered amines. These light stabilizers can be used singly or in combination of two or more.
• the total amount of component (C) used is generally 20% by mass or less relative to component (A).
• the adhesive paste of the present invention can be produced, for example, by a production method comprising the following steps (AI) and (AII).
• 1) adhesive paste As a method of obtaining a polysilsesquioxane compound by polycondensing at least one compound represented by the above formula (a-6) in the step (AI) in the presence of a polycondensation catalyst, 1) adhesive paste The same methods as those exemplified in the section can be mentioned. Solvent (S) and liquid component (L) used in step (AII) are the same as those exemplified as solvent (S) and liquid component (L) in 1) Adhesive paste.
• the method of dissolving the polysilsesquioxane compound in the solvent (S) includes, for example, the polysilsesquioxane compound and the liquid component (L), and optionally the component (B) and ( A method of mixing, defoaming, and dissolving component C) with a solvent (S) can be mentioned.
• a mixing method and a defoaming method are not particularly limited, and known methods can be used.
• the order of mixing is not particularly limited. According to the production method including the steps (AI) and (AII), the adhesive paste of the present invention can be produced efficiently and simply.
• the adhesive paste of the present invention After heating the adhesive paste at 170° C. for 2 hours, the adhesive paste of the present invention has a mass reduction rate of 170° C. for 2 hours before and after heating, preferably less than 55%, more preferably 10% or more and less than 45%. , particularly preferably 15% or more and less than 30%. Since the volume of the adhesive paste decreases at the same time as the mass decreases, if the mass decrease rate of 170°C for 2 hours exceeds the above upper limit, the horizontally mounted chip may tilt after the adhesive paste hardens. By being there, you can reduce that risk.
• the adhesive paste of the present invention has a mass reduction rate of 100° C. for 2 hours before and after heating after the adhesive paste is heated at 100° C. for 2 hours. %, particularly preferably 13% or more and less than 45%.
• the mass reduction rate of 100° C. for 2 hours is equal to or higher than the above lower limit
• the cured product obtained by heating at a low temperature has excellent adhesion.
• the mass reduction rate of 100° C. for 2 hours is equal to or higher than the above upper limit
• the amount of the active ingredient exhibiting the adhesive function of the cured product obtained by heating at a low temperature is reduced, so that high adhesive strength may not be exhibited.
• the fear can be reduced.
• the adhesive paste of the present invention has a mass reduction rate of 170° C. 2h - 100° C. 2h , which is preferably less than 14%, more preferably less than 12%, and particularly preferably 1% or more and less than 10%. . Since the mass reduction rate of 170°C for 2h - the mass reduction rate of 100°C for 2h is less than the above upper limit, when heated at a low temperature, the solvent evaporates efficiently in the same way as when heated at a high temperature, so that at a low temperature Since the cured product obtained by heating has better adhesiveness, the temperature range for heating and curing the adhesive paste can be adjusted, and the effect of heating on optical components and sensor chips can be reduced.
• the mass reduction rate of 170°C for 2h and the mass reduction rate of 100°C for 2h can be measured by the method described in Examples.
• a cured product can be obtained by heating the adhesive paste to volatilize the solvent (S) and cure it.
• the heating temperature for curing is usually 80 to 190°C, preferably 80 to 120°C or 150 to 190°C.
• the heating time for curing is usually 30 minutes to 10 hours, preferably 30 minutes to 5 hours, more preferably 30 minutes to 3 hours.
• a cured product obtained by curing the adhesive paste of the present invention has excellent adhesiveness.
• the adhesive paste of the present invention is applied to the mirror surface of a square silicon chip with a side length of 1 mm (area is 1 mm 2 ), and the coated surface is placed on a silver-plated copper plate and crimped (adhesive paste after crimping). thickness: about 2 ⁇ m) and cured by heat treatment (eg, 100° C. for 2 hours, 170° C. for 2 hours).
• the adhesive strength of the cured product obtained by curing the adhesive paste of the present invention is preferably 7 N/mm square or more at 23° C., more preferably 10 N/mm square or more, and 13 N/mm square or more. 15 N/mm square or more is particularly preferable. Further, the adhesive strength of the cured product obtained by curing the adhesive paste of the present invention is preferably 7 N/mm square or more at 100° C., more preferably 10 N/mm square or more, and 13 N/mm square. It is more preferably 15 N/mm square or more, and particularly preferably 15 N/mm ⁇ or more.
• “1 mm square” means “1 mm square", that is, "1 mm x 1 mm (square with a side length of 1 mm)".
• the adhesive paste of the present invention can be suitably used as an adhesive for semiconductor element fixing materials.
• semiconductor elements include light-emitting elements such as lasers and light-emitting diodes (LEDs), optical semiconductor elements such as light-receiving elements such as solar cells, transistors, sensors such as temperature sensors and pressure sensors, and integrated circuits.
• LEDs light-emitting elements
• optical semiconductor elements such as light-receiving elements such as solar cells
• transistors transistors
• sensors such as temperature sensors and pressure sensors
• integrated circuits an optical semiconductor element is preferable from the viewpoint that the effect of using the adhesive paste of the present invention is likely to be exhibited more preferably.
• Materials for supporting substrates for bonding semiconductor elements include glasses such as soda lime glass and heat-resistant hard glass; ceramics; sapphire; iron, copper, aluminum, gold, silver, platinum, chromium, titanium and these metals. alloys, metals such as stainless steel (SUS302, SUS304, SUS304L, SUS309, etc.); polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, ethylene-vinyl acetate copolymer, polystyrene, polycarbonate, polymethylpentene, polysulfone, polyether Synthetic resins such as ether ketone, polyethersulfone, polyphenylene sulfide, polyetherimide, polyimide, polyamide, acrylic resin, norbornene resin, cycloolefin resin, and glass epoxy resin;
• the adhesive paste of the present invention is preferably filled in a syringe. Since the syringe is filled with the adhesive paste, workability in the coating process is excellent.
• the material of the syringe may be synthetic resin, metal or glass, but synthetic resin is preferred.
• the capacity of the syringe is not particularly limited, and may be appropriately determined according to the amount of adhesive paste to be filled or applied.
• a commercial item can also be used as a syringe. Commercially available products include, for example, SS-01T series (manufactured by TERUMO), PSY series (manufactured by Musashi Engineering) and the like.
• the syringe filled with the adhesive paste descends vertically to approach the support substrate, and after discharging a predetermined amount of the adhesive paste from the tip of the syringe, the syringe rises to support the support substrate. As the substrate is separated, the support substrate moves laterally. By repeating this operation, the adhesive paste is continuously applied to the support substrate. After that, a semiconductor element is mounted on the applied adhesive paste and pressure-bonded to the support substrate.
• the amount of the adhesive paste to be applied is not particularly limited, and may be any amount that allows the semiconductor element to be adhered and the supporting substrate to be firmly adhered by curing. Usually, the amount is such that the thickness of the coating film of the adhesive paste is 0.5 ⁇ m or more and 5 ⁇ m or less, preferably 1 ⁇ m or more and 3 ⁇ m or less.
• the semiconductor element is fixed to the support substrate by heating and curing the adhesive paste of the obtained press-fit.
• the heating temperature and heating time are as described in the section 1) Adhesive paste.
• the semiconductor element is satisfactorily mounted on the adhesive paste, and the semiconductor element is fixed with high adhesive strength.
• thermosetting organopolysiloxane compound (A) obtained in Production Examples were converted to standard polystyrene values and measured using the following equipment and conditions.
• Apparatus name HLC-8220GPC, manufactured by Tosoh Corporation Column: TSKgelGMHXL, TSKgelGMHXL, and TSKgel2000HXL sequentially connected
• Solvent Tetrahydrofuran Injection volume: 20 ⁇ l Measurement temperature: 40°C Flow rate: 1 ml/min Detector: Differential refractometer
• thermosetting organopolysiloxane compound (A) obtained in Production Example was measured using a Fourier transform infrared spectrophotometer (Spectrum 100, manufactured by PerkinElmer).
• Viscosity evaluation Using a rheometer (manufactured by Anton Paar, product name “MCR301”), the viscosity was measured at 25° C. and a shear rate of 1 s ⁇ 1 using a cone plate with a radius of 50 mm and a cone angle of 0.5°.
• thermosetting organopolysiloxane compound (A1) had a mass average molecular weight (Mw) of 7,800 and a molecular weight distribution (Mw/Mn) of 4.52. IR spectrum data of the thermosetting organopolysiloxane compound (A1) are shown below. Si—CH 3 : 1272 cm ⁇ 1 , 1409 cm ⁇ 1 , Si—O: 1132 cm ⁇ 1
• thermosetting organopolysiloxane compound (A2) had a mass average molecular weight (Mw) of 5,500 and a molecular weight distribution (Mw/Mn) of 3.40.
• IR spectrum data of the thermosetting organopolysiloxane compound (A2) are shown below. Si—CH 3 : 1272 cm ⁇ 1 , 1409 cm ⁇ 1 , Si—O: 1132 cm ⁇ 1 , CF: 1213 cm ⁇ 1
• thermosetting organopolysiloxane compound (A3) had a mass average molecular weight (Mw) of 1,100 and a molecular weight distribution (Mw/Mn) of 1.2.
• IR spectrum data of the thermosetting organopolysiloxane compound (A3) are shown below.
• the liquid polysilsesquioxane (L5) had a mass average molecular weight (Mw) of 740 and a molecular weight distribution (Mw/Mn) of 1.48.
• Thermosetting organopolysiloxane compound (A1) Organopolysiloxane compound obtained in Production Example 1 (solid at 25°C)
• Thermosetting organopolysiloxane compound (A2) Organopolysiloxane compound obtained in Production Example 2 (solid at 25°C)
• Thermosetting organopolysiloxane compound (A3) Organopolysiloxane compound obtained in Production Example 3 (solid at 25°C)
• Example 1 28 parts of EDGAC (SL), 10 parts of (L3-1), 3 parts of (L2-1), and 35 parts of (L1) are added to 100 parts of the thermosetting organopolysiloxane compound (A1), and the whole content is sufficiently mixed. By mixing and defoaming, an adhesive paste 1 having a solid concentration of 84% was obtained.
• Adhesive pastes 2 to 24 and 1r to 3r were obtained in the same manner as in Example 1, except that the types and blending ratios of the compounds (each component) were changed to those shown in Table 1 below.
• fine particles (B1) and fine particles (B2) were added before adding EDGAC (SL) and each liquid component (L1 to L3).
• Adhesion strength evaluation (1) The adhesive paste obtained in Examples and Comparative Examples was applied to the mirror surface of a square silicon chip with a side length of 1 mm (area of 1 mm 2 ), and under standard environment (temperature: 23 ° C. ⁇ 1 ° C., relative humidity) : 50 ⁇ 5%). After 30 minutes, the coated surface was placed on an adherend [electroless silver-plated copper plate (average roughness Ra of silver-plated surface: 0.025 ⁇ m)], and the thickness of the adhesive paste after pressure bonding was about 2 ⁇ m. crimped to. After that, it was cured by heat treatment at 170° C. for 2 hours to obtain an adherend with a test piece.
• This adherend with the test piece is left on the measurement stage of a bond tester (manufactured by Daisy, series 4000) at 100 ° C. for 60 seconds, and is adhered at a speed of 200 ⁇ m / s from a position 100 ⁇ m above the adherend. Stress was applied in the horizontal direction (shearing direction) to the surface, and the adhesive strength (N/mm ⁇ ) between the test piece and the adherend was measured at 100°C.
• Adhesion strength evaluation (2) In the adhesive strength evaluation (1), the same as the adhesive strength evaluation (1) except that the temperature condition for heat treatment and curing is changed to 100 ° C., and the heating temperature and measurement temperature of the bond tester are changed to 23 ° C. Then, the adhesive strength (N/mm square) between the test piece and the adherend was measured.
• the mass loss rate of the adhesive paste before and after heating was 170 ° C. 2 h ( %) [ ⁇ [(mass of adhesive paste before heating) ⁇ (mass of adhesive paste after heating at 170° C. for 2 hours)]/(mass of adhesive paste before heating) ⁇ 100] was calculated. Further, from the measured mass loss rate, mass loss rate 170°C 2h - mass loss rate 100°C 2h (%) was calculated.
• the adhesive pastes 1 to 24 of Examples 1 to 24 have a long tack-free time, excellent chip mountability, and excellent adhesion strength of the cured product obtained by heating the adhesive paste at a high temperature.
• An adhesive paste containing a bifunctional silane compound, a trifunctional silane compound, and a silicone oil as the liquid component (L) has a longer tack-free time than an adhesive paste containing a polyfunctional silane compound. , chip mounting is possible for a long time (Examples 2-4, 12-17).
• the adhesive paste containing a trifunctional silane compound and silicone oil as the liquid component (L) is obtained by heating the adhesive paste at a lower temperature than the adhesive paste containing a bifunctional silane compound.
• the adhesive strength of the cured product is excellent (Examples 5 to 9). That is, by selecting the liquid component (L), the tack-free time (time left after applying the adhesive paste to the object to be coated) and the temperature range in which the adhesive paste is heated to obtain a cured product are taken into account to obtain the optimum adhesion. You can get a paste.
• the adhesive paste with a higher content of the organic solvent (SH) has a longer tack-free time.
• an adhesive paste with a high organic solvent (SL) content has a short tack-free time, but the adhesion of a cured product obtained by heating the adhesive paste under both high-temperature heating and low-temperature heating conditions Excellent strength (Examples 20 and 21). That is, by selecting the organic solvent (SL) and the organic solvent (SH), the tack-free time (time left after applying the adhesive paste to the object to be coated) and the temperature range for heating the adhesive paste to obtain a cured product are adjusted. It is possible to obtain the optimum adhesive paste by taking into consideration.
• An adhesive paste with a high solid content concentration (accordingly, a high content ratio of the (L) component with respect to the total mass of the adhesive paste) has a longer tack-free time and can be cured by heating the adhesive paste at a low temperature. Excellent adhesion strength to objects (Examples 1 and 22).
• An adhesive paste containing fine particles (B) has a lower tack-free time than an adhesive paste that does not contain fine particles (B), even though the content of component (L) relative to the total mass of the adhesive paste is small. It gives a cured product that is long, has excellent chip mountability, and has good adhesive strength under both high-temperature heating and low-temperature heating conditions (Examples 23 and 24).
• thermosetting organopolysiloxane compound (A) type of polysilsesquioxane compound side chain
• the tack-free time is long, the chip mountability is excellent, and the adhesive paste can be used.
• the adhesive strength of the resulting cured product is also excellent under both high temperature heating and low temperature heating conditions (Examples 1, 5, 11, etc.).
• the adhesive paste 1r of Comparative Example 1 since the content of the liquid component (L) is as small as 10% with respect to the total mass of the adhesive paste, the tack-free time is short, which is disadvantageous for chip mounting in a short time. In addition, after the silicon chip was mounted, the chip tilted, and the chip mountability was poor, so the adhesive strength could not be measured.
• the adhesive paste 2r of Comparative Example 2 contains a high-viscosity liquid component (L), and since the viscosity of the adhesive paste is high, the tack-free time is short, which is disadvantageous for chip mounting in a short time. In addition, after the silicon chip was mounted, the chip tilted, and the chip mountability was poor, so the adhesive strength could not be measured.
• the adhesive paste 3r of Comparative Example 3 contained only an organic solvent (SL) as the solvent (S), but the content of the liquid component (L) with respect to the total mass of the adhesive paste was as small as 10%. , the tack-free time is short, and it becomes disadvantageous for chip mounting in a short time. In addition, after the silicon chip was mounted, the chip tilted, and the chip mountability was poor, so the adhesive strength could not be measured.
• SL organic solvent
• L liquid component

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Adhesives Or Adhesive Processes (AREA)
• Die Bonding (AREA)

Priority Applications (1)

Applications Claiming Priority (2)

Publications (1)

Family

ID=83395620

Family Applications (1)

Country Status (3)

Citations (5)

• 2022
  • 2022-03-22 WO PCT/JP2022/013290 patent/WO2022202846A1/ja not_active Ceased
  • 2022-03-22 TW TW111110510A patent/TW202244235A/zh unknown
  • 2022-03-22 JP JP2023509215A patent/JPWO2022202846A1/ja active Pending

Patent Citations (5)

Also Published As

Similar Documents

Legal Events