WO2023234084A1 - Composition d'organopolysiloxane durcissable à température ambiante de type à deux composants et divers articles contenant ladite composition - Google Patents

Composition d'organopolysiloxane durcissable à température ambiante de type à deux composants et divers articles contenant ladite composition Download PDF

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WO2023234084A1
WO2023234084A1 PCT/JP2023/018853 JP2023018853W WO2023234084A1 WO 2023234084 A1 WO2023234084 A1 WO 2023234084A1 JP 2023018853 W JP2023018853 W JP 2023018853W WO 2023234084 A1 WO2023234084 A1 WO 2023234084A1
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carbon atoms
groups
room temperature
mass
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晃嗣 藤原
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信越化学工業株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/07—Aldehydes; Ketones
    • 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
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5425—Silicon-containing compounds containing oxygen containing at least one C=C bond
    • 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
    • C08K5/544—Silicon-containing compounds containing nitrogen
    • 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
    • C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions 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; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • 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
    • C09J183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers

Definitions

  • the present invention provides a room-temperature-curable organopolysiloxane composition (room-temperature-curable silicone rubber) that is cured at room temperature (23°C ⁇ 15°C) by atmospheric humidity (moisture) to give a cured silicone rubber product (silicone elastomer elastomer).
  • the composition relates to a hydrolyzed polysiloxane having two hydrolyzable silyl-vinylene groups on the same silicon atom, using as a base polymer an organopolysiloxane in which both ends of the molecular chain are capped with hydrolyzable silyl groups.
  • the first agent is a degradable organosilane compound as a crosslinking agent (curing agent)
  • the base polymer is an organopolysiloxane in which both ends of the molecular chain are blocked with hydroxyl groups to produce a specific hydrolyzable organosilane containing an amino functional group.
  • a two-component room temperature curable organopolysiloxane composition that has good curability (fast curability) and excellent adhesiveness, and is capable of providing a cured silicone rubber product that is highly durable even under moist heat conditions;
  • the present invention also relates to adhesives, sealants, and coatings containing the composition.
  • Room-temperature-curing (RTV) silicone rubber compositions room-temperature-curing organopolysiloxane compositions that crosslink and harden when exposed to moisture are easy to handle and have excellent weather resistance and electrical properties, so they are used as sealants for building materials. It is suitable for a variety of uses such as materials, adhesives and coating agents (sealants) in the electrical and electronic fields.
  • a typical room-temperature curable organopolysiloxane composition consists of a diorganopolysiloxane (base polymer) having a silanol group (a hydroxyl group bonded to a silicon atom) or an alkoxysilyl group at the end of the molecular chain, a curing agent, an alkoxysiloxane group containing an aminoalkyl group, etc. It contains silane and a curing catalyst, and various fillers are added as necessary to impart flame retardancy, thermal conductivity, tensile strength, etc.
  • Oxime-free room-temperature-curable organopolysiloxane compositions known as general architectural and structural sealants, are widely used due to their curability, durability, and adhesion to various adherends.
  • acetic acid-depleted room-temperature-curable organopolysiloxane compositions are commonly used as sealants for buildings and structures, and are known to have excellent curability and adhesive properties, and to show slight discoloration when exposed to UV irradiation.
  • workability is poor due to acetic acid generated during curing.
  • a dealcoholization type room temperature curable organopolysiloxane composition is not easy to prepare compared to the above-mentioned oxime removal type or acetic acid removal type room temperature curable organopolysiloxane composition.
  • an organopolysiloxane having silanol groups at both ends of the molecular chain is used as a base polymer, it is necessary to alkoxysilylate the silanol groups (terminate them with an alkoxysilyl group), but the reaction rate is slower than that of the above-mentioned deoxime type.
  • An organic tin compound or an organic titanium compound is generally known as a curing catalyst for a dealcoholization type room temperature curable organopolysiloxane composition.
  • organic tin compounds there are concerns about their adverse effects on the environment and the human body due to their toxicity.
  • organic titanium compounds although no toxicity problems have been confirmed yet, there are still problems such as the prepared room-temperature-curable organopolysiloxanes turning yellow over time.
  • Typical examples of dealcoholization-type room-temperature-curable organopolysiloxanes include compositions containing a silanol group-terminated polyorganosiloxane, an alkoxysilane, and an organic titanium compound, and an alkoxysilyl group-terminated polyorganosiloxane, an alkoxysilane, and an alkoxytitanium compound.
  • a composition comprising a linear polyorganosiloxane terminal-capped with an alkoxysilyl group via a silethylene group, an alkoxysilane, and an alkoxytitanium, further comprising a silanol-terminated polyorganosiloxane or Examples include compositions containing an alkoxysilyl end-capped polyorganosiloxane and an alkoxy- ⁇ -silyl ester compound (Patent Documents 1 to 4).
  • the room-temperature-curable organopolysiloxanes described in these patent documents have a certain degree of storage stability, water resistance, and humidity resistance, but do not yet satisfy all of these required properties. Furthermore, the fast curing properties were still insufficient.
  • Patent Document 5 discloses a dealcoholization-type room-temperature-curable organosiloxane composition, which uses an organosilane compound having a hydrolyzable silyl-vinylene group as a crosslinking agent, and is a two-component type with excellent fast curing properties.
  • organosiloxane composition that cures quickly at mold room temperature. Although there is discussion about quick curing properties, there is no discussion about durability to cured rubber.
  • the purpose of the present invention is to provide excellent fast curing and adhesive properties as well as good durability without adding metal condensation catalysts that have a large environmental impact and are commonly used in conventional room temperature curable organopolysiloxane compositions.
  • An object of the present invention is to provide a two-component room-temperature-curable organopolysiloxane composition, an adhesive, a sealing agent, and a coating agent that can provide a cured product having (heat resistance, moisture resistance).
  • the main material is an organopolysiloxane in which both ends of the molecular chain are capped with hydrolyzable silyl groups with or without sylalkylene groups.
  • the first agent is a hydrolyzable organosilane compound having two hydrolyzable silyl-vinylene groups on the same silicon atom as a crosslinking agent (curing agent), and the organosilane compound has two hydrolyzable silyl-vinylene groups on the same silicon atom.
  • Polysiloxane is used as the main agent (base polymer), a specific amino-functional group-containing hydrolyzable organosilane compound is blended as a condensation catalyst, and a second component is further blended with an organic compound having a ketone group in a specific compounding ratio.
  • RTV room temperature curable
  • the present invention provides the following two-component room temperature curable organopolysiloxane composition, adhesive, sealant, and coating agent.
  • R 1 is independently an unsubstituted or halogen-substituted monovalent hydrocarbon group having 1 to 10 carbon atoms
  • n is a number of 10 or more
  • X is independently an oxygen atom or a halogen-substituted monovalent hydrocarbon group having 1 to 4 carbon atoms.
  • R 2 is independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms, and a is independently 0 or 1 for each bonded silicon atom.
  • B 0.1 to 10 parts by mass of a hydrolyzable organosilane compound having two hydrolyzable silyl-vinylene groups on the same silicon atom represented by the following general formula (2), (In the formula, R 3 is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and R 4 is independently an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, or an unsubstituted or substituted alkyl group having 3 to 20 carbon atoms.
  • Y represents a monovalent or divalent hydrocarbon group having 1 to 15 carbon atoms containing two or more nitrogen atoms in its structure
  • Z represents a monovalent or divalent hydrocarbon group having 1 to 15 carbon atoms that may contain a hetero atom.
  • R is one or more selected from a hydrolyzable group having 1 to 6 carbon atoms and a monovalent hydrocarbon group having 1 to 6 carbon atoms. It is a monovalent group, and among the three R's bonded to the silicon atom, at least two R's are hydrolyzable groups.
  • the present invention aims to provide a cured product with durability (heat resistance, moisture resistance) without adding a metal condensation catalyst that has a large environmental impact and is commonly used in conventional room temperature curable organopolysiloxane compositions. It is possible to provide a two-component room temperature curable (RTV) silicone rubber composition with excellent fast curing properties and adhesive properties. Accordingly, the compositions of the present invention are useful as adhesives, sealants, and coatings.
  • Component (A) of the organopolysiloxane composition of the present invention acts as a main agent (base polymer) in the composition of the present invention, and is represented by the following general formula (1), and has both ends of the molecular chain silyl.
  • Hydrolysis that has an organooxy group bonded to two or three silicon atoms as a hydrolyzable group through an alkylene group (when X is an alkylene group) or without (when X is an oxygen atom) It is a linear organopolysiloxane blocked with silyl groups.
  • R 1 is independently an unsubstituted or halogen-substituted monovalent hydrocarbon group having 1 to 10 carbon atoms
  • n is a number of 10 or more
  • X is independently an oxygen atom or a halogen-substituted monovalent hydrocarbon group having 1 to 4 carbon atoms.
  • It is an alkylene group
  • R 2 is independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms
  • a is independently 0 or 1 for each bonded silicon atom.
  • R 1 is an unsubstituted or halogen-substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, such as a methyl group, ethyl group, propyl group, isopropyl group.
  • alkyl groups such as butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group; cyclopentyl group , cycloalkyl groups such as cyclohexyl group; alkenyl groups such as vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, pentenyl group, hexenyl group, cyclohexenyl group; phenyl group, tolyl group, xylyl group, ⁇ - , ⁇ -naphthyl group; aralkyl groups such as benzyl group, 2-phenylethyl group, 3-phenylpropyl group, and groups in which the hydrogen
  • n in the above formula (1) is a number of 10 or more, preferably a number of 10 to 2,000, more preferably a number of 20 to 1,500, even more preferably a number of 30 to 1,000, and a number of 50 to 1,000. A number of 800 is particularly preferred.
  • the value of n is a number such that the viscosity of the diorganopolysiloxane of component (A) at 23°C is in the range of 25 to 500,000 mPa ⁇ s, preferably in the range of 500 to 100,000 mPa ⁇ s. It is preferable.
  • n( which is the repeating number of bifunctional diorganosiloxane units represented by ((R 1 ) 2 SiO 2/2 ) constituting the main chain of the diorganopolysiloxane of component (A)
  • the degree of polymerization can usually be determined as the number average degree of polymerization (or number average molecular weight) in terms of polystyrene in gel permeation chromatography (GPC) analysis using toluene or the like as a developing solvent. Further, the viscosity can usually be measured at 23° C. using a rotational viscometer (eg, BL type, BH type, BS type, cone plate type, rheometer, etc.).
  • X is independently an oxygen atom or an alkylene group having 1 to 4 carbon atoms, and examples of the alkylene group having 1 to 4 carbon atoms include a methylene group, an ethylene group, a trimethylene group, and a tetramethylene group.
  • Straight-chain alkylene groups such as, and isomers thereof, such as branched alkylene groups such as propylene group (methylethylene group) and 2-methyl-trimethylene group, etc. are applicable.
  • X an ethylene group is particularly preferable.
  • ethylene group In the case of an ethylene group, it is very versatile because it can be easily produced by subjecting an ⁇ , ⁇ -divinyl-terminated organopolysiloxane to a hydrosilylation addition reaction of the corresponding hydrosilane in the presence of a metal catalyst.
  • R 2 is independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group.
  • a is independently 0 or 1 for each bonded silicon atom, preferably 0.
  • the linear organopolysiloxane having hydrolyzable silyl groups endblocked at both molecular chain ends of component (A) may be used alone or in combination of two or more.
  • Component (B) of the organopolysiloxane composition of the present invention is a hydrolyzable organosilane compound having two hydrolyzable silyl-vinylene groups on the same silicon atom (i.e., Two silicon atoms of the hydrolyzable silyl group (-Si(R 3 ) b (OR 4 ) 3-b ) exist in the molecule, and the silicon atoms of the diorganosilylene group (-Si(R 3 )
  • a hydrolyzable organotrisilane compound in which the silicon atom of 2- ) is linked with a vinylene group (-CH CH-), which acts as a crosslinking agent (curing agent) in the composition of the present invention. It is something.
  • R 3 is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms
  • R 4 is independently an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, or an unsubstituted or substituted alkyl group having 3 to 20 carbon atoms. is an unsubstituted or substituted cycloalkyl group.
  • b is an integer from 0 to 2.
  • the substituted or unsubstituted monovalent hydrocarbon group of R 3 has about 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and is the same. or may be different, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group Alkyl groups such as 2-ethylhexyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group,
  • Examples include groups substituted with halogen atoms, cyano groups, etc., such as 3-chloropropyl group, 3,3,3-trifluoropropyl group, and 2-cyanoethyl group.
  • groups substituted with halogen atoms, cyano groups, etc. such as 3-chloropropyl group, 3,3,3-trifluoropropyl group, and 2-cyanoethyl group.
  • methyl group, ethyl group, and phenyl group are preferable, and methyl group and phenyl group are particularly preferable from the viewpoint of availability, productivity, and cost.
  • the unsubstituted or substituted alkyl group of R 4 has about 1 to 20 carbon atoms, preferably about 1 to 6 carbon atoms, more preferably about 1 to 4 carbon atoms, and is, for example, a methyl group, an ethyl group, Propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group , dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, and is, for example,
  • the unsubstituted or substituted cycloalkyl group has about 3 to 20 carbon atoms, preferably about 4 to 8 carbon atoms, more preferably about 5 to 6 carbon atoms, and includes, for example, a cyclopentyl group and a cyclohexyl group. Further, some or all of the hydrogen atoms of these alkyl groups and cycloalkyl groups may be substituted with halogen atoms such as F, Cl, Br, etc., cyano groups, etc. Examples include propyl group, 3,3,3-trifluoropropyl group, and 2-cyanoethyl group. Among these, from the viewpoint of hydrolyzability, R 4 is preferably a methyl group or an ethyl group, and a methyl group is particularly preferable.
  • b is each independently an integer of 0 to 2, but preferably 0 or 1 from the viewpoint of curability.
  • component (B) is shown below.
  • the hydrolyzable organosilane compound having two hydrolyzable silyl-vinylene groups on the same silicon atom as component (B) is, for example, a silane having two ethynyl groups on the same silicon atom, and twice the mole of alkoxyhydrosilane.
  • Hydrolyzable group-containing hydrosilanes such as the following can be easily produced by an addition reaction using a hydrosilylation reaction. This reaction formula is expressed, for example, by the following formula [1].
  • the addition reaction catalyst used in adding the alkoxyhydrosilane includes platinum group metal catalysts, such as platinum-based, palladium-based, rhodium-based, and ruthenium-based catalysts, with platinum-based catalysts being particularly preferred.
  • platinum-based materials include platinum black, solid platinum supported on a carrier such as alumina or silica, chloroplatinic acid, alcohol-modified chloroplatinic acid, a complex of chloroplatinic acid and an olefin, or a complex of platinum and vinylsiloxane. Examples include complexes of.
  • the amount of platinum to be used may be a so-called catalytic amount, and for example, it can be used in a mass of 0.1 to 1,000 ppm, particularly 0.5 to 100 ppm in terms of platinum group metal, relative to the alkoxyhydrosilane.
  • This reaction is generally carried out at a temperature of 50 to 120°C, particularly 60 to 100°C, for 0.5 to 12 hours, particularly 1 to 6 hours, and can be carried out without using a solvent, but as mentioned above.
  • An appropriate solvent such as toluene or xylene may be used as necessary, as long as it does not adversely affect the addition reaction.
  • component (B) used in the present invention also has Z-form (cis-form), which does not adversely affect its properties, so these can be separated. It can be used without.
  • hydrolyzable organosilane compounds having two hydrolyzable silyl-vinylene groups such as alkoxysilyl-vinylene groups on the same silicon atom in the general formula (2) are, for example, those represented by the following structural formula:
  • component (B) one type of these can be used alone or two or more types can be used in combination.
  • the hydrolyzable organosilane compound as component (B) is used in an amount of 0.1 to 10 parts by mass, preferably 1 to 10 parts by mass, based on 100 parts by mass of organopolysiloxane as component (A). If it is less than 0.1 parts by mass, sufficient crosslinking will not be obtained and the composition will not have the desired fast-curing properties, and if it exceeds 10 parts by mass, the mechanical properties of the resulting rubber will deteriorate, Problems such as being economically disadvantaged may occur. Note that the hydrolyzable organosilane compound as the component (B) may be used alone or in combination of two or more.
  • the total amount of component (A) and component (B) in the first agent may be 100% by mass, but is preferably 20 to 95% by mass, more preferably 30 to 90% by mass. .
  • Component (C) is a linear diorganopolysiloxane whose molecular chain ends are blocked with silanol groups (hydroxyl groups bonded to silicon atoms), and is the main component (base polymer) of the second component of the composition of the present invention. It acts as a.
  • R 1 is independently an unsubstituted or halogen-substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and specific examples are those exemplified for R 1 in general formula (1) of component (A). It is similar to n is a number of 10 or more, preferably a number of 10 to 2,000, more preferably a number of 50 to 1,500, and still more preferably a number of 100 to 1,000, particularly when the diorganopolysiloxane is heated at 23°C.
  • the viscosity is 25 to 500,000 mPa ⁇ s, preferably 50 to 100,000 mPa ⁇ s, more preferably 100 to 50,000 mPa ⁇ s.
  • the viscosity is a value measured at 23°C using a rotational viscometer (for example, BL type, BH type, BS type, cone plate type, rheometer), etc.
  • Component (C) may be used alone or in combination of two or more.
  • Component (D) is an important compound that acts as a condensation catalyst in the present room temperature curable organopolysiloxane composition, and specifically contains 3 or more nitrogen atoms, preferably 3 to 6 nitrogen atoms in one molecule, More preferably a hydrolyzable organosilane compound containing 3 to 5 amino functional groups and/or a partially hydrolyzed condensate thereof, particularly a catalyst represented by the following general formula (4) or (4)'. Hydrolyzable organosilane compounds containing an amino functional group and/or partially hydrolyzed condensates thereof having a monovalent or divalent basic moiety (Y) that exhibits a function are preferred.
  • Y represents a monovalent or divalent hydrocarbon group having 1 to 15 carbon atoms containing two or more nitrogen atoms in its structure, and Z does not contain a heteroatom.
  • Z represents an unsubstituted or substituted divalent hydrocarbon group having 1 to 10 carbon atoms, which may be substituted or unsubstituted.
  • R is one or more monovalent groups selected from a hydrolyzable group having 1 to 6 carbon atoms and a monovalent hydrocarbon group having 1 to 6 carbon atoms; At least two of R are hydrolyzable groups.
  • the monovalent or divalent basic moiety (Y) that exhibits a catalytic function has 2 or more nitrogen atoms, preferably 2 to 5, or more, in its structure. It preferably represents a monovalent or divalent hydrocarbon group having 2 to 4 carbon atoms and having 1 to 15 carbon atoms, and among the basic moieties (Y), the monovalent group is, for example, represented by the following formula (5).
  • divalent groups such as groups derived from 1,5,7-triazabicyclo[4.4.0]dec-5-ene include N-substituted or non-substituted groups represented by the following formula (6). Examples include substituted guanidyl groups. Note that in the following formulas (5) and (6), the wavy line portion indicates a bonding site with the nitrogen atom of formula (4) or formula (4)'.
  • R 5 to R 8 each independently represent a hydrogen atom or a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, an alkenyl group, or an aryl group, such as a methyl group
  • examples include alkyl groups such as ethyl group and propyl group; cyclic alkyl groups such as cyclohexyl group; alkenyl groups such as vinyl group and allyl group; and aryl groups such as phenyl group and tolyl group.
  • methyl group, ethyl group, and phenyl group are preferred, and methyl group is particularly preferred.
  • R 5 to R 8 may be the same or different.
  • R is an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a tert-butoxy group, a vinyloxy group, an allyloxy group.
  • an alkenyloxy group such as a propenoxy group, an isopropenoxy group, a ketoxime group such as a dimethylketoxime group, a diethylketoxime group, a methylethylketoxime group, an acyloxy group such as an acetoxy group, etc. having 1 to 6 carbon atoms, preferably 1 to 6 carbon atoms.
  • hydrolyzable groups that is, groups that can bond to silicon atoms to form Si-O-C bonds
  • alkyl groups such as methyl groups and ethyl groups
  • alkenyl groups such as vinyl groups
  • phenyl groups etc.
  • at least two, preferably three R's are hydrolyzable groups.
  • the hydrolyzable silyl group (-SiR 3 ) is, for example, trimethoxysilyl group, methyldimethoxysilyl group, vinyldimethoxysilyl group, phenyldimethoxysilyl group, trimethoxysilyl group, Alkoxysilyl group such as ethoxysilyl group; Penoxysilyl group: Ketoxime silyl groups such as tris(dimethylketoxime)silyl group, tris(diethylketoxime)silyl group, tris(ethylmethylketoxime)silyl group, and the like.
  • Z is a straight chain, branched, carbon atom having 1 to 10 carbon atoms, particularly 3 to 6 carbon atoms, which may contain a hetero atom such as an oxygen atom or a nitrogen atom.
  • it represents an unsubstituted or substituted divalent hydrocarbon group such as a cyclic alkylene group, alkenylene group, arylene group, or a combination thereof.
  • Z examples include alkylene groups such as methylene group, ethylene group, trimethylene group, propylene group, tetramethylene group, hexamethylene group, octamethylene group, decamethylene group, and 2-methylpropylene group; arylene groups such as phenylene group; Examples include groups in which these alkylene groups and arylene groups are bonded, and the above-mentioned alkylene groups with intervening ketones, esters, amide, etc., but preferred are methylene groups, ethylene groups, trimethylene groups, propylene groups, and propylene groups via amide bonds. etc., and trimethylene group is particularly preferred.
  • amino-functional group-containing hydrolyzable organosilane represented by general formula (4) or general formula (4)' include those shown by general formulas (7) to (12) below. can. Note that Me, Et, and Ph represent a methyl group, an ethyl group, and a phenyl group, respectively.
  • the blending amount of component (D) is 0.1 to 10 parts by mass, preferably 0.1 to 5 parts by mass, and more preferably 0.5 to 5 parts by mass, per 100 parts by mass of component (C). . If it is less than 0.1 part by mass, it may not function as the intended curing catalyst. If it exceeds 10 parts by mass, it is not preferable because it is disadvantageous in terms of cost and curability decreases.
  • Component (E) is an organic compound (ketones) having a ketone group, and specific examples include linear ketone compounds such as acetone, 2-butanone, 3-pentanone, and 2-heptanone; methyl isobutyl ketone, 4- Branched ketone compounds such as methylhexan-2-one, 4-methylheptan-3-one, 6-methylheptan-3-one; cyclopentanone, cyclohexanone, cycloheptanone, 3-methylcyclopentan-1-one , 3,3-dimethylcyclopentan-1-one, 2-ethylcyclopentan-1-one, 3-methylcyclohexan-1-one, 4-methylcyclohexan-1-one, 2,5-dimethylcyclohexan-1-one Cyclic ketone compounds such as cyclopentane-1,3-dione, cyclopentane-1,2-dione, 3-methylcyclopentane-1,2-dione
  • the blending amount of component (E) is 0.1 to 5 parts by mass, preferably 0.1 to 3 parts by mass, and more preferably 0.5 to 2 parts by mass, per 100 parts by mass of component (C). . If the amount is less than 0.1 part by mass, the desired curability may not be achieved. If it exceeds 5 parts by mass, it is not preferable because it is not only disadvantageous in terms of cost, but also causes strong bleeding and odor from the cured rubber.
  • the total amount of component (C), component (D), and component (E) in the second agent may be 100% by mass, but preferably 20 to 95% by mass, and 30 to 90% by mass. It is more preferable that there be.
  • a silane coupling agent from nitrogen, sulfur, and oxygen in one molecule
  • a hydrolyzable silane compound such as an alkoxysilane having a monovalent hydrocarbon group having a functional group containing a selected heteroatom (however, excluding a guanidyl group), or a so-called carbon functional silane compound) is used as an adhesion imparting agent.
  • silane coupling agent examples include silane compounds having an alkoxysilyl group or an alkenoxysilyl group as a hydrolyzable group, such as vinyltris( ⁇ -methoxyethoxy)silane, ⁇ -methacryloxypropyltrimethoxysilane, ⁇ - (3,4-epoxycyclohexyl)ethyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropylmethyldiethoxysilane, N- ⁇ -(aminoethyl) ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, 3-(N-aminomethylbenzylamino)propyltrimethoxysilane, N,N'-bis[3-(trimethoxysilyl)propyl]ethylenediamine, N,N-bis[3-
  • a silane coupling agent When blending a silane coupling agent, it may be blended in either the first part or the second part, but it is preferably blended in the first part, and the blending amount is per 100 parts by mass of component (A). It is usually 0.1 to 20 parts by weight, preferably 0.1 to 15 parts by weight, particularly preferably 0.1 to 10 parts by weight. If it is less than 0.1 parts by mass, sufficient adhesiveness may not be obtained, and if it exceeds 20 parts by mass, good mechanical properties may not be obtained or it may be disadvantageous in terms of price.
  • an inorganic filler may be added to the composition as an optional component.
  • These inorganic fillers may not be surface-treated or may be surface-treated with a known treatment agent.
  • a hydrolyzable group-containing polysiloxane described in JP-A No. 2000-256558 is preferred, but the treatment agent is not limited thereto.
  • silica-based fillers such as ground silica, fumed silica, wet silica, and crystalline silica, or calcium carbonate are preferred.
  • the blending amount is 1 to 400 parts by mass per 100 parts by mass of components (A) to (C). Parts by weight are preferred, more preferably 1 to 350 parts by weight, particularly preferably 1 to 300 parts by weight. If the amount is less than 1 part by mass, it may be difficult to obtain a cured product having the desired rubber strength and rubber elasticity. If the amount exceeds 400 parts by mass, it becomes difficult to knead with the components (A) to (C), and it may be difficult to prepare a good room-temperature-curable organopolysiloxane composition.
  • the two-component room-temperature-curable organopolysiloxane composition of the present invention may contain various additives as optional components.
  • additives known additives may be added within a range that does not impair the purpose of the present invention.
  • polyether compounds as wetters and thixotropy improvers
  • non-reactive dimethyl silicone oil dimethyl polysiloxane blocked with trialkylsilyl groups at both ends of the molecular chain
  • isoparaffins trimethylsiloxy units as crosslinking density improvers [ (CH 3 ) 3 SiO 1/2 units]
  • organopolysiloxane resin having a three-dimensional network structure consisting of SiO 2 units.
  • colorants such as pigments, dyes, and optical brighteners; fungicides; antibacterial agents; non-reactive phenyl silicone oil (methylphenyl polysiloxane blocked with trialkylsilyl groups at both molecular chain ends), Bleed oil such as silicone oil (methyl (3,3,3-trifluoropropyl)polysiloxane blocked with trialkylsilyl groups at both ends of the molecular chain); Surface modifier such as organic liquid that is incompatible with silicone; and toluene Solvents such as , xylene, solvent volatile oils, cyclohexane, methylcyclohexane, and low boiling isoparaffins may also be added.
  • phenyl silicone oil methylphenyl polysiloxane blocked with trialkylsilyl groups at both molecular chain ends
  • Bleed oil such as silicone oil (methyl (3,3,3-trifluoropropyl)polysiloxane blocked with trialkylsilyl groups at
  • the two-component room-temperature fast-curing organopolysiloxane composition of the present invention comprises a first part containing component (A) and component (B), component (C), component (D) and ( and a second agent containing component E). Both the first part and the second part can be prepared by mixing the respective components according to a conventional method. The mixing method may be a conventional method, and the respective components may be mixed under reduced pressure.
  • the two-component room-temperature-curable organopolysiloxane composition of the present invention allows the first and second parts to be stored in an atmosphere that avoids moisture, and the first and second parts can be mixed in any desired combination.
  • the optional component may be blended in either the first part or the second part, or may be blended in either one or both.
  • the viscosity is a value measured by a rotational viscometer at 23° C.
  • the degree of polymerization indicates the number average degree of polymerization in terms of polystyrene in gel permeation chromatography analysis using toluene as a developing solvent.
  • compositions 1 to 6 were prepared by uniformly mixing the first agent and the second agent at a mixing ratio (volume ratio) of 1:1 using the combinations shown in Table 1 below.
  • the mixing method used a 250 ml x 250 ml cartridge manufactured by Mixpac.
  • compositions 1 to 6 were left to cure in a 23°C/50% RH environment for 3 days to a thickness of 3 mm to form a silicone rubber cured product (3 mm thick). ) was prepared, and a No. 2 dumbbell test piece was prepared according to JIS K 6249, and the hardness, elongation at cutting, and tensile strength were measured. In addition, the hardness was taken as the value of durometer A.
  • the composition was sandwiched and left in an environment of 23° C./50% RH for 3 days to cure the composition. Thereafter, each of the two aluminum substrates was pulled in the shear direction at a speed of 500 mm/min to determine the shear adhesive strength. The results are shown in Table 2.
  • compositions 1 to 4 all showed good adhesion.
  • compositions 5 and 6 showed higher values for hardness and tensile strength than compositions 1 to 4, but had low shear adhesive strength and poor adhesion.
  • compositions 1 to 4 had similar curability when compared with Compositions 5 and 6, both of which contained conventional organic tin.
  • compositions 1 to 4 tend to have a slight decrease in hardness, but the elongation and tensile strength at cutting tend to decrease slightly. There was no major change in strength, and it can be judged that the moisture resistance is good. The rate of change in physical properties was within 50% in all items. On the other hand, in compositions 5 and 6 containing organic tin, although the change in hardness was small compared to compositions 1 to 4, the elongation at break and tensile strength decreased significantly, and the rate of change was It became more than 50%.

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Abstract

La présente invention concerne une composition d'organopolysiloxane durcissable à température ambiante de type à deux composants qui présente à la fois d'excellentes propriétés de durcissement rapide et d'excellentes propriétés de liaison sans l'ajout d'un catalyseur de condensation à base de métal qui a une charge environnementale élevée, et qui est capable de fournir un produit durci ayant une bonne durabilité (résistance à la chaleur et résistance à l'humidité). La présente invention concerne une composition d'organopolysiloxane durcissable à température ambiante de type à deux composants qui est composée : d'un premier agent qui contient (A) un organopolysiloxane ayant à la fois des extrémités de chaîne moléculaire bloquées avec des groupes organo-oxy et (B) un composé organosilane hydrolysable ayant deux groupes silyle-vinylène hydrolysables sur le même atome de silicium ; et un second agent qui contient (C) un organopolysiloxane ayant à la fois des extrémités de chaîne moléculaire bloquées avec des groupes silanol, (D) un composé organosilane hydrolysable contenant un groupe fonctionnel amino ayant trois atomes d'azote ou plus dans chaque molécule et/ou un produit d'hydrolyse-condensation partielle de celui-ci, et (E) 0,1 à 5 parties en masse d'un composé organique ayant un groupe cétone.
PCT/JP2023/018853 2022-05-30 2023-05-22 Composition d'organopolysiloxane durcissable à température ambiante de type à deux composants et divers articles contenant ladite composition WO2023234084A1 (fr)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0649363A (ja) * 1992-08-04 1994-02-22 Shin Etsu Chem Co Ltd 室温硬化性オルガノポリシロキサン組成物
JP2000234057A (ja) * 1998-12-14 2000-08-29 Shin Etsu Chem Co Ltd 室温速硬化性組成物
JP2001107023A (ja) * 1999-07-30 2001-04-17 Three Bond Co Ltd 自動車用室温硬化性シール材組成物
JP2002226708A (ja) * 2001-01-30 2002-08-14 Three Bond Co Ltd 自動車用室温硬化性シール材組成物
WO2015093139A1 (fr) * 2013-12-17 2015-06-25 信越化学工業株式会社 Composition organopolysiloxane à plusieurs constituants durcissable à température ambiante, produit durci de ladite composition, et produit moulé comprenant ledit produit durci
WO2022009759A1 (fr) * 2020-07-07 2022-01-13 信越化学工業株式会社 Composition d'organopolysiloxane à durcissement rapide à température ambiante de type bicomposant, produit durci associé et article
WO2023068094A1 (fr) * 2021-10-19 2023-04-27 信越化学工業株式会社 Composition d'organopolysiloxane durcissable à température ambiante, adhésif, agent d'étanchéité et agent de revêtement

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0649363A (ja) * 1992-08-04 1994-02-22 Shin Etsu Chem Co Ltd 室温硬化性オルガノポリシロキサン組成物
JP2000234057A (ja) * 1998-12-14 2000-08-29 Shin Etsu Chem Co Ltd 室温速硬化性組成物
JP2001107023A (ja) * 1999-07-30 2001-04-17 Three Bond Co Ltd 自動車用室温硬化性シール材組成物
JP2002226708A (ja) * 2001-01-30 2002-08-14 Three Bond Co Ltd 自動車用室温硬化性シール材組成物
WO2015093139A1 (fr) * 2013-12-17 2015-06-25 信越化学工業株式会社 Composition organopolysiloxane à plusieurs constituants durcissable à température ambiante, produit durci de ladite composition, et produit moulé comprenant ledit produit durci
WO2022009759A1 (fr) * 2020-07-07 2022-01-13 信越化学工業株式会社 Composition d'organopolysiloxane à durcissement rapide à température ambiante de type bicomposant, produit durci associé et article
WO2023068094A1 (fr) * 2021-10-19 2023-04-27 信越化学工業株式会社 Composition d'organopolysiloxane durcissable à température ambiante, adhésif, agent d'étanchéité et agent de revêtement

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