Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
• • 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
  • C08K5/54—Silicon-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of 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; Compositions of derivatives of such polymers
  • C08L83/04—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
  • H10W74/00—Encapsulations, e.g. protective coatings
  • H10W74/10—Encapsulations, e.g. protective coatings characterised by their shape or disposition
• • 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
  • H10W74/00—Encapsulations, e.g. protective coatings
  • H10W74/40—Encapsulations, e.g. protective coatings characterised by their materials

Definitions

• a curable composition having excellent curability and storage stability, a cured product obtained by curing the curable composition, and the curable composition are subjected to an adhesive for an optical element fixing material or an optical element fixing.
• the present invention relates to a method of using it as a sealing material for materials.
• the curable composition has been variously improved according to the application, and has been widely used industrially as a raw material for optical parts and molded articles, an adhesive, a coating agent, and the like. Further, the curable composition has also attracted attention as a composition for an optical element fixing material such as an adhesive for an optical element fixing material and a sealing material for an optical element fixing material.
• Optical elements include various lasers such as semiconductor lasers (LDs), light emitting elements such as light emitting diodes (LEDs), light receiving elements, composite optical elements, and optical integrated circuits.
• LDs semiconductor lasers
• LEDs light emitting diodes
• optical integrated circuits optical elements of blue light or white light having a shorter peak wavelength of light emission have been developed and widely used. The brightness of such a light emitting element having a short peak wavelength of light emission is dramatically increased, and the amount of heat generated by the optical element tends to be further increased accordingly.
• the cured product of the composition for fixing the optical element is exposed to light of higher energy or higher temperature heat generated from the optical element for a long time, and the adhesive strength is reduced. There was a problem of doing.
• Patent Documents 1 to 3 propose compositions for optical device fixing materials containing a polysilsesquioxane compound as a main component.
• the composition for an optical element fixing material is usually heated and cured.
• Patent Document 4 describes a condensation reaction type silicone composition containing a specific polysilsesquioxane compound and a condensation reaction catalyst. Patent Document 4 also describes that the condensation reaction type silicone composition is excellent in various properties and also excellent in curability (initial curability).
• the condensation reaction type silicone composition described in Patent Document 4 is said to be excellent not only in various properties but also in curability.
• the curing conditions described in the examples of Patent Document 4 are that the mixture is heated at 120 ° C. for 1 hour and then further heated at 150 ° C. for 3 hours, and a curable composition having further excellent curability is desired. It had been.
• the present invention has been made in view of the above-mentioned actual conditions of the prior art, and is a curable composition having excellent curability and storage stability, a cured product obtained by curing the curable composition, and the curable property. It is an object of the present invention to provide a method of using the composition as an adhesive for an optical element fixing material or a sealing material for an optical element fixing material.
• excellent in curability means that when the curing reaction is carried out under predetermined conditions, the viscosity increases in a shorter time and the product is finally cured.
• the present inventors have made extensive studies on a curable composition containing a polysilsesquioxane compound. As a result, they have found that a curable composition containing a polysilsesquioxane compound and a thermoacid generator is excellent in curability and storage stability, and have completed the present invention.
• R 1 is an unsubstituted alkyl group having 1 to 10 carbon atoms, an alkyl group having a substituent having 1 to 10 carbon atoms, an aryl group having an unsubstituted carbon number of 6 to 12 carbon atoms, and a carbon number having a substituent (substituted group). It is a group selected from the group consisting of 6 to 12 aryl groups.
• the peak temperature (acid generation temperature) of the maximum endothermic peak obtained by differential scanning calorimetry under the conditions of a temperature range of 30 to 300 ° C. and a heating rate of 10 ° C./min is 80 to 180. °C.
• the curable composition according to any one of [1] to [7] which further contains the following component (C).
• (C) Component Silane coupling agent
• Composition [10] A cured product obtained by curing the curable composition according to any one of the above [1] to [9]. [11] The cured product according to [10], which is an optical element fixing material. [12] A method in which the curable composition according to any one of [1] to [9] above is used as an adhesive for an optical element fixing material. [13] A method in which the curable composition according to any one of [1] to [9] above is used as a sealing material for an optical element fixing material.
• a curable composition having excellent curability and storage stability, a cured product obtained by curing the curable composition, and the curable composition can be used as an adhesive for an optical element fixing material or light.
• a method for use as a sealing material for an element fixing material is provided.
• the present invention will be described in detail by dividing it into 1) a curable composition, 2) a cured product, and 3) a method of using the curable composition.
• Curable composition The curable composition of the present invention contains the following components (A) and (B).
• Component (A) Polysilsesquioxane compound having one or more repeating units represented by the above formula (a-1)
• the component (A) constituting the curable composition of the present invention is a polysilsesquioxane compound having one or more repeating units represented by the following formula (a-1) (hereinafter, “polysilsesqui”). It may be expressed as “oxane compound (A)").
• R 1 is an unsubstituted alkyl group having 1 to 10 carbon atoms, an alkyl group having a substituent and having 1 to 10 carbon atoms, an unsubstituted aryl group having 6 to 12 carbon atoms, and an unsubstituted alkyl group.
• the number of carbon atoms of the "alkyl group unsubstituted C 1 -C 10" represented by R 1 is preferably from 1 to 6, 1 to 3 more preferred.
• Examples of the "unsubstituted alkyl group having 1 to 10 carbon atoms” include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, a t-butyl group and an n-. Examples thereof include a pentyl group, an n-hexyl group, an n-octyl group, an n-nonyl group, an n-decyl group and the like.
• the number of carbon atoms of the "alkyl group having 1 to 10 carbon atoms having substituent" represented by R 1 is preferably from 1 to 6, 1 to 3 more preferred.
• the number of carbon atoms means the number of carbon atoms of the portion excluding the substituent (the portion of the alkyl group). Therefore, when R 1 is an "alkyl group having 1 to 10 carbon atoms having a substituent", the carbon number of R 1 may exceed 10.
• Examples of the alkyl group of the "alkyl group having 1 to 10 carbon atoms having a substituent" include those similar to those shown as the "unsubstituted alkyl group having 1 to 10 carbon atoms".
• the number of atoms of the substituent (excluding the number of hydrogen atoms) of the "alkyl group having 1 to 10 carbon atoms having a substituent” is usually 1 to 30, preferably 1 to 20.
• substituent of the "alkyl group having 1 to 10 carbon atoms having a substituent” include halogen atoms such as fluorine atom, chlorine atom and bromine atom; cyano group; formula: group represented by OG; and the like.
• G represents a hydroxyl-protecting group.
• the hydroxyl-protecting group is not particularly limited, and examples thereof include known protecting groups known as hydroxyl-protecting groups.
• acyl-based protecting groups For example, acyl-based protecting groups; silyl-based protecting groups such as trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, t-butyldiphenylsilyl group; methoxymethyl group, methoxyethoxymethyl group, 1-ethoxyethyl group.
• Acetal-based protecting groups such as tetrahydropyran-2-yl group and tetrahydrofuran-2-yl group; alkoxycarbonyl-based protecting groups such as t-butoxycarbonyl group; methyl group, ethyl group, t-butyl group, octyl group , Allyl group, triphenylmethyl group, benzyl group, p-methoxybenzyl group, fluorenyl group, trityl group, benzhydryl group and other ether-based protecting groups; and the like.
• the number of carbon atoms of the "unsubstituted aryl group having 6 to 12 carbon atoms" represented by R 1 6 is preferred.
• Examples of the "unsubstituted aryl group having 6 to 12 carbon atoms” include a phenyl group, a 1-naphthyl group, a 2-naphthyl group and the like.
• the number of carbon atoms of the "aryl group having 6 to 12 carbon atoms having a substituent" represented by R 1 6 is preferred.
• the number of carbon atoms means the number of carbon atoms of the portion excluding the substituent (the portion of the aryl group). Therefore, when R 1 is an "aryl group having 6 to 12 carbon atoms having a substituent", the carbon number of R 1 may exceed 12.
• Examples of the aryl group of the "aryl group having 6 to 12 carbon atoms having a substituent” include those similar to those shown as the "substituted aryl group having 6 to 12 carbon atoms".
• the number of atoms of the substituent (excluding the number of hydrogen atoms) of the "aryl group having 6 to 12 carbon atoms having a substituent” is usually 1 to 30, preferably 1 to 20.
• substituent of the "aryl group having a substituent and having 6 to 12 carbon atoms" include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an s-butyl group, an isobutyl group and a t-butyl.
• Alkyl groups such as groups, n-pentyl groups, n-hexyl groups, n-heptyl groups, n-octyl groups and isooctyl groups; halogen atoms such as fluorine atom, chlorine atom and bromine atom; alkoxy such as methoxy group and ethoxy group. Group; etc.
• R 1 is an unsubstituted alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms having a fluorine atom, an alkyl group having 1 to 10 carbon atoms having a cyano group, or an unsubstituted alkyl group.
• the aryl group having 6 to 12 carbon atoms is preferable.
• the polysilsesquioxane compound (A) in which R 1 is an unsubstituted alkyl group having 1 to 10 carbon atoms it becomes easy to obtain a curable composition that gives a cured product having better heat resistance and adhesiveness. ..
• the "cured product having excellent adhesiveness” means a "cured product having high adhesive strength”.
• the content ratio of the repeating unit represented by the above formula (a-1) in the polysilsesquioxane compound (A) is preferably 70 to 100 mol%, more preferably 80 to 100 mol%, based on all the repeating units. 90 to 100 mol% is more preferable.
• the content ratio of the repeating unit represented by the above formula (a-1) in the polysilsesquioxane compound (A) can be determined by measuring 1 1 H-NMR as described later.
• the repeating unit represented by the formula (a-1) is represented by the following formula (a-2).
• O 1/2 means that an oxygen atom is shared with adjacent repeating units.
• the polysilsesquioxane compound (A) has three oxygen atoms bonded to a silicon atom, which is generally called a T site, and other groups (R 1 ). Has a partial structure in which one is combined.
• T site contained in the polysilsesquioxane compound (A) include those represented by the following formulas (a-3) to (a-5).
• R 1 has the same meaning as described above.
• R 2 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Examples of the alkyl group having 1 to 10 carbon atoms R 2, a methyl group, an ethyl group, n- propyl group, an isopropyl group, n- butyl group, s- butyl group, an isobutyl group, a t- butyl group and the like can be mentioned. A plurality of R 2 to each other may all be different mutually be the same. Further, in the above formulas (a-3) to (a-5), a Si atom is bonded to *.
• the polysilsesquioxane compound (A) is a ketone solvent such as acetone; an aromatic hydrocarbon solvent such as benzene; a sulfur-containing solvent such as dimethyl sulfoxide; an ether solvent such as tetrahydrofuran; an ester solvent such as ethyl acetate. It is soluble in various organic solvents such as a solvent; a halogen-containing solvent such as chloroform; and a mixed solvent composed of two or more of these. Therefore, using these solvents, 29 Si-NMR in a solution state of the polysilsesquioxane compound (A) can be measured.
• the polysilsesquioxane compound (A) used in the present invention preferably contains 10 to 45 mol% of T2 sites, more preferably 15 to 40 mol%, from the viewpoint of improving the adhesiveness of the cured product. , 20-35 mol% is more preferable.
• the polysilsesquioxane compound (A) used in the present invention preferably contains 50 to 90 mol% of T3 sites, preferably 55 to 85 mol%, from the viewpoint of obtaining a cured product which is hard and has excellent heat resistance. Those containing 60 to 80 mol% are more preferable, and those containing 60 to 80 mol% are even more preferable.
• the polysilsesquioxane compound (A) may be one having one kind of R 1 (monopolymer) or one having two or more kinds of R 1 (copolymer).
• the polysilsesquioxane compound (A) is a copolymer
• the polysilsesquioxane compound (A) is any of a random copolymer, a block copolymer, a graft copolymer, an alternating copolymer and the like.
• a random copolymer is preferable.
• the structure of the polysilsesquioxane compound (A) may be any of a ladder type structure, a double decker type structure, a cage type structure, a partially cleaved cage type structure, a cyclic type structure, and a random type structure. ..
• the mass average molecular weight (Mw) of the polysilsesquioxane compound (A) is usually 500 to 20,000, preferably 1,000 to 15,000, and more preferably 1,500 to 12,000.
• the molecular weight distribution (Mw / Mn) of the polysilsesquioxane compound (A) is not particularly limited, but is usually 1.0 to 10.0, preferably 1.1 to 6.0.
• Mw / Mn molecular weight distribution
• the mass average molecular weight (Mw) and the number average molecular weight (Mn) can be determined, for example, as standard polystyrene-equivalent values by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent.
• the polysilsesquioxane compound (A) can be used alone or in combination of two or more.
• the content of the polysilsesquioxane compound (A) is preferably 40% by mass or more and less than 100% by mass, more preferably 48 to 95% by mass, and further preferably 56 in the solid content of the curable composition. It is ⁇ 90% by mass.
• the "solid content” refers to a component other than the solvent in the curable composition.
• the method for producing the polysilsesquioxane compound (A) is not particularly limited.
• the polysilsesquioxane compound (A) can be produced by polycondensing at least one of the silane compounds (1) represented by the following formula (a-6).
• R 1 has the same meaning as described above.
• R 3 represents an alkyl group having 1 to 10 carbon atoms
• X 1 represents a halogen atom
• p represents an integer of 0 to 3.
• a plurality of R 3, and a plurality of X 1 are each, be the same as each other, may be different from each other.
• Examples of the alkyl group having 1 to 10 carbon atoms of R 3 include those similar to those shown as the alkyl group having 1 to 10 carbon atoms of R 2.
• Examples of the halogen atom of X 1 include a chlorine atom and a bromine atom.
• 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, and ethyltripropoxy
• Substituent 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-cyanoethyldich
• Phenyltrialkoxysilane compounds having or not having a substituent such as phenyltrimethoxysilane and 4-methoxyphenyltrimethoxysilane
• Phenylhalogenoalkoxysilane compounds having or not having a substituent such as phenylchlorodimethoxysilane, phenyldichloromethoxysilane, 4-methoxyphenylchlorodimethoxysilane, 4-methoxyphenyldichloromethoxysilane
• Phenyltrihalogenosilane compounds having or not having a substituent such as phenyltrichlorosilane and 4-methoxyphenyltrichlorosilane; and the like can be mentioned.
• These silane compounds (1) can be used alone or in combination of two or more.
• the method for polycondensing the silane compound (1) is not particularly limited.
• a method of adding a predetermined amount of polycondensation catalyst to the silane compound (1) in a solvent or without a solvent and stirring at a predetermined temperature can be mentioned. More specifically, a method of adding a predetermined amount of an acid catalyst to (a) a silane compound (1) and stirring at a predetermined temperature, and (b) adding a predetermined amount of a base catalyst to the silane compound (1).
• a method of stirring at a predetermined temperature, (c) a predetermined amount of an acid catalyst is added to the silane compound (1), and after stirring at a predetermined temperature, an excess amount of a base catalyst is added to make the reaction system basic.
• a method of stirring at a predetermined temperature and the like is preferable because the desired polysilsesquioxane compound (A) can be efficiently obtained.
• the polycondensation catalyst used may be either an acid catalyst or a base catalyst. Further, two or more polycondensation catalysts may be used in combination, but at least an acid catalyst is preferably used.
• the acid catalyst include inorganic acids such as phosphoric acid, hydrochloric acid, boric acid, sulfuric acid and nitrate; organic acids such as citric acid, acetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid and p-toluenesulfonic acid; etc. Can be mentioned. Among these, at least one selected from phosphoric acid, hydrochloric acid, boric acid, sulfuric acid, citric acid, acetic acid, and methanesulfonic acid is preferable.
• aqueous ammonia As the base catalyst, aqueous ammonia; trimethylamine, triethylamine, lithium diisopropylamide, lithium bis (trimethylsilyl) amide, pyridine, 1,8-diazabicyclo [5.4.0] -7-undecene, aniline, picolin, 1,4- Diazabicyclo [2.2.2]
• Organic bases such as octane and imidazole; organic hydroxides such as tetramethylammonium hydroxide and tetraethylammonium hydroxide; sodium methoxydo, 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; Metallic hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen
• the amount of the polycondensation catalyst used is usually in the range of 0.05 to 10 mol%, preferably 0.1 to 5 mol%, based on the total mol amount of the silane compound (1).
• the solvent to be used can be appropriately selected according to the type of the silane compound (1) and the like.
• 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, t-butyl alcohol; and the like. These solvents can be used alone or in combination of two or more.
• a polycondensation reaction is carried out in an aqueous system in the presence of an acid catalyst, and then an organic solvent and an excessive amount of a base catalyst (ammonia water or the like) are added to the reaction solution.
• the polycondensation reaction may be further carried out under basic conditions.
• the amount of the solvent used is 0.1 liter or more and 10 liters or less, preferably 0.1 liter or more and 2 liters or less, per 1 mol of the total mol amount of the silane compound (1).
• the temperature at which the silane compound (1) is polycondensed is usually in the temperature range from 0 ° C. to the boiling point of the solvent used, preferably in the range of 20 ° C. or higher and 100 ° C. or lower. If the reaction temperature is too low, the progress of the polycondensation reaction may be insufficient. On the other hand, if the reaction temperature becomes too high, it becomes difficult to suppress gelation. The reaction is usually complete in 30 minutes to 30 hours.
• the monomer R 1 is an alkyl group having a fluorine atom, it tends to be inferior in reactivity than the monomer wherein R 1 is normal alkyl group.
• the polysilsesquioxane compound (A) having the desired molecular weight can be easily obtained.
• the portion of OR 3 or X 1 of the silane compound (1) in which dealcoholization or the like does not occur is the polysilsesquioxane compound (A).
• T sites represented by the formulas (a-4) and (a-5) are included. May be included.
• thermoacid generator is a compound that generates an acid component such as Lewis acid or Bronsted acid by heating. Since the curable composition of the present invention contains a thermoacid generator, it is excellent in curability and storage stability.
• thermoacid generator the peak temperature (acid generation temperature) of the maximum endothermic peak obtained by differential scanning calorimetry under the conditions of a temperature range of 30 to 300 ° C. and a temperature rise rate of 10 ° C./min is 80 to 80 to The one at 180 ° C. is preferable.
• a curable composition containing a thermoacid generator having an acid generation temperature of 80 ° C. or higher under the above conditions is more excellent in storage stability.
• the curable composition containing a thermoacid generator having an acid generation temperature of 180 ° C. or lower under the above conditions is more excellent in curability. Since these effects are more easily obtained, the acid generation temperature under the above conditions is preferably 90 to 170 ° C, more preferably 100 to 160 ° C.
• thermoacid generator examples include an onium salt-based thermoacid generator.
• the onium salt-based thermoacid generator is a thermoacid generator containing an onium cation component and an anion component.
• the onium cation component include organic sulfonium ion, organic ammonium ion, organic phosphonium ion, and organic iodonium ion.
• organic sulfonium ion constituting the onium salt-based thermoacid generator examples include cations represented by the following formula (b-1).
• R 4 , R 5 , and R 6 are independently substituted alkyl groups having 1 to 10 carbon atoms, alkyl groups having substituents and having 1 to 10 carbon atoms, and unsubstituted. It is a group selected from the group consisting of an aryl group having 6 to 12 carbon atoms and an aryl group having 6 to 12 carbon atoms having a substituent.
• R 4 ⁇ carbon atoms in the "unsubstituted alkyl group having 1 to 10 carbon atoms" represented by R 6 is preferably 1 to 6, 1 to 3 more preferred.
• the "unsubstituted alkyl group having 1 to 10 carbon atoms" include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, a t-butyl group and an n-. Examples thereof include a pentyl group, an n-hexyl group, an n-octyl group, an n-nonyl group, an n-decyl group and the like.
• R 4 ⁇ carbon atoms represented by "alkyl group having 1 to 10 carbon atoms having substituent" in R 6 is preferably 1 to 6, 1 to 3 more preferred.
• the number of carbon atoms means the number of carbon atoms of the portion excluding the substituent (the portion of the alkyl group). Therefore, when R 4 to R 6 are "alkyl groups having 1 to 10 carbon atoms having a substituent", the number of carbon atoms of R 4 to R 6 may exceed 10.
• Examples of the alkyl group of the "alkyl group having 1 to 10 carbon atoms having a substituent" include those similar to those shown as the "unsubstituted alkyl group having 1 to 10 carbon atoms".
• the number of atoms of the substituent (excluding the number of hydrogen atoms) of the "alkyl group having 1 to 10 carbon atoms having a substituent” is usually 1 to 30, preferably 1 to 20.
• substituent of the "alkyl group having a substituent and having 1 to 10 carbon atoms" include an aryl such as a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a 1-naphthyl group and a 2-naphthyl group. The group is mentioned.
• R 4 ⁇ carbon atoms in the "unsubstituted aryl group having 6 to 12 carbon atoms" represented by R 6 is 6 are preferred.
• Examples of the "unsubstituted aryl group having 6 to 12 carbon atoms" include a phenyl group, a 1-naphthyl group, a 2-naphthyl group and the like.
• the "aryl group having a substituent and having 6 to 12 carbon atoms" represented by R 4 to R 6 preferably has 6 carbon atoms.
• the number of carbon atoms means the number of carbon atoms of the portion excluding the substituent (the portion of the aryl group). Therefore, when R 4 to R 6 are "aryl groups having 6 to 12 carbon atoms having a substituent", the number of carbon atoms of R 4 to R 6 may exceed 12.
• Examples of the aryl group of the "aryl group having 6 to 12 carbon atoms having a substituent” include those similar to those shown as the "substituted aryl group having 6 to 12 carbon atoms".
• the number of atoms of the substituent (excluding the number of hydrogen atoms) of the "aryl group having 6 to 12 carbon atoms having a substituent” is usually 1 to 30, preferably 1 to 20.
• substituent of the "aryl group having a substituent and having 6 to 12 carbon atoms" include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an s-butyl group, an isobutyl group and a t-butyl.
• Alkyl group such as group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group; alkoxy group such as methoxy group and ethoxy group; hydroxy group; acetyloxy group, propionyloxy group and the like. Examples thereof include the acyloxy group of.
• Examples of the organic ammonium ion constituting the onium salt-based thermoacid generator include cations represented by the following formula (b-2).
• R 7 , R 8 , R 9 , and R 10 are independently unsubstituted alkyl groups having 1 to 10 carbon atoms and alkyl groups having 1 to 10 carbon atoms having substituents, respectively. It is a group selected from the group consisting of an unsubstituted aryl group having 6 to 12 carbon atoms and an aryl group having a substituent and having 6 to 12 carbon atoms. Examples of R 7 to R 10 include the same as those represented by R 4 to R 6.
• organic phosphonium ion constituting the onium salt-based thermoacid generator examples include cations represented by the following formula (b-3).
• R 11 , R 12 , R 13 and R 14 are independently substituted alkyl groups having 1 to 10 carbon atoms and alkyl groups having 1 to 10 carbon atoms having substituents, respectively. It is a group selected from the group consisting of an unsubstituted aryl group having 6 to 12 carbon atoms and an aryl group having a substituent and having 6 to 12 carbon atoms. Examples of R 11 to R 14 include the same as those represented by R 4 to R 6.
• organic iodonium ion constituting the onium salt-based thermoacid generator examples include cations represented by the following formula (b-4).
• R 15 and R 16 are independently an unsubstituted alkyl group having 1 to 10 carbon atoms, an alkyl group having a substituent and having 1 to 10 carbon atoms, and an unsubstituted alkyl group having 6 carbon atoms, respectively. It is a group selected from the group consisting of an aryl group of up to 12 and an aryl group having 6 to 12 carbon atoms having a substituent. Examples of R 15 and R 16 include the same as those represented by R 4 to R 6.
• the onium cation component is organic because it has an appropriate acid generation temperature from the viewpoint of achieving both curability and storage stability of the curable composition and it is easy to control the reactivity of the acid generation reaction.
• Sulfonium ion or organic ammonium ion is preferable, and organic sulfonium ion represented by the following formula (b-5) is more preferable.
• Ar has a substituent such as a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a 1-naphthyl group, a 2-naphthyl group, or a substituent.
• a substituent such as a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a 1-naphthyl group, a 2-naphthyl group, or a substituent.
• the anion components of the onium salt-based thermoacid generator include trifluoromethanesulfonic acid anion, hexafluorophosphate anion, hexafluoroantimonic acid anion, perfluorobutanesulfonic acid anion, tetrakis (pentafluorophenyl) borate anion, and tetrafluoro.
• Anion borate and the like can be mentioned.
• hexafluorophosphate anion, hexafluoroantimonate anion, and tetrax (pentafluorophenyl) borate anion are preferable as the anion component because a cured product having excellent optical properties can be easily obtained.
• Anions are more preferred.
• the thermal acid generator can be used alone or in combination of two or more.
• the content of the thermoacid generator is usually more than 0 parts by mass and 5 parts by mass or less, preferably 0.001 to 3.0 parts by mass, more preferably with respect to 100 parts by mass of the polysilsesquioxane compound (A). Is 0.005 to 2.0 parts by mass, more preferably 0.010 to 1.5 parts by mass, and particularly preferably 0.015 to 1.0 parts by mass. If the content of the thermoacid generator is too large, the adhesiveness of the cured product may decrease.
• the curable composition of the present invention may contain a silane coupling agent as the component (C).
• a silane coupling agent refers to a silane compound having a silicon atom, a functional group, and a hydrolyzable group bonded to the silicon atom.
• the functional group means a group having a reactivity with another compound (mainly an organic substance), for example, a group having a nitrogen atom such as an amino group, a substituted amino group, an isocyanate group, a ureido group, and a group having an isocyanurate skeleton.
• the silane coupling agent can be used alone or in combination of two or more.
• the content of the silane coupling agent is usually 95 parts by mass or less, preferably 65 parts by mass or less, and more preferably 35 parts by mass or less with respect to 100 parts by mass of the polysilsesquioxane compound (A).
• silane coupling agent a silane coupling agent having a nitrogen atom in the molecule or a silane coupling agent having an acid anhydride structure in the molecule is preferable.
• a curable composition containing a silane coupling agent having a nitrogen atom in the molecule or a silane coupling agent having an acid anhydride structure in the molecule tends to give a cured product having better heat resistance and adhesiveness.
• silane coupling agent having a nitrogen atom in the molecule examples include a trialkoxysilane compound represented by the following formula (c-1), a dialkoxyalkylsilane compound represented by the formula (c-2), or dialkoxy. Examples thereof include arylsilane compounds.
• R a represents a methoxy group, an ethoxy group, n- propoxy group, isopropoxy group, n- butoxy group, an alkoxy group having 1 to 6 carbon atoms such as t- butoxy.
• R b is an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group and a t-butyl group; or a phenyl group, a 4-chlorophenyl group and a 4-.
• R c represents an organic group having 1 to 10 carbon atoms and having a nitrogen atom. Further, R c may be bonded to a group containing another silicon atom. Specific examples of the organic group having 1 to 10 carbon atoms R c is, N-2- (aminoethyl) -3-aminopropyl group, 3-aminopropyl group, N-(1,3-dimethyl - butylidene) amino Examples thereof include a propyl group, a 3-ureidopropyl group and an N-phenyl-aminopropyl group.
• the compound in which Rc is an organic group bonded to a group containing another silicon atom is a silane cup having an isocyanurate skeleton.
• examples thereof include a ring agent (isocyanurate-based silane coupling agent) and a silane coupling agent having a urea skeleton (urea-based silane coupling agent).
• the silane coupling agent having a nitrogen atom in the molecule an isocyanurate-based silane coupling agent and a urea-based silane coupling agent are preferable because a cured product having better adhesiveness can be easily obtained.
• the molecule has 4 or more alkoxy groups bonded to a silicon atom. Having 4 or more alkoxy groups bonded to a silicon atom means that the total count of the alkoxy groups bonded to the same silicon atom and the alkoxy groups bonded to different silicon atoms is 4 or more.
• Examples of the isocyanurate-based silane coupling agent having 4 or more alkoxy groups bonded to a silicon atom include a compound represented by the following formula (c-3).
• Examples of the urea-based silane coupling agent having 4 or more alkoxy groups bonded to a silicon atom include compounds represented by the following formula (c-4).
• Ra has the same meaning as above.
• t1 to t5 independently represents an integer of 1 to 10, preferably an integer of 1 to 6, and particularly preferably 3.
• 1,3,5-N-tris (3-trimethoxysilylpropyl) isocyanurate and 1,3,5-N-tris (3-) are examples of the silane coupling agent having a nitrogen atom in the molecule.
• Triethoxysilylpropyl) isocyanurate hereinafter referred to as "isocyanurate compound”
• N, N'-bis (3-trimethoxysilylpropyl) urea N, N'-bis (3-triethoxysilylpropyl) urea
• urea compound a combination of the above isocyanurate compound and urea compound is preferably used.
• the content thereof is not particularly limited, but the amount thereof has the above component (A) and a nitrogen atom in the molecule.
• the mass ratio of the silane coupling agent [(A component: silane coupling agent having a nitrogen atom in the molecule], preferably 100: 0.1 to 100: 90, more preferably 100: 0.3 to 100:
• the amount is 60, more preferably 100: 1 to 100: 50, still more preferably 100: 3 to 100: 40, and particularly preferably 100: 5 to 100: 35.
• the cured product of the curable composition containing the component (A) and the silane coupling agent having a nitrogen atom in the molecule at such a ratio becomes excellent in heat resistance and adhesiveness.
• a silane coupling agent having an acid anhydride structure in a molecule is an organosilicon compound having both a group having an acid anhydride structure and a hydrolyzable group in one molecule. Specific examples thereof include compounds represented by the following formula (c-5).
• Q represents a group having an acid anhydride structure
• R d represents an alkyl group, or have a substituent, or having no substituent phenyl group having 1 to 6 carbon atoms
• R e is a carbon It represents an alkoxy group or a halogen atom of the number 1 to 6
• i and k represent an integer of 1 to 3
• j represents an integer of 0 to 2
• i + j + k 4.
• R ds may be the same or different from each other.
• k is 2 or 3
• among a plurality of R e may be different from each be the same.
• i 2 or 3
• a plurality of Qs may be the same or different from each other.
• Examples of Q include a group represented by the following formula, and a group represented by (Q1) is particularly preferable.
• h represents an integer from 0 to 10.
• silane coupling agent having an acid anhydride structure in the molecule examples include 2- (trimethoxysilyl) ethyl succinic anhydride, 2- (triethoxysilyl) ethyl anhydride succinic anhydride, and 3- (trimethoxysilyl) propyl succinic anhydride.
• Tri (1 to 6 carbon atoms) alkoxysilyl (2 to 8 carbon atoms) alkyl succinic anhydride such as acid, 3- (triethoxysilyl) propyl succinic anhydride
• Di (1 to 6 carbon atoms) alkoxymethylsilyl (2 to 8 carbon atoms) alkyl succinic anhydride such as 2- (dimethoxymethylsilyl) ethyl succinic anhydride
• (1 to 6 carbon atoms) alkoxydimethylsilyl (2 to 8 carbon atoms) alkyl succinic anhydride
• Trihalogenosilyl (2-8 carbon atoms) alkyl succinic anhydride such as 2- (trichlorosilyl) ethyl succinic anhydride, 2- (tribromosilyl) ethyl succinic anhydride;
• Dihalogenomethylsilyl (2-8 carbon atoms) alkyl succinic anhydride such as 2- (dichloromethylsilyl) ethyl succinic anhydride;
• Examples thereof include halogenodimethylsilyl (2 to 8 carbon atoms) alkyl succinic anhydride, such as 2- (chlorodimethylsilyl) ethyl succinic anhydride.
• silane coupling agent having an acid anhydride structure in the molecule tri (1 to 6 carbon atoms) alkoxysilyl (2 to 8 carbon atoms) alkyl succinic anhydride is preferable, and 3- (trimethoxysilyl) is preferable.
• silane coupling agent having an acid anhydride structure in the molecule tri (1 to 6 carbon atoms) alkoxysilyl (2 to 8 carbon atoms) alkyl succinic anhydride is preferable, and 3- (trimethoxysilyl) is preferable.
• Succinic anhydride or 3- (triethoxysilyl) propyl succinic anhydride is particularly preferred.
• the content of the silane coupling agent having an acid anhydride structure in the molecule is the mass ratio of the above component (A) to the silane coupling agent having an acid anhydride structure in the molecule [(A component): acid in the molecule.
• a silane coupling agent having an anhydride structure preferably 100: 0.1 to 100:30, more preferably 100: 0.3 to 100: 20, more preferably 100: 0.5 to 100: 15, More preferably, the amount is 100: 1 to 100:10.
• the cured product of the curable composition containing the component (A) and the silane coupling agent having an acid anhydride structure in the molecule at such a ratio becomes more excellent in adhesiveness.
• the curable composition of the present invention may contain other components as long as the object of the present invention is not impaired.
• other components include fine particles, antioxidants, ultraviolet absorbers, light stabilizers, solvents and the like.
• the materials of the fine particles include metals; metal oxides; minerals; metal carbonates such as calcium carbonate and magnesium carbonate; metal sulfates such as calcium sulfate and barium sulfate; metal hydroxides such as aluminum hydroxide; aluminum silicate and silicic acid.
• metal silicates such as calcium and magnesium silicate; inorganic components such as silica; silicones; organic components such as acrylic polymers; and the like.
• the fine particles used may have a modified surface.
• fine particles can be used alone or in combination of two or more.
• the content of the fine particles is not particularly limited, but is usually preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 35% by mass or less, based on the component (A).
• Antioxidants are added to prevent oxidative deterioration during heating.
• examples of the antioxidant include phosphorus-based antioxidants, phenol-based antioxidants, sulfur-based antioxidants, and the like.
• Examples of phosphorus-based antioxidants include phosphites, oxaphosphaphenanthrene oxides, and the like.
• Examples of the phenolic antioxidant include monophenols, bisphenols, and high molecular weight phenols.
• Examples of the sulfur-based antioxidant include dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate and the like.
• antioxidants can be used alone or in combination of two or more.
• the content of the antioxidant is not particularly limited, but is usually 10% by mass or less with respect to the component (A).
• the UV absorber is added for the purpose of improving the light resistance of the obtained cured product.
• examples of the ultraviolet absorber include salicylic acids, benzophenones, benzotriazoles, hindered amines and the like.
• the ultraviolet absorber may be used alone or in combination of two or more.
• the content of the ultraviolet absorber is not particularly limited, but is usually 10% by mass or less with respect to the component (A).
• the light stabilizer is added for the purpose of improving the light resistance of the obtained cured product.
• the light stabilizer include poly [ ⁇ 6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl ⁇ ⁇ (2,2,6). , 6-Tetramethyl-4-piperidin) imino ⁇ hexamethylene ⁇ (2,2,6,6-tetramethyl-4-piperidine) imino ⁇ ] and other hindered amines.
• These light stabilizers can be used alone or in combination of two or more.
• the content of the light stabilizer is usually 20% by mass or less with respect to the component (A).
• the solvent is not particularly limited as long as it can dissolve or disperse the components of the curable composition of the present invention.
• the solvent include acetates such as diethylene glycol monobutyl ether acetate and 1,6-hexanediol diacetate; tripropylene glycol-n-butyl ale; glycerin diglycidyl ether, butanediol diglycidyl ether, diglycidyl aniline, neopentyl glycol glycidyl.
• Diglycidyl ethers such as ethers, cyclohexanedimethanol diglycidyl ethers, alkylene diglycidyl ethers, polyglycol diglycidyl ethers, polypropylene glycol diglycidyl ethers; triglycidyl ethers such as trimethylolpropane triglycidyl ethers and glycerin triglycidyl ethers; Examples thereof include vinylhexene oxides such as 4-vinylcyclohexene monooxide, vinylcyclohexendioxide, and methylated vinylcyclohexendioxide.
• the solvent can be used alone or in combination of two or more.
• the solid content concentration is preferably 50% by mass or more and less than 100% by mass, more preferably 60 to 90% by mass, still more preferably 65.
• the amount is up to 85% by mass.
• the curable composition of the present invention can be prepared, for example, by mixing the above-mentioned component (A), component (B), and, if desired, other components at a predetermined ratio and defoaming.
• the mixing method and defoaming method are not particularly limited, and known methods can be used.
• the curable composition of the present invention contains a polysilsesquioxane compound (A) and a thermoacid generator. Therefore, the curable composition of the present invention is excellent in curability and storage stability.
• the curable composition of the present invention has excellent curability. That is, when a sample of the curable composition is put on a stainless steel plate heated to 150 ° C. and stirred using an automatic curing time measuring device (manufactured by Cyber Co., Ltd., trade name "Madoka"), the stirring torque increases. .. Therefore, the curability can be quantified by measuring the time until the stirring torque reaches 0.049 N ⁇ cm.
• the time until the stirring torque reaches 0.049 N ⁇ cm is preferably 1000 seconds or less, more preferably 800 seconds or less, still more preferably 500 seconds or less.
• the curable composition of the present invention has excellent curability. Therefore, by using the curable composition of the present invention, the working time can be shortened as compared with the case of using the conventional curable composition.
• the excellent storage stability of the curable composition of the present invention can be confirmed, for example, by the method described in Examples. That is, using a rheometer with a cone plate having a radius of 50 mm and a cone angle of 0.5 °, the viscosity at 25 ° C. and a shear rate of 2s-1 was measured to obtain the initial viscosity, and then the sample was measured at 25 ° C. Let stand for 24 hours, measure the viscosity under the same conditions, and obtain the viscosity after standing. Storage stability can be quantified by calculating the rate of increase in viscosity from the obtained measured values based on the following formula.
• [Viscosity increase rate] [Viscosity after standing] / [Initial viscosity]
• the viscosity increase rate under the above measurement conditions is preferably 1.40 or less, more preferably 1.25 or less, and even more preferably 1.10 or less.
• the curable composition of the present invention has excellent storage stability. Therefore, the curable composition of the present invention can be stored for a long period of time without freezing or refrigerating.
• the cured product of the present invention is obtained by curing the curable composition of the present invention.
• Examples of the method for curing the curable composition of the present invention include heat curing.
• the heating temperature at the time of curing is usually 80 to 140 ° C, more preferably 90 to 120 ° C.
• the heating time is usually 30 minutes to 5 hours, preferably 1 to 3 hours.
• the cured product of the present invention preferably has excellent heat resistance and adhesiveness.
• the heat resistance and adhesiveness of the cured product can be evaluated, for example, as follows. That is, a predetermined amount of the curable composition of the present invention is applied to the mirror surface of the silicon chip, the coated surface is placed on the adherend, pressure-bonded, and heat-treated to cure. This is left on the measurement stage of a bond tester preheated to a predetermined temperature (for example, 100 ° C.) for 30 seconds, and from a position at a height of 100 ⁇ m from the adherend, in the horizontal direction (shear direction) with respect to the adhesive surface. Apply stress and measure the adhesive force between the test piece and the adherend.
• a predetermined temperature for example, 100 ° C.
• the adhesive strength of the cured product of the present invention is preferably 15N / 4mm 2 or more, more preferably 25N / 4mm 2 or more, and 30N / 4mm 2 or more under the measurement conditions described in the examples. Is even more preferable.
• “4 mm 2” means "2 mm square", that is, 2 mm ⁇ 2 mm (a square having a side of 2 mm).
• a cured product having excellent heat resistance and adhesiveness can be efficiently formed by, for example, curing a curable composition containing the component (C).
• a cured product having excellent heat resistance and adhesiveness is more preferably used as an optical element fixing material.
• the method of the present invention is a method of using the curable composition of the present invention as an adhesive for an optical element fixing material or a sealing material for an optical element fixing material.
• the optical element include a light emitting element such as an LED and an LD, a light receiving element, a composite optical element, and an optical integrated circuit.
• the curable composition of the present invention can be suitably used as an adhesive for an optical element fixing material.
• the composition is applied to one or both adhesive surfaces of a material to be adhered (optical element and its substrate, etc.). , After crimping, heat-curing to firmly bond the materials to be bonded to each other.
• the amount of the curable composition of the present invention applied is not particularly limited as long as it can firmly bond the materials to be bonded to each other by curing.
• the thickness of the coating film of the curable composition is 0.5 to 5 ⁇ m, preferably 1 to 3 ⁇ m.
• Substrate materials for adhering optical elements include glasses such as soda lime glass and heat-resistant hard glass; ceramics; sapphire; iron, copper, aluminum, gold, silver, platinum, chromium, titanium and alloys of these metals. , Stainless steel (SUS302, SUS304, SUS304L, SUS309, etc.); polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, ethylene-vinyl acetate copolymer, polystyrene, polycarbonate, polymethylpentene, polysulfone, polyether ether ketone , Polyethersulfone, polyphenylene sulfide, polyetherimide, polyimide, polyamide, acrylic resin, norbornene-based resin, cycloolefin resin, synthetic resin such as glass epoxy resin; and the like.
• glasses such as soda lime glass and heat-resistant hard glass
• ceramics such as soda lime glass and heat-resistant hard glass
• sapphire iron,
• the heating temperature at the time of heat curing depends on the curable composition used and the like, but is usually 80 to 150 ° C, more preferably 90 to 130 ° C.
• the heating time is usually 30 minutes to 5 hours, preferably 1 to 3 hours.
• the curable composition of the present invention can be suitably used as a sealing material for an optical element fixing material.
• a method of using the curable composition of the present invention as a sealing material for an optical element fixing material for example, the composition is molded into a desired shape to obtain a molded body containing an optical element, and then this Examples thereof include a method of manufacturing an optical device encapsulant by heating and curing the material.
• the method for molding the curable composition of the present invention into a desired shape is not particularly limited, and a known molding method such as a normal transfer molding method or a casting method can be adopted.
• the heating temperature at the time of heat curing depends on the curable composition used and the like, but is usually 80 to 150 ° C, more preferably 90 to 130 ° C.
• the heating time is usually 30 minutes to 5 hours, preferably 1 to 3 hours.
• the mass average molecular weight (Mw) and the number average molecular weight (Mn) of the polysilsesquioxane compound obtained in the production example were set to standard polystyrene conversion values and measured with the following equipment and conditions.
• Solvent tetrahydrofuran Injection amount: 80 ⁇ l Measurement temperature: 40 ° C Flow rate: 1 ml / min Detector: Differential refractometer
• the IR spectrum of the polysilsesquioxane compound obtained in the production example was measured using a Fourier transform infrared spectrophotometer (Spectrum100, manufactured by PerkinElmer).
• 29 Si-NMR measurement In order to investigate the repeating unit of the polysilsesquioxane compound obtained in the production example and its amount, 29 Si-NMR measurement was carried out under the following conditions. Equipment: AV-500 manufactured by Bruker Biospin 29 Si-NMR resonance frequency: 99.352 MHz Probe: 5 mm ⁇ solution Probe measurement temperature: Room temperature (25 ° C) Sample rotation speed: 20 kHz Measurement method: inverse gate decoupling method 29 Si flip angle: 90 ° 29 Si 90 ° pulse width: 8.0 ⁇ s Repeat time: 5s Number of integrations: 9200 observations Width: 30 kHz
• thermoacid generator For each thermoacid generator, use a differential scanning calorimeter (manufactured by TA Instruments; product name: DSC Q2000Auto) under the conditions of a starting temperature of 30 ° C, a measurement temperature range of 30 to 300 ° C, and a heating rate of 10 ° C / min. The differential scanning calorimetry was performed using this. From the obtained DSC curve, the peak temperature (° C.) of the maximum endothermic peak was calculated, and the acid generation temperature of each thermoacid generator was obtained.
• DSC Q2000Auto differential scanning calorimeter
• the mass average molecular weight (Mw) of PSQ (A1) was 7,800, and the molecular weight distribution (Mw / Mn) was 4.52.
• the IR spectrum data of PSQ (A1) is shown below. Si-CH 3 : 1272 cm -1 , 1409 cm -1 , Si-O: 1132 cm -1 Moreover, as a result of performing 29 Si-NMR spectrum measurement, the peak integral value ratio of T1, T2, and T3 was 0:24:76.
• the reaction solution was concentrated to 50 ml with an evaporator, 100 ml of ethyl acetate was added to the concentrate, and the mixture was neutralized with saturated aqueous sodium hydrogen carbonate solution. After allowing to stand for a while, the organic layer was separated. Then, the organic layer was washed twice with distilled water and then dried over anhydrous magnesium sulfate. After the magnesium sulfate was filtered off, the filtrate was concentrated to 50 ml with an evaporator, the obtained concentrate was added dropwise to a large amount of n-hexane to precipitate, and the precipitate was separated by decantation.
• PSQ (A3) polysilsesquioxane compound
• Mw mass average molecular weight
• Mw / Mn molecular weight distribution
• Thermoacid generator (B1) Compound represented by the following formula (acid generation temperature: 150 ° C)
• Thermoacid generator (B2) Compound represented by the following formula (acid generation temperature: 125 ° C)
• Thermoacid generator (B3) Compound represented by the following formula (acid generation temperature: 125 ° C)
• Curing accelerator (X1) Hydrochloric acid curing accelerator (X2): Ti complex
• Silane Coupling Agent (C1) 1,3,5-N-Tris [3- (trimethoxysilyl) propyl] Isocyanurate Silane Coupling Agent (C2): 3- (Trimethoxysilyl) Propyl succinic anhydride
• B1 thermoacid generator
• Examples 2 to 19, Comparative Examples 1 to 7 A curable composition was obtained in the same manner as in Example 1 except that each component was changed to that shown in Table 1.
• the curing time of the curable composition was measured by the following method using an automatic curing time measuring device "Madoka" (manufactured by Cyber Co., Ltd.). A 0.30 mL sample was placed on a stainless steel plate heated to 150 ° C. and stirred. Since the stirring torque increases with time, the time (seconds) until the stirring torque reaches 0.049 N ⁇ cm was measured.
• the stirring conditions are as follows. ⁇ Rotation speed of stirring blade: 200 rpm ⁇ Revolution speed of stirring blade: 80 rpm (The stirring blade is made of polytetrafluoroethylene.) ⁇ Gap (distance between heating plate and stirring blade): 0.3 mm
• the curable compositions of Examples 1 to 19 were obtained in a short time of 1000 seconds or less, and are excellent in curability. Further, the cured products obtained in Examples 1 to 19 have a small viscosity increase rate and are excellent in storage stability. On the other hand, the curable compositions of Comparative Examples 1 to 3 and Comparative Example 6 are inferior in curability. Further, the curable compositions of Comparative Examples 4 and 5 are gelled due to a large viscosity increase rate and are inferior in storage stability.

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