US20090118401A1 - Curable Composition - Google Patents

Curable Composition Download PDF

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US20090118401A1
US20090118401A1 US11/992,404 US99240405A US2009118401A1 US 20090118401 A1 US20090118401 A1 US 20090118401A1 US 99240405 A US99240405 A US 99240405A US 2009118401 A1 US2009118401 A1 US 2009118401A1
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Prior art keywords
curable composition
silyl group
crosslinkable silyl
meth
component
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US11/992,404
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Inventor
Atsushi Saito
Masaki Ito
Shingo Kano
Hisashi Maekawahara
Naomi Okamura
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Cemedine Co Ltd
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Cemedine Co Ltd
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Assigned to CEMEDINE CO., LTD. reassignment CEMEDINE CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ITO, MASAKI, KANO, SHINGO, MAEKAWAHARA, HISASHI, OKAMURA, NAOMI, SAITO, ATSUSHI
Publication of US20090118401A1 publication Critical patent/US20090118401A1/en
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    • 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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/062—Copolymers with monomers not covered by C09J133/06
    • C09J133/068—Copolymers with monomers not covered by C09J133/06 containing glycidyl groups
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C08G59/681—Metal alcoholates, phenolates or carboxylates
    • C08G59/685—Carboxylates
    • 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
    • C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
    • C09D143/04—Homopolymers or copolymers of monomers containing silicon
    • 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
    • C09J143/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Adhesives based on derivatives of such polymers
    • C09J143/04—Homopolymers or copolymers of monomers containing silicon
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking
    • C08L2312/08—Crosslinking by silane
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/062—Copolymers with monomers not covered by C08L33/06
    • C08L33/068—Copolymers with monomers not covered by C08L33/06 containing glycidyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L43/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium or a metal; Compositions of derivatives of such polymers
    • C08L43/04—Homopolymers or copolymers of monomers containing silicon

Definitions

  • the present invention firstly relates to a curable composition excellent in weather resistance, and a sealing material using the curable composition as an available ingredient and excellent in weather resistance.
  • the present invention secondly relates to a curable composition excellent in restoring property, durability, weather resistance, and paint anti-staining property, and a sealing material using the curable composition as an available ingredient.
  • the present invention thirdly relates to a curable composition excellent in fire resistance, a sealing material using the curable composition as an available ingredient and having fire resistance, and a method of forming a fire-resistant structure involving the use of the sealing material.
  • a sealing material has been conventionally blended with a stabilizer in order that weather resistance may be imparted to the material.
  • whitening problems as described below occur, and have been serious problems to be solved in the field of sealing material construction.
  • One of the whitening problems is as described below.
  • a stabilizer having good weather resistance to be blended into the sealing material include a combination of a benzotriazole based ultraviolet ray absorbing agent and a hindered phenol based antioxidant as described in Patent Document 1, a combination of a benzotriazole based ultraviolet ray absorbing agent and a specific hindered amine based light stabilizer as described in Patent Document 2, and a combination of a benzotriazole based ultraviolet ray absorbing agent and a hindered amine based light stabilizer containing a specific triazine skeleton as described in Patent Document 3.
  • thick layer portion Those stabilizers are effective for, for example, sealing materials at thick (for example, 5 mm or more in thickness) joint portions (hereinafter collectively referred to as “thick layer portion”), but none of those stabilizers is effective for the thin layer portion, and no stabilizer formulation capable of improving the weather resistance of the thin layer portion and that of the thick layer portion simultaneously is known.
  • Patent Document 4 describes that a combination of a benzotriazole based ultraviolet ray absorbing agent, a hindered amine based compound having a molecular weight of 200 to 1,000 and free of a triazine skeleton in any one of its molecules, and a hindered amine compound having a triazine skeleton in any one of its molecules as light stabilizers is a stabilizer formulation having good weather resistance in each of a thin layer portion, and a thick layer portion.
  • the weather resistance is sufficient.
  • an oxypropylene polymer having a crosslinkable silyl group capable of curing into a rubber-like substance by virtue of moisture or the like has been conventionally utilized, for example, in an elastic sealant for structures or the like.
  • a composition obtained by blending the polymer with a plasticizer, a filler, and the like has been utilized in terms of physical properties and of cost.
  • the restoring property of the sealant for filling a joint of the structure plays an important role in following the fluctuation of the joint due to a humidity difference.
  • a curable resin composition having fire resistance has been currently produced on an industrial scale, and has been finding use in a wide variety of fields including structure-, automobile-, and electric machinery-related fields.
  • a sealing material superior in fire resistance compared to a conventional one has been requested in association with the recent increase of interest in safety.
  • Sealing materials each containing a polyphosphate compound as a foaming agent have been known as examples of fire resistant sealing materials that have already been on the market.
  • a material containing ammonium polyphosphate is effective; the generation of an ammonia gas caused by the hydrolysis of the material and phosphorus in the material promote the carbonization of any other substance to cause the substance to produce an incombustible carbonized layer, whereby the material has fire resistance (see, for example, Patent Documents 7 and 8).
  • sealing materials each containing a polyphosphate compound can obtain predetermined fire resistance unless the loading of the polyphosphate compound is equal to or higher than a certain level.
  • blending each of the sealing materials with the polyphosphate compound involves the following problems: reductions in physical properties of each of the sealing materials and an increase in cost for the production of each of the sealing materials.
  • a sealing material obtained by adding a foaming agent to a vinyl based organic polymer has been known as examples of any other sealing material having fire resistance; the material is formed on the basis of the vinyl based organic polymer having good heat resistance, and the foaming agent in the material expands or generates a gas to form a foaming layer having heat insulating property, whereby the material has fire resistance (see, for example, Patent Document 9).
  • the vinyl based organic polymer is inherently poor in elongation property.
  • blending the vinyl based organic polymer with the foaming agent involves the following problem: additional reductions in the physical properties of the polymer.
  • a method of making a part other than a sealing material (mainly a back-up material) fire-resistant has been employed for the purpose of imparting fire resistance to a joint portion.
  • a foaming asbestos body cut to be adjusted to be the width of a joint for example, trade name “Litoflex” manufactured by NICHIAS Corporation
  • an ordinary sealing material is loaded into the upper portion of the resultant, whereby compatibility between fire resistance and water resistance is achieved.
  • a silicone based sealing material different from the present invention in composition has also been attracting attention because of its excellent flame resistance.
  • the material involves the following problems: the material is poor in coating property, and causes water-repellent staining.
  • Patent Document 1 JP 5-287186 A
  • Patent Document 2 JP61-233043A
  • Patent Document 3 JP8-48888A
  • Patent Document 4 JP2001-271057A
  • Patent Document 5 JP55-9669A
  • Patent Document 6 JP01-29821B
  • Patent Document 7 JP2832222B
  • Patent Document 8 JP8-253761A
  • Patent Document 9 JP2001-354830A
  • a first object of the present invention is to provide a curable composition and a sealing material each having improved weather resistance in each of a thin layer portion and a thick layer portion.
  • a second object of the present invention is to provide a curable composition and a sealing material each of which are excellent in weather resistance, paint anti-staining property, restoring property, and durability.
  • a third object of the present invention is to provide an excellent curable composition and an excellent sealing material each having economical productivity, good physical properties, safety, and fire resistance.
  • Another object of the present invention is to provide a method of forming a fire-resistant structure with ease at a low cost.
  • the curable composition comprises: (A) an organic polymer containing a crosslinkable silyl group; (B) an ultraviolet ray absorbing agent having a triazine skeleton; and (C) a hindered amine based light stabilizer.
  • a curable composition having improved weather resistance in each of a thin layer portion and a thick layer portion can be obtained from the curable composition of the present invention.
  • the organic polymer containing a crosslinkable silyl group is preferably one or more kinds of compounds selected from the group consisting of a polyoxyalkylene based polymer containing a crosslinkable silyl group, a (meth)acrylic-modified polyoxyalkylene based polymer containing a crosslinkable silyl group, and a (meth)acrylic polymer containing a crosslinkable silyl group, or is more preferably a (meth)acrylic polymer having a crosslinkable silyl group at a terminal of its molecular chain, or the mixture of the (meth)acrylic polymer having a crosslinkable silyl group at a terminal of its molecular chain and a polyoxyalkylene based polymer containing a crosslinkable silyl group.
  • the terms “acrylic” and “methacrylic” are collectively referred to as “(meth)acrylic” in the present invention.
  • a method of producing the (meth)acrylic polymer having a crosslinkable silyl group at a terminal is not particularly limited; a controlled radical polymerization method is preferable, a living radical polymerization method is more preferable, and an atom transfer radical polymerization method is still more preferable.
  • the curable composition suitably further contains (D) a compound that reacts with water to produce an amine compound.
  • D a curable composition excellent in anti-staining property as well as weather resistance can be obtained.
  • the hindered amine based light stabilizer a hindered amine based compound having a triazine skeleton or a hindered amine based compound free of a triazine skeleton may be used.
  • the hindered amine based light stabilizer a mixture of a hindered amine based compound having a triazine skeleton and a hindered amine based compound free of a triazine skeleton may be used.
  • the sealing material comprises the first aspect of the curable composition of the present invention as an available ingredient, and has excellent weather resistance.
  • the curable composition comprises: (E) an organic polymer containing a crosslinkable silyl group; (F) a (meth)acrylic polymer containing an epoxy group; (G) a divalent tin organic carboxylate; and (H) an organic amine compound.
  • E an organic polymer containing a crosslinkable silyl group
  • F a (meth)acrylic polymer containing an epoxy group
  • G a divalent tin organic carboxylate
  • H an organic amine compound
  • the organic polymer containing a crosslinkable silyl group is preferably a (meth)acrylic polymer containing a crosslinkable silyl group.
  • the (meth)acrylic polymer containing a crosslinkable silyl group is preferably a (meth)acrylic organic polymer having a crosslinkable silyl group at a terminal of its molecular chain, or the mixture of the (meth)acrylic polymer having a crosslinkable silyl group at a terminal of its molecular chain and an organic polymer containing a crosslinkable silyl group.
  • a method of producing the (meth)acrylic polymer having a crosslinkable silyl group at a terminal is not particularly limited; a controlled radical polymerization method is preferable, a living radical polymerization method is more preferable, and an atom transfer radical polymerization method is still more preferable.
  • the (meth)acrylic polymer containing an epoxy group has a weight average molecular weight within the range of preferably 1,000 to 7,500.
  • the sealing material comprises the second aspect of the curable composition of the present invention as an available ingredient, and is excellent in weather resistance, paint anti-staining property, restoring property, and durability.
  • the curable composition comprises: (I) a reactive organic polymer containing at least one crosslinkable silyl group in any one of its molecules; (J) a reactive organic polymer containing less than one crosslinkable silyl group in any one of its molecules; and (K) thermally expandable hollow spheres as essential components, wherein the curable composition contains the component (K) in an amount within the range of 0.01 part by mass to 20 parts by mass with respect to a total of 100 parts by mass of the components (I) and (J).
  • An excellent curable composition having economical productivity, good physical properties, safety, and fire resistance can be provided by the curable composition of the present invention.
  • the reactive organic polymer containing at least one crosslinkable silyl group in any one of its molecules is preferably a (meth)acrylic polymer containing a crosslinkable silyl group.
  • the (meth)acrylic polymer containing a crosslinkable silyl group is preferably a (meth)acrylic polymer having a crosslinkable silyl group at a terminal of its molecular chain, or the mixture of the (meth)acrylic polymer having a crosslinkable silyl group at a terminal of its molecular chain and a polyoxyalkylene based polymer containing a crosslinkable silyl group.
  • a method of producing the (meth)acrylic polymer having a crosslinkable silyl group at a terminal is not particularly limited; a controlled radical polymerization method is preferable, a living radical polymerization method is more preferable, and an atom transfer radical polymerization method is still more preferable.
  • the reactive organic polymer containing less than one crosslinkable silyl group in any one of its molecules is suitably a (meth)acrylic polymer.
  • the reactive organic polymer containing less than one crosslinkable silyl group in any one of its molecules has a weight average molecular weight of preferably 2,000 to 50,000.
  • the curable composition contains the component (J) in an amount of preferably 10 to 300 parts by weight with respect to 100 parts by weight of the component (I).
  • the hardness of a rubber-like elastic body after the curing of the composition measured with a rubber hardness meter is preferably 40 or less.
  • the sealing material comprises the third aspect of the curable composition of the present invention as an available ingredient, and has excellent fire resistance.
  • a forming method of the present invention comprises forming a fire-resistant structure using a wall material having fire resistance and the sealing material having fire resistance according to the present invention.
  • a curable composition and a sealing material each having improved weather resistance in each of a thin layer portion and a thick layer portion can be obtained. Further, according to the present invention, a curable composition and a sealing material each of which is excellent in anti-staining property as well as weather resistance and has a high elongation rate can also be obtained.
  • a curable composition which is excellent in weather resistance, paint anti-staining property, restoring property, and durability and which is suitably used particularly in, for example, a sealing material for the structure can be obtained.
  • a sealing material excellent in weather resistance, paint anti-staining property, restoring property, and durability can be obtained.
  • a curable composition which has a high elongation rate and is suitably used in a sealing material, and a sealing material having a high elongation rate.
  • an excellent curable composition which has economical productivity, good physical properties, safety, and fire resistance. Further, according to the present invention, a curable composition having a high elongation rate as well as the above effects can be obtained.
  • the third aspect of the curable composition of the present invention is most suitably used in a sealing material; the composition can be used in, for example, an adhesive, a pressure-sensitive adhesive, a coating material, or a potting material as long as the composition is used in applications where fire resistance is expected from the composition.
  • the sealing material having fire resistance of the present invention exerts the following significant effects: the sealing material maintains good physical properties, has high cost performance, can be applied, does not cause water-repellent staining, and can be turned into a one-component liquid. Furthermore, the sealing material forms a foaming heat insulating layer when exposed to flame to shield, for example, heat, flame, smoke, and a gas generated by combustion. According to the formation method of the present invention, a fire-resistant structure can be formed with ease at a low cost.
  • any one of the first to third aspects of the curable composition of the present invention is particularly suitably used in a sealing material; any one of the aspects can be used in, for example, an adhesive, a pressure-sensitive adhesive, a coating material, or a potting material.
  • the curable composition of the present invention can be used for, for example, various structures, automobiles, civil engineering, and electrical and electronic fields.
  • FIG. 1 is a schematic explanatory view showing an example of a fire-resistant structure to be formed by a formation method of the present invention.
  • FIG. 2 is a top view of FIG. 1 .
  • the first aspect of the curable composition of the present invention comprises the following components (A), (B) and (C):
  • An organic polymer containing a silicon-containing group having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and capable of crosslinking by the formation of a siloxane bond, that is, a crosslinkable silyl group is used as the component (A).
  • Examples of such an organic polymer containing crosslinkable silyl group-containing (A) include those disclosed in JP5-287186A, JP61-233043A, JP1-58219B, JP3062625B, JP8-337713A, JP2003-138151A, JP11-12480A, JP52-73998A, JP55-9669A, JP59-122541A, JP60-6747A, JP63-112642A, JP03-79627A, JP04-283259A, JP05-70531A, JP11-80571A, JP11-116763A, JP11-130931A, JP2001-40037A, JP3313360B, JP2004-51830A, JP2004-59782A, JP2001-329065A, and JP2001-271055A.
  • organic polymer containing a crosslinkable silyl group (A) examples include a polyoxyalkylene based polymer, a vinyl-modified polyoxyalkylene based polymer, a vinyl based polymer, a polyester polymer, and a (meth)acrylate polymer each of which contains a crosslinkable silyl group and the main chain of each of which may contain organosiloxane, and a copolymer or mixture of two or more of them.
  • One molecule of the polymer generally contains 1 to 6 crosslinkable silyl groups in terms of, for example, the curing property of the composition and the physical properties of the composition after the curing of the composition, though the number of the groups is not particularly limited.
  • the crosslinkable silyl group is preferably a group represented by the following general formula (1) because the group can be easily crosslinked, and can be easily produced:
  • R 1 represents a substituted or unsubstituted, monovalent organic group having 1 to 20 carbon atoms, preferably represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, or most preferably represents a methyl group, and, when multiple R 1 's are present, the multiple R 1 's may be identical to or different from each other, X represents a hydroxyl group or a hydrolyzable group, preferably represents a group selected from a halogen atom, a hydrogen atom, a hydroxyl group, an alkoxy group, an acyloxy group, a ketoximate group, an amide group, an acid amide group, a mercapto group, an alkenyloxy group, and an aminooxy group, more preferably represents an alkoxy group, or most preferably represents a methoxy group, and, when multiple X's are present, the multiple X
  • the groups may be identical to or different from each other. Further, the numbers of a in the formula (1) may be identical to or different from each other. In addition, two or more kinds of organic polymers containing different crosslinkable silyl groups may be used.
  • the main chain of the organic polymer containing a crosslinkable silyl group (A) is preferably, for example, a polyoxyalkylene based polymer, (meth)acrylic-modified polyoxyalkylene polymer, or (meth)acrylic polymer which may contain organosiloxane, or a copolymer or mixture of two or more of them in terms of physical properties such as tensile strength and modulus after the curing of the composition.
  • the organic polymer containing a crosslinkable silyl group (A) is particularly preferably a vinyl based polymer having a crosslinkable silyl group at a terminal, or is more preferably a (meth)acrylic polymer having a crosslinkable silyl group at a terminal, or the mixture of the (meth)acrylic polymer having a crosslinkable silyl group and a polyoxyalkylene based polymer having a crosslinkable silyl group.
  • the use of the (meth)acrylic polymer having a crosslinkable silyl group at a terminal of any one of its molecules as the component (A) can achieve a high elongation rate particularly useful in a sealing material.
  • a method of producing the organic polymer containing a crosslinkable silyl group (A) is not particularly limited, and a known synthesis method can be utilized.
  • a polymer which contains a crosslinkable silyl group and the main chain of which is a vinyl based polymer such as an acrylic polymer is used as the organic polymer containing a crosslinkable silyl group
  • a vinyl based polymer synthesized by a radical polymerization method is preferably used.
  • the radical polymerization methods are classified into a general radical polymerization method involving merely copolymerizing a monomer having a specific functional group and a vinyl based monomer by using an azo based compound, a peroxide, or the like as a polymerization initiator and a controlled radical polymerization method by which a specific functional group can be introduced to a controlled position such as a terminal.
  • a vinyl based polymer synthesized by the controlled radical polymerization method is more effective than a polymer synthesized by the former method.
  • the controlled radical polymerization methods are further classified into a chain transfer agent method by which a vinyl based polymer having a specific functional group at a terminal can be obtained as a result of polymerization using a chain transfer agent having the functional group and a living radical polymerization method by which a polymerization growth terminal grows without causing a termination reaction or the like.
  • living radical polymerization method is particularly preferable because a polymer having an arbitrary molecular weight, a narrow molecular weight distribution, and a low viscosity can be obtained, and a monomer having a specific functional group can be introduced to an arbitrary position.
  • living polymerization includes pseudo-living polymerization in which a molecular chain with an inactivated terminal and a molecular chain with an activated terminal grow while they are in an equilibrium state in addition to polymerization in which a molecular chain grows while a terminal of the chain continues to have activity at all times.
  • Examples of the living radical polymerization method include: a method involving the use of a cobalt porphyrin complex as disclosed in J. Am. Chem. Soc., 1994, vol. 116, p. 7943; a method involving the use of a radical scavenger such as a nitroxide compound as disclosed in Macromolecules, 1994, vol. 27, p. 7228; and an atom transfer radical polymerization (ATRP) method involving polymerizing a vinyl based monomer by using an organic halogen compound, a halogenated sulfonyl compound, or the like as an initiator and a transition metal complex as a catalyst as disclosed in J. Am. Chem. Soc., 1995, vol. 117, p.
  • the living radical polymerization method which is not particularly limited, is preferably the atom transfer radical polymerization method.
  • the atom transfer radical polymerization method includes a reverse atom transfer radical polymerization method, that is, a method involving causing a general radical initiator such as a peroxide to act on a high oxide state when an ordinary atom transfer radical polymerization catalyst generates a radical such as Cu(II′) when Cu(I) is used as a catalyst to produce equilibrium similar to that of atom transfer radical polymerization as a result of the action (see, for example, Macromolecules, 1999, vol. 32, p. 2872).
  • a reverse atom transfer radical polymerization method that is, a method involving causing a general radical initiator such as a peroxide to act on a high oxide state when an ordinary atom transfer radical polymerization catalyst generates a radical such as Cu(II′) when Cu(I) is used as a catalyst to produce equilibrium similar to that of atom transfer radical polymerization as a result of the action (see, for example, Macromolecules, 1999, vol. 32, p. 2872
  • Examples of the chain transfer agent method include: a method involving the use of a halogenated hydrocarbon as a chain transfer agent to obtain a polymer having a halogen at a terminal as disclosed in JP4-132706A; and a method involving the use of, for example, a hydroxyl group-containing mercaptan or a hydroxyl group-containing polysulfide as a chain transfer agent to obtain a polymer having a hydroxyl group at a terminal as disclosed in JP61-271306A, JP2594402B, or JP54-47782A.
  • An organic halide in particular, an organic halide having a highly reactive carbon-halogen bond (such as a carbonyl compound having a halogen at ⁇ -position or a compound having a halogen at a benzyl position), a halogenated sulfonyl compound, or the like is used as an initiator for the atom transfer radical polymerization method.
  • an organic halide having a highly reactive carbon-halogen bond such as a carbonyl compound having a halogen at ⁇ -position or a compound having a halogen at a benzyl position
  • a halogenated sulfonyl compound or the like
  • an organic halide or halogenated sulfonyl compound having a functional group except a functional group for initiating atom transfer radical polymerization such as an alkenyl group, a crosslinkable silyl group, a hydroxyl group, an epoxy group, an amino group, or an amide group can also be used as an initiator for the polymerization.
  • a vinyl based polymer having the functional group at one main chain terminal and the growth terminal structure of the atom transfer radical polymerization at the other main chain terminal is synthesized.
  • an organic halide or halogenated sulfonyl compound having a crosslinkable silyl group is preferably used. In this case, a polymer having the crosslinkable silyl group at one terminal and a halogen at the other terminal is obtained, and a polymer having crosslinkable silyl groups at both terminals can be obtained by substituting the halogen terminal.
  • the vinyl based monomer to be used in the polymerization is not particularly limited; in the present invention, one or more kinds of acrylic monomers such as (meth)acrylic acid, a (meth)acrylate, (meth)acrylonitrile, and (meth)acrylamide are preferably used as main components, and a (meth)acrylate such as an alkyl (meth)acrylate or an alkoxyalkyl (meth)acrylate is more preferably used as a main component.
  • acrylic monomers such as (meth)acrylic acid, a (meth)acrylate, (meth)acrylonitrile, and (meth)acrylamide
  • a (meth)acrylate such as an alkyl (meth)acrylate or an alkoxyalkyl (meth)acrylate is more preferably used as a main component.
  • the transition metal complex to be used as a polymerization catalyst is not particularly limited; a metal complex using an element belonging to Group 7, 8, 9, 10, or 11 in the periodic table as a central metal is preferable, a complex of zero-valent copper, monovalent copper, divalent ruthenium, divalent iron, or divalent nickel is more preferable, and a complex of copper is particularly preferable.
  • a monovalent copper compound is, for example, cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, or cuprous perchlorate.
  • any one of the ligands such as 2,2′-bipyridyl and a derivative of 2,2′-bipyridyl, 1,10-phenanthroline and a derivative of 1,10-phenanthroline, and polyamines such as tetramethylethylene diamine, pentamethyl diethylene triamine, and hexamethyltris(2-aminoethyl)amine is added to the compound for improving the catalytic activity of the compound.
  • a tristriphenylphosphine complex of divalent ruthenium chloride [RuCl 2 (PPh 3 ) 3 ], a bistriphenylphosphine complex of divalent iron [FeCl 2 (PPh 3 ) 2 ], a bistriphenylphosphine complex of divalent nickel [NiCl 2 (PPh 3 ) 2 ], and a bistributylphosphine complex of divalent nickel [NiBr 2 (PBu 3 ) 2 ] are also suitably used as catalysts.
  • a ruthenium compound is used as a catalyst, any one of the aluminum alkoxides is added as an activator.
  • the polymerization can be performed in the absence of a solvent or in any one of various solvents.
  • the polymerization is performed in the temperature range of preferably 0 to 200° C., or more preferably room temperature to 150° C.
  • An acrylic polymer having a halogen at a terminal is produced by the radical polymerization of a vinyl based monomer mainly composed of an acrylic monomer using an organic halogen compound, a halogenated sulfonyl compound, or the like as an initiator and a transition metal complex as a catalyst.
  • the (meth)acrylic polymer having a crosslinkable silyl group at a terminal of its molecular chain to be used in the present invention can be obtained by transforming the halogen of the acrylic polymer having the halogen at a terminal into the crosslinkable silyl group.
  • a method for the transformation is not particularly limited, and a known method (see, for example, JP11-80571A, JP11-116763A, JP11-130931A, JP2004-51830A, JP2004-59782A, JP2001-329065A, or JP2001-271055A) can be employed.
  • the organic polymer containing a crosslinkable silyl group (A) desirably has a number average molecular weight of 1,000 or more to 100,000 or less, in particular, 3,000 to 50,000 and a narrow molecular weight distribution because the viscosity of the polymer before the curing of the composition is so low that the polymer can be easily handled, and the physical properties of the composition after the curing of the composition such as strength, an elongation rate, and a modulus are suitable. Only one kind of the organic polymer containing a crosslinkable silyl group (A) may be used, or two or more kinds of such polymers may be used in combination.
  • the component (B) is not particularly limited as long as the component is an ultraviolet ray absorbing agent having a triazine skeleton, and any one of a wide variety of known compounds can be used as the component.
  • Specific suitable examples of the component (B) include triazine based compounds each represented by the following formula (2):
  • R 2 to R 7 each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, or a substituted or unsubstituted, monovalent organic group, or preferably a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms.
  • a 2-(2-hydroxyphenyl)-1,3,5-triazine based compound in which R 2 in the formula (2) represents a hydrogen atom, a polymerizable triazine compound represented by the following general formula (3), or the like is preferable:
  • R 3 , R 5 , and R 7 each have the same meaning as that described above, or each preferably represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
  • R 8 represents a hydrogen atom or a methyl group
  • R 9 represents a substituted or unsubstituted, divalent organic group, or preferably an alkylene group having 1 to 6 carbon atoms, a —(—CH 2 CH 2 —O—) m group (m represents an integer of 1 to 5), or a —CH 2 CH(OH)—CH 2 O— group.
  • Examples of the 2-(2-hydroxyphenyl)-1,3,5-triazine-based compound include 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxyl-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-tri
  • R 10 and R 11 each represent a methyl group or an alkoxy group having 1 to 8 carbon atoms
  • R 12 represents a hydrogen atom, a chlorine atom, a methyl group, or a methoxy group
  • R 13 represents an alkoxy group having 1 to 8 carbon atoms
  • R 14 represents a hydrogen atom or a methoxy group.
  • R 14 represents the same as described above, and R 15 represents a hydrogen atom or a methyl group.
  • polymerizable triazine compound examples include 2,4-diphenyl-6-[2-hydroxy-4-(2-acryloyloxyethoxy)]-s-triazine, 2,4-diphenyl-6-[2-hydroxy-4-(2-acryloyloxyethoxy)]-s-triazine, 2,4-bis(2-methylphenyl)-6-[2-hydroxy-4-(3-acryloyloxy-2-hydroxypropy oxy)]-s-triazine, 2,4-bis(2-methoxyphenyl)-6-[2-hydroxy-4-(2-acryloyloxyethoxy)-s-triazine, 2,4-bis(2-ethylphenyl)-6-[2-hydroxy-4-(2-acryloyloxyethoxy)]-s-triazine, 2,4-bis(2-ethoxyphenyl)-6-[2-hydroxy-4-(2-acryloyloxyethoxy)]-s-triazine, 2,4-bis(2-ethoxyphenyl
  • a ratio at which the above component (B) is blended is not particularly limited; the component is blended in an amount of preferably 0.1 to 50 parts by mass, or particularly preferably 1.0 to 10 parts by mass with respect to 100 parts by mass of the component (A).
  • One kind of the above ultraviolet ray absorbing agent having a triazine skeleton may be used alone, or two or more kinds of such agents may be used in combination.
  • a hindered amine based compound having a triazine skeleton (C1) or a hindered amine based compound free of a triazine skeleton (C2) may be used as the component (C), that is, the hindered amine based light stabilizer without any particular limitation. Only one kind of such hindered amine based light stabilizer may be used, or two or more kinds of such stabilizers may be used in combination. When two or more kinds of such stabilizers are used in combination, the combination is not particularly limited, and the mixture of a hindered amine based compound having a triazine skeleton and a hindered amine based compound free of a triazine skeleton can also be used.
  • Examples of the hindered amine based compound (C1) having a triazine skeleton include a hindered amine compound having a triazine skeleton in any one of its molecules such as 1,5,8,12-tetrakis[4,6-bis ⁇ N-(2,2,6,6-tetramethyl-4-pyperidyl)butylamino ⁇ -1,3,5-triazine-2-yl]-1,5,8,12-tetraazadodecane, N,N′,N′′,N′′′-tetrakis[4,6-bis ⁇ butyl-(N-methyl-2,2,6,6-tetramethylpyperidine-4-yl)amino ⁇ -triazine-2-yl]-4,7-diazadecane-1,10-diamine, poly[ ⁇ 6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl ⁇ (2,2,6,6-te
  • Examples of the hindered amine based compound free of a triazine skeleton (C2) include hindered amine compounds such as 2,2,6,6-tetramethyl-4-pyperidylstearate, 1,2,2,6,6-pentamethyl-4-pyperidylstearate, 2,2,6,6-tetramethyl-4-pyperidylbenzoate, N-(2,2,6,6-tetramethyl-4-pyperidyl)dodecyl succinimide, 1-[(3,5-ditertiarybutyl-4-hydroxyphenyl)propionyloxyethyl]-2,2,6,6-tetramethyl-4-pyperidinyl-(3,5-ditertiarybutyl-4-hydroxyphenyl)propionate, bis(2,2,6,6-tetramethyl-4-pyperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-pyperidyl)sebacate,
  • a ratio at which the above component (C) is blended is not particularly limited; the component is blended in an amount of preferably 0.1 to 50 parts by mass, or particularly preferably 1.0 to 10 parts by mass with respect to 100 parts by mass of the component (A).
  • the curable composition suitably further contains (D) a compound that reacts with water to produce an amine compound because the anti-staining property of the composition can be significantly improved.
  • a compound that reacts with water to produce an amine compound because the anti-staining property of the composition can be significantly improved.
  • Specific suitable examples of the above component (D) include ketimine compounds, enamine compounds, and/or aldimine compounds of amine compounds in terms of, for example, the easy availability of a raw material, storage stability, and reactivity with water.
  • Each of the above ketimine, enamine, and aldimine compounds can be obtained by a dehydration reaction between (D1) an amine compound and (D2) a carbonyl compound.
  • a method of producing the above component (D) is not particularly limited, and a known method can be employed.
  • Examples of the above amine compound (D1) include, but not particularly limited to, a primary amine and/or a secondary amine, and an amine compound having at least one alkoxysilyl group in any one of its molecules.
  • the amine compound having at least one alkoxysilyl group in any one of its molecules is preferable because of its particularly excellent adhesiveness.
  • Examples of the primary amine include: monoamines such as butylamine, hexylamine, heptylamine, 2-ethylhexylamine, octylamine, 3-methoxypropylamine, tetradecylamine, pentadecylamine, cetylamine, stearylamine, trimethylcyclohexylamine, benzylamine, and aniline; diamines such as ethylenediamine, 1,3-diaminopropane, 1,2-diaminopropane, 1,4-diaminobutane, hexamethylenediamine, 1,7-diaminoheptane, trimethylhexamethylene diamine, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,13-
  • Examples of the secondary amine include: monoamines such as dilaurylamine, distearylamine, and methyllaurylamine; and diamines such as N,N′-dilaurylpropylamine, N,N′-distearylbutylamine, N-butyl-N′-laurylethylamine, N-butyl-N′-laurylpropylamine, and N-lauryl-N′-stearylbutylamine.
  • Examples of the mixture of primary and secondary amine include N-laurylpropylenediamine and N-stearylpropylenediamine.
  • Examples of the mixture of primary and secondary polyamine include diethylenetriamine, triethylenetetramine, and methylaminopropylamine.
  • Examples of the above amine compound having at least one alkoxysilyl group in any one of its molecules include compounds each represented by the following general formula (9):
  • R 16 and R 17 may be identical to or different from each other, and each represent a hydrocarbon group having 1 to 4 carbon atoms, R 18 represents a hydrocarbon group having 1 to 10 carbon atoms, and Y represents a hydrogen atom or an aminoalkyl group having 1 to 4 carbon atoms.
  • examples of the group represented by each of R 16 and R 17 include: alkyl groups such as methyl, ethyl, propyl, and butyl groups; and alkenyl groups such as vinyl, allyl, propenyl, and butenyl groups.
  • alkyl group is preferable.
  • examples of the group represented by R 18 include: alkylene groups such as methylene, ethylene, propylene, and butylene; arylene groups such as a phenylene group; and alkylenearylene groups.
  • n preferably represents 0 or 1.
  • amine compound examples include: compounds represented by the following formulae (10) to (17); and aminosilanes typified by N-( ⁇ -aminoethyl)- ⁇ -aminopropyltrimethoxysilane and N-( ⁇ -aminoethyl)- ⁇ -aminopropylmethyldimethoxysilane.
  • ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropylmethyldimethoxysilane, N-( ⁇ -aminoethyl)- ⁇ -aminopropyltrimethoxysilane, or the like is particularly preferable because in addition improved adhesiveness can be obtained.
  • the carbonyl compound (D2) includes known compounds, and examples thereof include, but not limited to: aldehydes such as acetaldehyde, propionealdehyde, n-butylaldehyde, isobutylaldehyde, n-amylaldehyde, isohexylaldehyde, diethylacetaldehyde, glyoxal, benzaldehyde, and phenylacetaldehyde; cyclic ketones such as cyclopentanone, trimethylcyclopentanone, cyclohexanone, methylcyclohexanone, and trimethylcyclohexanone; aliphatic ketones such as acetone, methylethylketone, methylpropylketone, methylisopropylketone, methylisobutylketone, methyl-tert-butylketone, diethylketone, dipropylketone, di
  • methyl isobutyl ketone, dipropyl ketone, phenylacetaldehyde, and a ⁇ -dicarbonyl compound having an active methylene group are more preferable:
  • R 19 and R 20 may be identical to or different from each other, and each represent an alkyl group having 1 to 16 carbon atoms (such as a methyl, ethyl, propyl, butyl, heptyl, hexyl, octyl, nonyl, decyl, undecyl, or hexadecyl group), an aryl group having 6 to 12 carbon atoms (such as a phenyl, tolyl, hexyl, or naphthyl group), or an alkoxyl group having 1 to 4 carbon atoms (such as a methoxy, ethoxy, propoxy, or butoxy group).]
  • an alkyl group having 1 to 16 carbon atoms such as a methyl, ethyl, propyl, butyl, heptyl, hexyl, octyl, nonyl, decyl, undecyl, or hexadecyl
  • the above compound that reacts with water to produce an amine compound having at least one alkoxysilyl group in any one of its molecules in the component (D) of the present invention is not particularly limited, and a compound obtained by a known production method can be used; a compound having a monomer purity of 50 to 95%, preferably 70 to 95%, or more preferably 80 to 95%, and an amino group sealing rate of 90% or more, or preferably 95% or more is suitably used.
  • a ratio at which the above component (D) is blended is not particularly limited; the component (D) is blended in an amount of preferably 0.05 to 50 parts by mass, or particularly preferably 1.0 to 20 parts by mass with respect to 100 parts by mass of the component (A).
  • One kind of the above the compound that reacts with water to produce an amine compound may be used alone, or two or more kinds of such compounds may be used in combination.
  • the curable composition suitably further contains (D1) an amine compound and (D2) a carbonyl compound in order that the anti-staining property of the composition may be improved.
  • the amine compound and the carbonyl compound exemplified in the description of the component (D) can be similarly used as the components (D1) and (D2), respectively.
  • the above components (D1) and (D2) cause a dehydration reaction in the blend of the components.
  • the dehydration reaction which may be performed while a treatment such as a heat treatment is performed as required, can be advanced with the passage of time without the performance of any particular step.
  • a ratio at which each of the components (D1) and (D2) is blended is not particularly limited; each of the components (D1) and (D2) is blended in an amount of preferably 0.05 to 50 parts by mass, or particularly preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the component (A). Further, a ratio “[molar amount of component (D1)]/[molar amount of component (D2)]” is in the range of preferably 0.1 to 5.0, or more preferably 0.5 to 2.0.
  • One kind of the amine or carbonyl compound may be used alone, or two or more kinds of such amine or carbonyl compounds may be used in combination.
  • the curable composition may be blended with any one of: substances such as an adhesion imparting agent, a physical property adjuster, a filler, a curing catalyst, a plasticizer, a thixotropic agent, a dehydrating agent (storage stability improver), a tackifier, a sagging inhibitor, an antioxidant, a flame retardant, a colorant, and a radical polymerization initiator; and various solvents such as toluene and an alcohol in addition to the above-mentioned components as required, or may be blended with any other polymer compatible with the curable composition.
  • substances such as an adhesion imparting agent, a physical property adjuster, a filler, a curing catalyst, a plasticizer, a thixotropic agent, a dehydrating agent (storage stability improver), a tackifier, a sagging inhibitor, an antioxidant, a flame retardant, a colorant, and a radical polymerization initiator
  • various solvents such as tol
  • an ultraviolet ray absorbing agent except the component (B), that is, the triazine based ultraviolet ray absorbing agent such as a benzotriazole based, triazine based, benzophenone based, benzoate based, or salicylic acid based ultraviolet ray absorbing agent or a light stabilizer except the component (C), that is, the hindered amine based light stabilizer may be further added to the curable composition of the present invention.
  • the above other polymer compatible with the curable composition is particularly preferably any one of various polyethers, especially, for example, a polyether having a silicon functional group.
  • adhesion imparting agent examples include various silane coupling agents such as: aminosilanes including aminoethylaminopropyltrimethoxysilane, aminoethylaminopropylmethyldimethoxysilane, aminoethylaminopropylmethylmethoxysilane; epoxy silanes including ⁇ -glycidoxypropyltrimethoxysilane; acrylsilanes including ⁇ -methacryloxypropyltrimethoxy silane; mercaptosilanes including ⁇ -mercaptopropyltrimethoxy silane; and isocyanate silanes including ⁇ -isocyanate propyltrimethoxysilane.
  • Those adhesion imparting agents may be used alone, or two or more thereof may be used in combination.
  • the above physical property adjuster is added for the purpose of improving the tensile property of the curable composition.
  • Examples of the above physical property adjuster include silicon compounds each having one silanol group in any one of its molecules, such as triphenylsilanol, trialkylsilanol, dialkylphenylsilanol, and diphenylalkylsilanol.
  • the examples further include various silane coupling agents such as silicon compounds each of which hydrolyzes to produce a compound having one silanol group in any one of its molecules including triphenylmethoxysilane, trialkylmethoxysilane, dialkylphenylmethoxysilane, diphenylalkylmethoxysilane, triphenylethoxysilane, and trialkylethoxysilane.
  • silane coupling agents such as silicon compounds each of which hydrolyzes to produce a compound having one silanol group in any one of its molecules including triphenylmethoxysilane, trialkylmethoxysilane, dialkylphenylmethoxysilane, diphenylalkylmethoxysilane, triphenylethoxysilane, and trialkylethoxysilane.
  • silicon compounds each of which hydrolyzes to produce a compound having one silanol group in any one of its molecules including triphenylmethoxysilane,
  • the above filler is added for the purpose of reinforcing a cured product made of the curable composition.
  • examples of the above filler include calcium carbonate, magnesium carbonate, diatomaceous earth hydrate silicic acid, hydrate silicic acid, silicic acid anhydride, calcium silicate, silica, titanium dioxide, clay, talc, carbon black, slate powder, mica, kaolin, and zeolite.
  • calcium carbonate is preferable, and calcium carbonate treated with an aliphatic acid is more preferable.
  • a glass bead, a silica bead, an alumina bead, a carbon bead, a styrene bead, a phenol bead, an acrylic bead, porous silica, a Shirasu balloon, a glass balloon, a silica balloon, a saran balloon, an acrylic balloon, or the like can also be used.
  • the acrylic balloon is more preferable because a reduction in elongation of the composition after the curing of the composition is small.
  • One kind of the above fillers may be used alone, or two or more kinds of them may be used in combination.
  • the above plasticizer is added for the purposes of: improving the elongation property of the composition after the curing of the composition; and enabling a reduction in modulus of a cured product.
  • the plasticizer include: phosphates such as tributyl phosphate and tricresyl phosphate; phthalates such as dioctyl phthalate (DOP), dibutyl phthalate, and butyl benzyl phthalate; aliphatic monobasic acid esters such as glycerin monooleate; aliphatic dibasic acid esters such as dibutyl adipate and dioctyl adipate; glycol esters such as polypropylene glycol; aliphatic esters; epoxy plasticizers; polyester based plasticizers; polyethers; and polystyrenes.
  • One kind of the above plasticizers may be used alone, or two or more kinds of them may be used in combination.
  • thixotropic agent examples include: an inorganic thixotropic agent such as colloidal silica or asbestos powder; an organic thixotropic agent such as organic bentonite, modified polyester polyol, or an aliphatic amide; a hydrogenated castor oil derivative; an aliphatic amide wax; aluminum stearate; and barium stearate.
  • an inorganic thixotropic agent such as colloidal silica or asbestos powder
  • organic thixotropic agent such as organic bentonite, modified polyester polyol, or an aliphatic amide
  • a hydrogenated castor oil derivative an aliphatic amide wax
  • aluminum stearate aluminum stearate
  • barium stearate examples include: an inorganic thixotropic agent such as colloidal silica or asbestos powder; an organic thixotropic agent such as organic bentonite, modified polyester polyol, or an aliphatic amide; a hydrogenated castor oil derivative; an aliphatic
  • the above dehydrating agent is added for the purpose of removing moisture during the storage of the composition.
  • the dehydrating agent include silane compounds such as vinyltrimethoxysilane, dimethyldimethoxysilane, tetraethoxysilane, methyltrimethoxysilane, and methyltriethoxysilane.
  • the above antioxidant is used for preventing the oxidation of a cured sealing material to improve the weather resistance of the material, and is, for example, a hindered phenol based antioxidant.
  • the hindered phenol based antioxidant include, but not limited to, pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], thiodiethylene-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N′-hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenylpropioamide], benzene propionic acid 3,5-bis(1,1-dimethylethyl)-4-hydroxy C7-C9 side chain
  • the second aspect of the curable composition of the present invention contains the following components (E), (F), (G), and (H) as essential components:
  • the organic polymer containing a crosslinkable silyl group exemplified in the description of the component (A) according to the first aspect of the curable composition of the present invention can be similarly used as (E) the organic polymer containing a crosslinkable silyl group.
  • the (meth)acrylic polymer containing an epoxy group has a weight average molecular weight of preferably 1,000 to 7,500, more preferably 1,500 to 6,000, or still more preferably 2,000 to 5,500.
  • a weight average molecular weight in excess of 7,500 is not preferable because a sufficient plasticizing effect is not exerted, and workability deteriorates.
  • a weight average molecular weight of less than 1,000 is not preferable too because a low-molecular-weight polymer bleeds, and hence the anti-staining property of the composition is reduced.
  • the number of epoxy groups in the polymer (F), which is not particularly limited, is preferably 0.05 or more, or more preferably 0.1 or more on average in one molecule of the polymer.
  • the (meth)acrylic polymer containing an epoxy group functions as a plasticizer and an amine catcher.
  • An epoxy group has polarity, and an increase in polarity of the polymer improves the affinity of the polymer for top coating paint, so adhesiveness between the polymer and the top coating paint may improve.
  • the polymer can be specifically obtained by copolymerizing a (meth)acrylic monomer containing an epoxy group (such as glycidyl (meth)acrylate) or by causing an epoxy group-containing compound to react with a (meth)acrylic polymer containing a functional group.
  • the latter method involving causing an epoxy group-containing compound to react with a (meth)acrylic polymer containing a functional group is, for example, a method involving causing glycidol to react with a polymer having an isocyanate group.
  • the (meth)acrylic polymer can be produced, but not particularly limited to, by (co)polymerizing one or more kinds of (meth)acrylic monomers such as (meth)acrylic acid, (meth)acrylate, (meth)acrylonitrile, and (meth)acrylamide with a known method.
  • (meth)acrylic monomer (meth)acrylate is particularly preferred.
  • Examples of the (meth)acrylate include: alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, neopentyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, and stearyl (meth)acrylate; aliphathic alkyl (meth)acrylates such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and tricyclodecynyl (meth)acrylate; and hetero atom-
  • methyl methacrylate, ethyl acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, methoxyethyl acrylate, and cyclohexyl acrylate are preferred in regard to obtaining the balance of plasticity.
  • any other copolymerizable monomer may be used to such an extent that the physical properties of the composition are not impaired.
  • Examples of such monomer include: ⁇ -olefins such as ethylene, propylene, and isobutylene; chloroethylenes such as vinyl chloride and vinylidene chloride; and alkyl vinyl ethers such as ethyl vinyl ether and butyl vinyl ether.
  • a ratio at which the component (F) is blended is not particularly limited; the component is used in an amount of preferably 5 to 150 parts by mass, more preferably 10 to 120 parts by mass, or still more preferably 15 to 100 parts by mass with respect to 100 parts by mass of the component (E).
  • the amount is less than 5 parts by mass, a sufficient plasticizing effect or sufficient restoring property cannot be obtained.
  • the amount exceeds 150 parts by mass, the component bleeds on the surface of the composition, so the anti-staining property of the composition deteriorates in some cases.
  • Only one kind of the (meth)acrylic polymer containing an epoxy group may be used, or two or more kinds of such polymers may be used in combination.
  • Examples of (G) the divalent tin organic carboxylate include tin(II) octylate, tin(II) naphthenate, and tin(II) stearate.
  • a ratio at which the component (G) is blended is not particularly limited; the component is blended in an amount of preferably 0.001 to 10 parts by mass with respect to 100 parts by mass of the component (E). Only one kind of the divalent tin organic carboxylate may be used, or two or more kinds of such salts may be used as a mixture.
  • Examples of the organic amine compound (H) include diethylenetriamine, triethyelenetetramine, tetraethylenepentamine, butylamine, hexylamine, octylamine, decylamine, laurylamine, hexamethylenediamine, triethanolamine, dibutylamine, diethanolamine, N,N,N′,N′-tetramethyl-1,3-butanediamine, benzylamine, cyclohexylamine, dodecamethylenediamine, diemethylethylenediamine, dim ethylaminoethanol, N,N,N′,N′-tetramethylethylenediamine, triethylamine, N,N-dimethylaniline, and diemethylbenzylaniline.
  • a compound that reacts with water to produce an organic amine such as ketimine can also be used as the organic amine compound.
  • a ratio at which the above component (H) is blended is not particularly limited; the component is blended in an amount of preferably about 0.001 to 10 parts by mass with respect to 100 parts by mass of the component (E).
  • One kind of the above organic amine compound may be used alone, or two or more kinds of such compounds may be used in combination.
  • the curable composition may be blended with any one of: various other additives such as a curing catalyst, an adhesion imparting agent, a physical property adjuster, a filler, a plasticizer, a thixotropic agent, a dehydrating agent (storage stability improver), a tackifier, a sagging inhibitor, an ultraviolet ray absorbing agent, an antioxidant, a flame retardant, a colorant, and a radical polymerization initiator; and various solvents such as toluene and an alcohol in addition to the above-mentioned components as required.
  • various other additives such as a curing catalyst, an adhesion imparting agent, a physical property adjuster, a filler, a plasticizer, a thixotropic agent, a dehydrating agent (storage stability improver), a tackifier, a sagging inhibitor, an ultraviolet ray absorbing agent, an antioxidant, a flame retardant, a colorant, and a radical polymerization initiator
  • the third aspect of the curable composition of the present invention contains the following components (I), (J), and (K) as essential components:
  • the above thermally expandable hollow spheres are microcapsules each made of a thermoplastic resin and each including a volatile expansive additive that is brought into a gas state at a temperature equal to or lower than the softening point of the resin.
  • the thermally expandable hollow spheres are the following substances: a volatile substance in each of the substances expands by virtue of heating, and, at the same time, a resin composition as the outer shell of each of the substances softens, whereby the volume of each of the substances expands to be many times as large as that in an initial state.
  • a hydrocarbon based liquid having a low boiling point has been conventionally used as the volatile expansive additive, and it has not been acknowledged that the thermally expandable hollow spheres are each a substance having high combustibility and imparting flame resistance.
  • the inventors of the present invention have found that a curable composition having excellent fire resistance while maintaining good physical properties and safety can be obtained at a low cost by incorporating the thermally expandable hollow spheres (K) in an amount of 0.01 part by mass or more to less than 20 parts by mass, preferably 0.01 part by mass or more to less than 15 parts by mass, or more preferably 0.03 part by mass or more to 10 parts by mass or less with respect to a total of 100 parts by mass of the reactive organic polymer containing at least one crosslinkable silyl group in any one of its molecules (I) and the reactive organic polymer containing less than one crosslinkable silyl group in any one of its molecules (J).
  • thermally expandable hollow spheres (K) 20 parts by mass or more is not desirable because the physical properties of the curable composition are reduced, and a foaming heat insulating layer to be formed when the composition is exposed to flame becomes so huge that the fire resistance of the composition is reduced.
  • the hardness of a rubber-like elastic body after the curing of the composition is preferably 40 or less, or more preferably 35 or less.
  • a reactive organic polymer containing at least one crosslinkable silyl group in any one of its molecules (I) to be used in the present invention will be described.
  • a reactive organic polymer containing at least one crosslinkable silyl group in any one of its molecules is used as the polymer (I).
  • An organic polymer containing at least one crosslinkable silyl group in any one of its molecules out of the organic polymers each containing a crosslinkable silyl group exemplified in the description of the component (A) according to the first aspect of the curable composition of the present invention can be similarly used as the organic polymer containing a crosslinkable silyl group (I).
  • the reactive organic polymer containing less than one crosslinkable silyl group in any one of its molecules (J) to be used in the present invention will be described.
  • An organic polymer containing zero or more and less than one crosslinkable silyl group in any one of its molecules is used as the polymer (J).
  • the crosslinkable silyl group is preferably one represented by the general formula (1).
  • polystyrene resin examples include a polyoxyalkylene based polymer, a vinyl-modified polyoxyalkylene based polymer, a vinyl based polymer, a polyester polymer, and a (meth)acrylate polymer each of which contains zero or more and less than one crosslinkable silyl group on average in any one of its molecules and the main chain of each of which may contain organosiloxane, and a copolymer or mixture of two or more of them.
  • a polyoxyalkylene based polymer examples include a polyoxyalkylene based polymer, a vinyl-modified polyoxyalkylene based polymer, a vinyl based polymer, a polyester polymer, and a (meth)acrylate polymer each of which contains zero or more and less than one crosslinkable silyl group on average in any one of its molecules and the main chain of each of which may contain organosiloxane, and a copolymer or mixture of two or more of them.
  • a polyoxyalkylene based polymer, a (meth) acrylic polymer, and a (meth)acrylic-modified polyoxypropylene polymer each of which contains less than one, or preferably less than 0.7 crosslinkable silyl group on average in any one of its molecules and the main chain of each of which may contain organosiloxane, and a copolymer or mixture of two or more of them are preferable, and such (meth)acrylic polymer is more preferable.
  • a method of producing the polymer (J) is not particularly limited, and the polymer can be produced by, for example, setting the number of crosslinkable silyl groups present in one molecule of an organic polymer containing a crosslinkable silyl group to less than one in the method of producing the organic polymer described in the description of the polymer (A).
  • a method of producing the polymer (J) is specifically, for example, a production method employed in Synthesis Example 4 to be described later.
  • the above reactive organic polymer (J) desirably has a weight average molecular weight of 2,000 or more to 50,000 or less, or preferably 2,000 or more to 30,000 or less and a narrow molecular weight distribution because the viscosity of the polymer before the curing of the composition is so low that the polymer can be easily handled, and the physical properties of the composition after the curing of the composition such as strength, an elongation rate, and a modulus are suitable. Only one kind of the above polymer (J) may be used, or two or more kinds of such polymers may be used in combination.
  • a ratio at which the polymer (J) is blended is not particularly limited; the polymer (J) is used in an amount of preferably 10 to 300 parts by mass, or more preferably 20 to 200 parts by mass with respect to 100 parts by mass of the polymer (I).
  • thermally expandable hollow spheres (K) to be used in the present invention will be described.
  • thermally expandable hollow spheres (K) include those disclosed in JP 42-26524B, JP49-14381B, JP63-122713A, JP63-122745A, JP4-08534A, JP56-113338A, JP11-209504A, JP 2000-191817A, JP 2002-12693A, JP 2002-363537A, and U.S. Pat. No. 4,722,943.
  • spheres each containing a foaming agent in a shell part composed of, for example, polyvinylidene chloride, a copolymer of vinylidene chloride and acrylonitrile, polyacrylonitrile, or a copolymer of acrylonitrile and methyl acrylate and each having a particle diameter of about 1 to 50 ⁇ m like a “Microsphere” manufactured by Matsumoto Yushi-Seiyaku Co., Ltd are used.
  • foaming agent examples include: low-boiling-point hydrocarbons such as ethane, propane, butane, pentane, hexane, heptane, and cyclopentane; halogenated hydrocarbons such as methyl chloride and ethyl chloride; HCFCs such as 1,1-dichloro-1-fluoroethane; and HFCs such as 1,1,1,2-tetrafluoroethane. Only one kind of the above hollow spheres (K) may be used, or two or more kinds of the spheres may be used in combination.
  • low-boiling-point hydrocarbons such as ethane, propane, butane, pentane, hexane, heptane, and cyclopentane
  • halogenated hydrocarbons such as methyl chloride and ethyl chloride
  • HCFCs such as 1,1-dichloro-1-fluoroethane
  • HFCs such
  • any other foaming agent may be added to the composition according to the third aspect of the curable composition of the present invention.
  • the kind of the foaming agent is not particularly limited, and an ordinary agent can be used.
  • multiple agents may be combined.
  • Ammonium polyphosphate is particularly desirably used as the other foaming agent; the generation of an ammonia gas caused by the hydrolysis of ammonium polyphosphate and phosphorus in ammonium polyphosphate promote the carbonization of any other substance to cause the substance to produce an incombustible carbonized layer, whereby ammonium polyphosphate has an action of improving the fire resistance of the composition.
  • ammonium polyphosphate described above has poor water resistance, so coated ammonium polyphosphate with improved water resistance is more desirable.
  • additives are not particularly limited, and an ordinary additive can be used. In addition, multiple additives may be combined.
  • the curable composition of the present invention can be turned into a one-component liquid or a two-component liquid as required.
  • the curable composition of the present invention which is most suitably used in a sealing material, can be used in, for example, an adhesive, a pressure-sensitive adhesive, a coating material, or a potting material as required.
  • the curable composition of the present invention can be used for, for example, various structures, automobiles, civil engineering, and electrical and electronic fields.
  • a fire-resistant structure capable of passing a fire resistance test described in JIS A 1304 can be formed with ease at a low cost by the combined use of a sealing material having fire resistance and using the third aspect of the curable composition of the present invention as an available ingredient and a wall material having fire resistance.
  • FIG. 1 is a perspective view showing an example of a fire-resistant structure to be formed by the formation method of the present invention.
  • FIG. 2 is a top view of FIG. 1 .
  • a wall material 10 having fire resistance and a wall material 11 having fire resistance are brought into abutment with each other through a filler 14 such as a back-up material or a bond breaker provided for an abutting portion A, and the abutting portion A is filled with a sealing material 12 of the present invention, whereby a fire-resistant structure 13 is formed.
  • Examples of the above wall material 10 having fire resistance include precast concrete (PC), an autoclaved lightweight aerated concrete panel (ALC), and a ceramic covering material for a fire-resistant structure.
  • the above filler 14 such as a back-up material or a bond breaker is not particularly limited, and a wide variety of known fillers can be used; a fire-resistant filler such as the “Litoflex” manufactured by NICHIAS Corporation is more preferably used because the fire resistance of the fire-resistant structure is additionally improved.
  • the fire-resistant structure to be obtained by the present invention can form a foaming heat insulating layer when exposed to flame to shield, for example, heat, flame, smoke, and a gas generated by combustion.
  • a structure having extremely excellent fire resistance not only when a special back-up material having fire resistance is used but also when an ordinary back-up material (such as a product extruded or cut out from polyethylene) is used.
  • a primary amine dissolved by heating (stearylamine; trade name “FIRMIN 80” manufactured by KAO CORPORATION, amine value 207) were loaded into a stirring vessel provided with a heating device and an ester tube.
  • 203 g of a carbonyl compound (methyl isobutyl ketone, molecular weight: 100.2) were added to the vessel while the amine was stirred.
  • 130 g of toluene were further added to the mixture.
  • the resultant was heated to 110 to 150° C., continuously stirred for 3 hours, and dehydrated from the ester tube. Next, excessive amounts of the carbonyl compound and toluene were removed under reduced pressure, whereby a ketimine compound was obtained.
  • the temperature of a pressure stirring tank type reactor provided with an electrothermal heater and having a volume of 1,000 ml was kept at 200° C.
  • a monomer mixture composed of 84 parts of butyl acrylate as an acrylate monomer, 16 parts of ⁇ -methacryloxypropyltrimethoxysilane as a hydrolyzable silyl group-containing monomer, and 1 part of di-t-butyl peroxide as a polymerization initiator started to be continuously supplied from a raw material tank to the reactor at a constant supply speed (80 g/min, residence time: 12 minutes), and a reaction liquid corresponding to the supplied amount of the monomer mixture was continuously pulled out from the outlet of the reactor.
  • reaction temperature Immediately after the initiation of the reaction, the reaction temperature reduced once, and then an increase in temperature due to heat of polymerization was observed.
  • the reaction temperature was kept at 250 to 251° C. by controlling the heater.
  • the time point when the temperature became stable after the initiation of the supply of the monomer mixture was defined as the starting point of the collection of the reaction liquid.
  • the reaction was continued for 25 minutes from the starting point, whereby 2 kg of the monomer mixed liquid were supplied, and 1.9 kg of the reaction liquid were recovered. After that, the reaction liquid was introduced to a thin-film evaporator, and volatile components such as an unreacted monomer were separated, whereby a condensed liquid was obtained. Gas chromatographic analysis confirmed that no unreacted monomer was present in the condensed liquid.
  • the resultant polymer had a number average molecular weight of 2,000 in terms of polystyrene measured by gel permeation chromatography using tetrahydrofuran as a solvent and a weight average molecular weight of 4,800 in terms of polystyrene similarly measured.
  • the number of crosslinkable silyl groups per one molecule of the polymer was 1.29.
  • An acrylic polymer 1 having 1.29 crosslinkable silyl groups on average in any one of its molecules was obtained.
  • a modified silicone polymer SA 100S manufactured by Kaneka Corporation
  • component (A) that is, the organic polymer containing a crosslinkable silyl group, a 1577 FF (manufactured by Ciba Specialty Chemicals) as the component (B), that is, the triazine based ultraviolet ray absorbing agent, a CHIMASSORB 119FL (manufactured by Ciba Specialty Chemicals) as the component (C), that is, the light stabilizer, a plasticizer, a filler, and a dehydration treatment agent were loaded, and the blended substances were mixed and stirred under heat and reduced pressure at 110° C.
  • SA 100S manufactured by Kaneka Corporation
  • Curable compositions were each prepared in the same manner as in Example 1 except that the blended substances and a ratio at which each of the substances was blended were changed as shown in each of Tables 1 and 2.
  • each of the above curable compositions was molded into a sheet having a thickness of 5 mm, and the sheet was aged at 23° C. for 7 days and subsequently at 30° C. for 7 days, whereby the thick layer portion of a cured product sheet was obtained.
  • each of the above curable compositions was molded into a sheet having a thickness of 0.2 mm by using a metal spacer as a sheet having a thickness of 0.2 mm, and the resultant sheet was aged at 23° C. for 7 days and subsequently at 30° C. for 7 days, whereby the thin layer portion of the cured product sheet was obtained.
  • Each of the resultant thick layer portion and the resultant thin layer portion was irradiated with light from a Daipla Metal Weather (manufactured by Daipla Wintes Co., Ltd., model KU-R4-A), and the deterioration of the surface of each of the layers with time was visually observed.
  • Daipla Metal Weather manufactured by Daipla Wintes Co., Ltd., model KU-R4-A
  • the thin layer portion was evaluated for time period needed complete whitening.
  • x less than 200 hours, ⁇ : 200 hours or more and less than 500 hours, ⁇ : 500 hours or more and less than 1,000 hours, ⁇ : 1,000 hours or more.
  • the thick layer portion was evaluated for time period needed for the generation of a crack.
  • x less than 500 hours, ⁇ : 500 hours or more and less than 800 hours, ⁇ : 800 hours or more and less than 1,200 hours, ⁇ : 1,200 hours or more.
  • Each of the above curable compositions was molded into a sheet having a thickness of 10 mm.
  • the sheet was exposed to the outdoors in the south direction at an angle of 45° for 6 months, and the presence or absence of staining on the surface of the sheet was visually observed.
  • the case where the staining was severe was denoted by x
  • the case where nearly no staining was present was denoted by ⁇
  • the case where no staining was present was denoted by ⁇ .
  • An abutting test body having a joint length of 50 mm, a joint width of 12 mm, and a joint depth of 12 mm was produced by using each of the resultant curable compositions and a ceramic siding material (trade name “MOEN M” manufactured by NICHIHA CORPORATION). It should be noted that the body was aged under standard conditions of 23° C. and 50% RH for 14 days. The produced test body was subjected to a tensile strength test at a tension speed of 50 mm/min, and its maximum elongation rate was measured.
  • each of the curable compositions of Examples 1 to 12 showed excellent weather resistance in not only a thick layer portion but also a thin layer portion.
  • each of the curable compositions of Examples 1 and 2 to each of which the ketimine compound had been added showed significantly improved anti-staining property.
  • each of the curable compositions of Examples 1 to 9 each using a (meth)acrylic polymer having a crosslinkable silyl group at a terminal of any one of its molecules as the component (A) showed extremely good weather resistance and a high elongation rate particularly useful in a sealing material.
  • n-butyl acrylate 85 parts by weight of n-butyl acrylate, 15 parts by weight of methyl methacrylate, 10 parts by weight of ⁇ -methacryloxypropyltrimethoxysilane, and 0.1 part by weight of titanocene dichloride as a metal catalyst were loaded into a flask provided with a stirring device, a nitrogen gas-introducing tube, a temperature gauge, and a reflux condenser, and the contents in the flask were heated to 70° C. while a nitrogen gas was introduced into the flask.
  • a modified silicone polymer SA 100S (manufactured by Kaneka Corporation: trade name “SA 100S”) as the component (E), that is, the organic polymer containing a crosslinkable silyl group, an XG-4010 (manufactured by TOAGOSEI CO., LTD.) as the component (F), that is, the (meth)acrylic polymer containing an epoxy group, ground calcium carbonate, surface-treated calcium carbonate, an antioxidant, a NEOSTAN U-28 (manufactured by NITTO KASEI CO., LTD.) as the component (G), that is, the divalent tin organic carboxylate, and a FIRMIN 20D (manufactured by KAO CORPORATION) as the component (H), that is, the organic amine compound were loaded, whereby a curing composition was prepared.
  • Curable compositions were each prepared in the same manner as in Example 13 except that the blended substances and a ratio at which each of the substances was blended were changed as shown in each of Table 5.
  • An H-shaped test body in accordance with JIS A 1439 was produced, and was aged under an environment of 23° C. and 50% RH for 7 days, an environment of 50° C. for 7 days, and an environment of 90° C. for 14 days. After that, the body was left at rest under an environment of 23° C. and 50% RH for 24 hours. The thickness at that time (about 12.00 mm) was defined as an initial thickness. Next, the body was left at rest under an environment of 23° C. and 50% RH for 24 hours while being elongated so as to be twice as thick as the initial thickness (about 24.00 mm) with a predetermined jig. 24 hours after that, the jig was released, and the body was left at rest for 1 hour. After that, the thickness was measured, and restoring property was obtained by using the following equation.
  • Restoring property (%) (thickness after elongation ⁇ thickness after release)/initial thickness ⁇ 100
  • a durability test (durability category 9030) was performed in accordance with JIS A 1439 (1997) 4. 17. In the durability test, a passing result was denoted by ⁇ , and an unsatisfactory result was denoted by x.
  • Evaluation method the heating of the sealing material was promoted in a dryer at 50° C. for 7 days. After that, black silica sand was sprinkled on the paint, and the presence or absence of staining was visually observed on the basis of the extent to which the sand adhered to the paint. All paints were evaluated as follows: the case where no staining was observed was denoted by ⁇ , and the case where staining was observed in any one of the paints was denoted by x.
  • Paints; Buildec solvent based acryl, manufactured by DAI NIPPON TORYO CO., LTD.
  • Vinylose solvent based vinyl chloride, manufactured by DAI NIPPON TORYO CO., LTD.
  • Odecoat G aqueous acryl, manufactured by Nippon Paint Co., Ltd.
  • DAN UNI aqueous acryl, manufactured by Nippon Paint Co., Ltd.
  • New Topless Clean aqueous acrylic silicone, manufactured by SK KAKEN Co., Ltd.
  • Tilelac U urethane based, manufactured by Nippon Paint Co., Ltd.
  • New Softlithin aqueous acryl, manufactured by SK KAKEN Co., Ltd.
  • a weather resistance test was performed in a sunshine weatherometer, and the external appearance of each of the curable compositions was investigated 1,000 hours, 2,000 hours, 3,000 hours, and 4,000 hours after the initiation of the test.
  • the symbol ⁇ means that no crack is present
  • the symbol ⁇ means that a small number of cracks are present
  • the symbol x means that a large number of cracks are present.
  • Each of the resultant curable compositions was subjected to an elongation rate test in the same manner as in Example 1, and its maximum elongation rate was measured.
  • each of the curable compositions of Examples 13 to 17 was excellent in weather resistance, paint anti-staining property, and durability, and had extremely good restoring property; each of the compositions had a restoring property of 95% or more.
  • each of the curable compositions of Examples 13 and 14 each using a (meth)acrylic polymer having a crosslinkable silyl group at a terminal of any one of its molecules as the component (E) was excellent in restoring property, durability, and paint anti-staining property, had extremely high weather resistance, and showed an excellent elongation rate.
  • each of the curable compositions of Comparative Examples 5 and 6 was poor in paint anti-staining property and weather resistance.
  • each of the curable compositions of Comparative Examples 6 to 8 was poor in restoring property, and failed in the durability test.
  • a mixed liquid composed of 670 g of butyl acrylate, 300 g of 2-ethylhexyl acrylate, 30 g of ⁇ -methacryloxypropyltrimethoxysilane, 200 g of 2-propanol, and 10 g of di-t-butyl peroxide was supplied into the autoclave at a constant speed, and a reaction was initiated. The addition and the reaction were performed over 2 hours, and, 10 minutes after the completion of the addition, the mixture was cooled to 30° C., whereby 1,350 g of a polymerization liquid were obtained. The resultant polymerization liquid was condensed under reduced pressure, whereby the solvent was removed. An acrylic polymer containing a crosslinkable silyl group, the polymer having Mw of 1,800, Mn of 4,400, and a silylation rate of 0.22, was obtained.
  • Curable compositions were each prepared in the same manner as in Example 18 except that the blended substances and a ratio at which each of the substances was blended were changed as shown in each of Tables 7 and 8.
  • An abutting test body having a joint length of 50 mm, a joint width of 10 mm, and a joint depth of 6 mm is produced by using each of the resultant curable compositions and a ceramic siding material (MOEN M manufactured by NICHIHA CORPORATION). It should be noted that the body is aged under standard conditions of 23° C. and 50% RH for 14 days.
  • the test body is exposed to flame from a Bunsen gas burner, the flame having a height adjusted to 40 mm, in such a manner that the lower portion of the joint of the test body has a height of 20 mm from the uppermost portion of the Bunsen burner.
  • the temperature of the back surface of the joint portion is measured 30 minutes and 60 minutes after the initiation of the exposure, and the test body is evaluated for its fire resistance on the basis of the following criteria:
  • ⁇ a considerable amount of the rubber-like elastic body remains; ⁇ : a small amount of the rubber-like elastic body remains; ⁇ : no rubber-like elastic body remains, and the back surface becomes a hard film; and x: the joint itself falls within 60 minutes, and does not remain.
  • a test body is produced in the same manner as in the above fire resistance test, and the hardness of the cured curable composition is measured with a rubber hardness meter (JIS A type).
  • An abutting test body was produced in the same manner as in the above fire resistance test by using each of: a composition before the addition of the component (K) or a foaming agent of each of the resultant curable compositions [Composition Before Addition]; and each of the resultant curable compositions [composition after the addition of the component (K) or a foaming agent, Composition After Addition]. It should be noted that each body was aged under standard conditions of 23° C. and 50% RH for 14 days. Each of the test bodies was subjected to a tensile strength test at a tension speed of 50 mm/min, and its maximum elongation rate was measured. The maximum elongation rates of Composition Before Addition and Composition After Addition were compared, and a physical property retentivity (%) was determined. Each of the compositions was evaluated for its physical property retentivity on the basis of the following criteria:
  • ⁇ the physical property retentivity is 50% or more; and x: the physical property retentivity is less than 50%.
  • Each of the resultant curable compositions was mixed and kneaded with a pigment so as to be provided with a color tone.
  • Each of the compositions was evaluated for its color tone on the basis of the following criteria:
  • ⁇ a composition can be provided with an arbitrary color tone
  • x a composition cannot be provided with an arbitrary color tone
  • Each of the resultant curable compositions was subjected to an elongation rate test in the same manner as in Example 1, and its maximum elongation rate was measured.
  • each of the curable compositions of Examples 18 to 30 had fire resistance, and showed a good physical property retentivity and a good color tone.
  • Each of the curable compositions of Examples 18 to 26 and 28 each using an acrylic polymer as each of the components (I) and (J) showed particularly excellent fire resistance, and the state of a rubber-like elastic body made of each of the curable compositions on the back surface of a joint was extremely good.
  • each of the curable compositions of Examples 18 to 27 each using a (meth)acrylic polymer having a crosslinkable silyl group at a terminal of any one of its molecules as the component (I) not only had fire resistance but also showed a high elongation rate particularly useful in a sealing material.
  • each of the curable composition of Comparative Example 9 not blended with the component (K) and the curable composition of Comparative Example 16 blended with a large amount of the component (K) could not obtain fire resistance, and showed a poor physical property retentivity.
  • the curable composition of Comparative Example 17 not blended with the component (J) could not obtain fire resistance.
  • each of the curable compositions of Comparative Examples 2 to 7 was also poor in physical property retentivity.
  • a composition was prepared in the same manner as in Example 23 except that the component (I) was not blended. However, the resultant composition did not cure.

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EP2942334A1 (de) * 2014-05-06 2015-11-11 Siemens Aktiengesellschaft Schichtsystem für ein Bauteil
US20170022400A1 (en) * 2013-12-04 2017-01-26 Three Bond Co., Ltd. Moisture curable composition
WO2018069530A1 (en) 2016-10-14 2018-04-19 Basf Se Stabilizer composition
US11505702B2 (en) * 2019-04-05 2022-11-22 Prc-Desoto International, Inc. Controlled cure rate using polyether-coated synergists
US11591790B2 (en) * 2014-08-26 2023-02-28 Iso-Chemie Gmbh Sealing tape for sealing a joint
KR102666685B1 (ko) * 2017-09-05 2024-05-20 세메다인 가부시키 가이샤 내화용 경화성 조성물

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