WO2005108494A1 - 硬化性組成物 - Google Patents
硬化性組成物 Download PDFInfo
- Publication number
- WO2005108494A1 WO2005108494A1 PCT/JP2005/007803 JP2005007803W WO2005108494A1 WO 2005108494 A1 WO2005108494 A1 WO 2005108494A1 JP 2005007803 W JP2005007803 W JP 2005007803W WO 2005108494 A1 WO2005108494 A1 WO 2005108494A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- polymer
- curable composition
- weight
- titanium
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/336—Polymers modified by chemical after-treatment with organic compounds 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/014—Stabilisers against oxidation, heat, light or ozone
-
- 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
- C08K5/0091—Complexes with metal-heteroatom-bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- 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
- C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
- C09D171/02—Polyalkylene oxides
-
- 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
- C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
- C09J171/02—Polyalkylene oxides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
Definitions
- the present invention relates to a silicon-containing group having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and capable of crosslinking by forming a siloxane bond (hereinafter also referred to as “reactive silicon group”).
- the present invention relates to a curable composition containing a polyoxyalkylene polymer having the formula (1) and a Z or (meth) acrylate polymer (hereinafter also referred to as “organic polymer”).
- Organic polymers containing at least one reactive silicon group in the molecule can be crosslinked at room temperature by the formation of siloxane bonds involving hydrolysis of the reactive silicon group by moisture or the like. Then, when a rubber-like cured product is obtained, it is known that it has a property.
- an organic polymer whose main chain skeleton is a polyoxyalkylene-based polymer and a z- or (meth) acrylate-based polymer is disclosed in It is disclosed in 1) and (Patent Document 2), etc., and is already industrially produced and widely used for applications such as sealing materials, adhesives, and paints.
- the curable composition containing the organic polymer having a reactive silicon group is cured using a silanol condensation catalyst, and is usually cured with dibutyltin bis (acetyl acetate).
- Organic tin-based catalysts having a carbon-tin bond such as, for example, are widely used.
- the toxicity of organotin compounds has been pointed out, and the development of non-organotin catalysts has been demanded.
- Patent Document 15 As disclosed in (Patent Document 16), (Patent Document 17), (Patent Document 18), (Patent Document 19), (Patent Document 20), (Patent Document 21), (Patent Document 22)
- an organic polymer containing a reactive silicon group is added with various light stabilizers for the purpose of improving weather resistance. There are cases.
- Patent Document 1 JP-A-52-73998
- Patent Document 2 JP-A-59-74149
- Patent Document 3 Japanese Patent Publication No. 39-27643 (US Patent No. 3175993)
- Patent Document 4 U.S. Patent No. 3334067
- Patent Document 5 JP-A-58-17154 (JP-B-3-57943)
- Patent Document 6 Japanese Patent Application Laid-Open No. 62-146959 (Japanese Patent Publication No. 5-45635)
- Patent Document 7 JP-A-5-311063
- Patent Document 8 JP 2001-302929 A
- Patent Document 9 JP 2001-302302 A
- Patent Document 10 JP 2001-302931 A
- Patent Document 12 JP 2001-348528 A
- Patent Document 13 JP 2002-249672 A
- Patent Document 15 Japanese Patent Laid-Open No. 2001 — 19842
- Patent Document 16 Japanese Patent Application Laid-Open No. 61--233043
- Patent Document 17 JP-A-5-287186
- Patent Document 18 JP-A-5-70531
- Patent Document 19 JP-A-9 194731
- Patent Document 21 JP-A-11-172110
- Patent Document 22 JP-A-11--21442
- Patent Document 23 JP 2000-273439 A
- the present inventors have found that when a titanium chelate is used as a curing catalyst for a polyoxyalkylene polymer having a reactive silicon group and a Z or (meth) acrylate polymer, a benzotriazole ring It has been found that there is a problem that the curability is reduced by the addition of a light-resistant stabilizer having the following problem, and that the composition is significantly colored.
- the present invention provides a polyoxyalkylene polymer having a reactive silicon group and Z or
- a curable composition containing a (meth) acrylate polymer as a main component, and using a non-organic tin catalyst, has good curability, adhesion and weather resistance without coloring the composition. It is intended to provide a neutral composition.
- the present inventors have conducted intensive studies in order to solve such a problem.
- a titanium chelate (B) having a specific structure was used as a curing catalyst for the polymer, and a light-resistant stabilizer (C)
- a light-resistant stabilizer (C-1) with a specific structure was used as the main component of the composition, it is possible to obtain good curability, adhesion and weather resistance without coloring the composition, even though it is a non-organic tin catalyst.
- the present inventors have found that a curable composition having the same can be obtained, and completed the present invention.
- the present invention provides:
- (C) A curable composition characterized in that a main component of the light stabilizer is (C 1) a light stabilizer having no benzotriazole ring.
- n R 1 s are each independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms.
- 4 n R 2 s are each independently a hydrogen atom or a substituted Alternatively, it is an unsubstituted hydrocarbon group having 1 to 20 carbon atoms.
- 4—n R 3 and 4—n R ′ are each independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. It is a hydrogen group, and ⁇ is the deviation force of 0, 1, 2, and 3.
- the curable composition of the present invention does not contain (C-2) a light stabilizer having a benzotriazole ring as the light stabilizer (C).
- the content of (C-2) is preferably less than 0.1 part by weight based on 100 parts by weight of the polymer ( ⁇ ).
- the polymer (A) is preferably a polyoxypropylene-based polymer having a silicon-containing group that can be crosslinked by forming a siloxane bond, and a Z- or (meth) acrylate-based polymer. .
- the glass transition temperature of the polymer (A) is 20 ° C. or less.
- Examples of the light-resistant stabilizer having no benzotriazole ring of (C-1) include a benzoate ultraviolet absorber, a triazine ultraviolet absorber, a cyanoacrylate ultraviolet absorber, and a benzophenone ultraviolet absorber.
- One or more light stabilizers selected from the group consisting of hindered amine light stabilizers are more preferable, and benzoate ultraviolet absorbers and Z or hindered amine light stabilizers are more preferable.
- the above hindered amine light stabilizer is preferably a hindered amine light stabilizer having no NH group.
- a preferable mixing ratio of the above (A), (B) and (C1) is 100 parts by weight of the polymer (A).
- a preferred embodiment of the curable composition according to the present invention includes a sealing material or an adhesive using the curable composition described in any one of the above.
- the curable composition of the present invention has no coloring of the composition while using a non-organic tin catalyst, and has excellent curability, adhesiveness, and weather resistance.
- a polyoxyalkylene polymer having a reactive silicon group and a (meth) acrylate polymer having a Z or a reactive silicon group (hereinafter, referred to as “A”) Organic polymer ").
- A a polyoxyalkylene polymer having a reactive silicon group and a (meth) acrylate polymer having a Z or a reactive silicon group
- A Organic polymer
- the polyoxygen such as the component (A) of the present invention Alkylene-based polymers and (meth) acrylate-based polymers are more preferable than polyoxyalkylene-based polymers because they have excellent deep-curing properties when formed into a one-part composition with high moisture permeability. preferable.
- the glass transition temperature of the organic polymer as the component (A) is not particularly limited, but is preferably 20 ° C or less, more preferably 0 ° C or less, and 20 ° C or less. It is particularly preferred that it is C or less. If the glass transition temperature is higher than 20 ° C, the viscosity in winter or in a cold region may increase and the workability may deteriorate, and the flexibility of the cured product may decrease and the elongation may decrease.
- the glass transition temperature is a value measured by DSC.
- the reactive silicon group contained in the polyoxyalkylene polymer having a reactive silicon group and the (meth) acrylate polymer having a reactive silicon group according to the present invention is A group having a hydroxyl group or a hydrolyzable group bonded to an elemental atom and capable of being crosslinked by a reaction accelerated by a curing catalyst.
- the reactive silicon group the general formula (3):
- R 6 and R 7 are each independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or (R ′) SiO
- -(R ' is each independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms), and is a triorganosiloxy group.
- X is each independently a hydroxyl group or a hydrolyzable group.
- b is 0, 1, or 2
- a is 0, 1, 2, or 3, and b and a do not become 0 at the same time.
- m is 0 or an integer of 1 to 19).
- the hydrolyzable group is not particularly limited, and may be any conventionally known hydrolyzable group! Specific examples include a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, and an alkoxycarbonyl group. Among them, hydrogen atoms, alkoxy groups, acyloxy groups, ketoxime groups, amino groups, amide groups, aminooxy groups, mercapto groups and alkoxy groups are preferred because of their mild hydrolytic properties. From the viewpoint of /, and! /, An alkoxy group is particularly preferred.
- Hydrolyzable groups and hydroxyl groups can be bonded to one silicon atom in the range of 1 to 3 groups.
- (A + ⁇ b) is preferably in the range of 1 to 5.
- two or more hydrolyzable groups or hydroxyl groups are bonded to the reactive silicon group, they may be the same or different.
- the number of silicon atoms forming a reactive silicon group is one or more. In the case of silicon atoms linked by a siloxane bond or the like, the number is preferably 20 or less.
- a reactive silicon group represented by (c is an integer of 1 to 3) is preferred because it is easily available.
- R 6 and R 7 in the general formulas (3) and (4) include, for example, an alkyl group such as a methyl group and an ethyl group; a cycloalkyl group such as a cyclohexyl group; And an aralkyl group such as a benzyl group, and a triorganosiloxy group represented by (R ′) SiO— wherein R is a methyl group or a phenyl group.
- Particularly preferred is a phenyl group.
- the reactive silicon group include a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, a dimethoxymethylsilyl group, a diethoxymethylsilyl group, and a diisopropoxy group. And a methylsilyl group.
- a trimethoxysilyl group, a trimethoxysilyl group, and a dimethoxymethylsilyl group, which are more preferred, are particularly preferred because of high activity and good curability. From the viewpoint of storage stability, a dimethoxymethylsilyl group is particularly preferred.
- a triethoxysilyl group is an alcoholic ethanol produced by a hydrolysis reaction of a reactive silicon group, and is particularly preferable because it has higher safety.
- Introduction of a reactive silicon group may be performed by a known method! That is, for example, the following method can be used.
- An organic polymer having a functional group such as a hydroxyl group in a molecule is reacted with an organic compound having an active group and an unsaturated group having reactivity to the functional group, and containing an unsaturated group.
- an organic polymer is obtained by copolymerization with an unsaturated group-containing epoxy resin conjugate.
- the hydrosilylation is carried out by reacting the reaction product obtained in step (1) with hydrosilane having a reactive silicon group.
- Mouth A compound having a mercapto group and a reactive silicon group is reacted with the unsaturated group-containing organic polymer obtained in the same manner as in the method (a).
- the method (a) or the method (c) of reacting a polymer having a hydroxyl group at the terminal with a compound having an isocyanate group and a reactive silicon group is a comparative method. It is preferable because a high reaction rate can be obtained in a short reaction time. Furthermore, the organic polymer having a reactive silicon group obtained by the method (a) becomes a curable composition having lower viscosity and better workability than the organic polymer obtained by the method (c). In addition, since the organic polymer obtained by the method of (mouth) has a strong odor based on mercaptosilane, the method of (ii) is particularly preferred.
- hydrosilane conjugate used in the method (a) include, for example, halogen silanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane, and phenyldichlorosilane; trimethoxysilane, trimethoxysilane, and the like.
- Alkoxysilanes such as ethoxysilane, methylethoxysilane, methyldimethoxysilane and phenyldimethoxysilane; acyloxysilanes such as methyldiacetoxysilane and phenyldiacetoxysilane; bis (dimethylketoximate) methylsilane, bis (Cyclohexyl ketoximate) Powers of ketoxime silanes such as methylsilane are not limited to these. Of these, halogenated silanes and alkoxysilanes are particularly preferred, and alkoxysilanes are particularly preferred because the resulting curable composition has a mild hydrolyzability and is easy to handle! .
- methyldimethoxysilane is easily available.
- the curability of the curable composition containing the obtained organic polymer, the storage stability, the elongation characteristics, and the bow I tensile strength are high. Like,.
- a compound having a mercapto group and a reactive silicon group is converted into an organic polymer by a radical addition reaction in the presence of a radical initiator and Z or a radical generating source.
- a radical addition reaction in the presence of a radical initiator and Z or a radical generating source.
- examples include a method of introducing the compound into an unsaturated bond site, but the method is not particularly limited.
- Examples of the body include, for example, ⁇ -mercaptopropyltrimethoxysilane, ⁇ -mercaptopylpyrmethyldimethoxysilane, ⁇ -mercaptopropyltriethoxysilane, ⁇ -mercaptopropylmethylethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltrimethylsilane Ethoxysilane, (mercaptomethyl) methyljetoxysilane, (mercaptomethyl) methyldimethoxysilane, etc.
- the power is not limited to these! /.
- the compound having an isocyanate group and a reactive silicon group include, for example, ⁇ -isocyanatepropyltrimethoxysilane, ⁇ -isocyanatepropylmethyldimethoxysilane, ⁇ -isocyanatepropyltriethoxysilane , ⁇ -isocyanate propynolemethyl ethoxysilane, (isocyanate methyl) trimethoxy silane, (iso cyanate methyl) triethoxy silane, (iso cyanate methyl) dimethoxy methyl silane, (iso cyanate methyl) di
- ethoxymethylsilane etc. is not limited to these.
- the disproportionation reaction of a silane compound may proceed.
- rather dangerous compounds such as dimethoxysilane are formed.
- such disproportionation does not proceed with ⁇ -mercaptopropyltrimethoxysilane or ⁇ -isocyanatepropyltrimethoxysilane. Therefore, when three hydrolyzable groups such as a trimethoxysilyl group are bonded to one silicon atom as a silicon-containing group, and a group is used, the synthesis method of (Port) or (C) is used. Preferably, it is used.
- the organic polymer having a reactive silicon group may have a linear or branched organic polymer having a number average molecular weight of about 500 to 100,000 in terms of polystyrene by GPC, more preferably ⁇ 1 , 000 to 50,000, especially preferred ⁇ 3,000 to 30,000. If the number average molecular weight is less than 500, the cured product tends to be inferior in elongation characteristics, and if it exceeds 100,000, the viscosity tends to be high, and the workability tends to be inconvenient.
- an organic polymer In order to obtain a rubber-like cured product having high strength, high elongation and low elastic modulus, an organic polymer must be used. It is preferable that at least one, preferably 1.1 to 5 reactive silicon groups are contained in one molecule of the polymer on average. If the number of reactive silicon groups contained in the molecule is less than one on average, the curability will be insufficient and good rubber elasticity will be exhibited.
- the reactive silicon group may be at the terminal of the main chain of the organic polymer molecular chain, and may be at the terminal of the side chain, or may be at both terminals.
- the effective mesh length of the organic polymer component contained in the finally formed cured product becomes long, and therefore, high strength and high strength are obtained. Elongation makes it easier to obtain a rubber-like cured product having a low elastic modulus.
- the polyoxyalkylene polymer is essentially represented by the general formula (5):
- R 8 is from 1 -C 14.
- R 8 in the general formula (5) has a number of carbon atoms Preferred are 1 to 14, more preferably 2 to 4, linear or branched alkylene groups.
- Specific examples of the repeating unit represented by the general formula (5) include:
- the main chain skeleton of the polyoxyalkylene polymer may have only one kind of repeating unit force, or may have two or more kinds of repeating unit forces.
- those made of a polymer containing a propylene oxide polymer as a main component are preferable because they are amorphous and have relatively low viscosity.
- Examples of the method for synthesizing the polyoxyalkylene polymer include a polymerization method using an alkali catalyst such as KOH, and a method in which an organoaluminum compound described in JP-A-61-215623 is reacted with porphyrin. Transition metal compound such as complex-polymerization method using vorphyrin complex catalyst, JP-B-46-27250, JP-B-59-15336, US Patent 3278457, US Patent 3278458, US Patent 3278459, US Patent 3427256 US Pat. No. 3,427,334, US Pat. No.
- the method for producing the polyoxyalkylene polymer having a reactive silicon group of the present invention is described in JP-B-45-36319, JP-B-46-12154, JP-A-50-156599, and JP-A-54-6096. No. 55-13767, No. 55-13468, No. 57-164123, Japanese Patent Publication No. 3-2450, U.S. Pat.No. 3,632,557, U.S. Pat. No. 4,345,053, U.S. Pat.No. 4,366,307, U.S. Pat.
- JP-A-61-197631, JP-A-61-215622, JP-A-61-215623, JP-A-61-218632, JP-A-3-72527, JP-A-3-47825, JP-A-8- The ability to exemplify a polyoxyalkylene polymer having a high molecular weight and a narrow molecular weight distribution with a MwZMn of 1.6 or less and a number average molecular weight of 6,000 or more proposed in each publication of 231707, especially those limited to these is not.
- the polyoxyalkylene polymer having a reactive silicon group may be used alone or in combination of two or more.
- the (meth) acrylate-based monomer constituting the main chain of the (meth) acrylate-based polymer is not particularly limited, and various types can be used.
- the following vinyl monomers can be copolymerized together with the (meth) acrylate monomer.
- the vinyl monomers include styrene monomers such as styrene, vinyltoluene, ⁇ -methylstyrene, chlorstyrene, styrenesulfonic acid and salts thereof; perfluoroethylene, perfluoropropylene, bilidene fluoride, and the like.
- butyl monomers such as butyltrimethoxysilane and butyltriethoxysilane; monoalkyl esters and dialkyl esters of maleic anhydride, maleic acid, and maleic acid; Alkyl esters and dialkyl esters; maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexinolemaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenolmaleimide, silicone Maleimide monomers such as hexylmaleimide; butyl monomers containing -tolyl groups such as acrylonitrile and methallyl-tolyl; butyl monomers containing amide groups such as acrylamide and methacrylamide; butyl acetate, butyl propionate, butyl pivalate, Butyl esters such as benzoate and cinnamate;
- a polymer composed of a styrene-based monomer and a (meth) acrylic-acid-based monomer is preferable in view of the physical properties of the product. More preferred are (meth) acrylic polymers having an acrylate monomer and methacrylate monomer capability, and particularly preferred are acryl polymers having an acrylate monomer capability. In general building applications, the viscosity of the compound is low, the cured product has low modulus, high elongation, weather resistance, A butyl acrylate-based monomer is more preferable because physical properties such as thermal properties are required.
- copolymers mainly containing ethyl acrylate are more preferred.
- This polymer mainly composed of ethyl acrylate is excellent in oil resistance, but tends to be slightly inferior in low-temperature characteristics (cold resistance).
- a part of ethyl acrylate is converted to butyl acrylate. It is also possible to replace it.
- the ratio is preferably set to 40% or less. More preferably, it is 30% or less.
- the ratio is preferably 40% or less. It is possible to obtain a suitable polymer by taking into account the required properties such as oil resistance, heat resistance, and low temperature properties, and changing the ratio according to various uses and required purposes.
- examples of excellent physical properties such as oil resistance, heat resistance, and low-temperature properties include ethyl acrylate, butyl acrylate, and 2-methoxyethyl acrylate (40 to 50 Z20 to 30 Z30 to 20 by weight ratio). )).
- these preferred monomers may be copolymerized with other monomers, or furthermore, may be subjected to block copolymerization.In this case, it is preferable that these monomers be contained in a weight ratio of 40% or more. Is preferred,.
- (meth) acrylic acid means acrylic acid and ⁇ or methacrylic acid.
- the method for synthesizing the (meth) acrylate polymer is not particularly limited, and may be a known method.
- a polymer obtained by a normal free radical polymerization method using an azo compound, a peroxide, or the like as a polymerization initiator has a problem in that the viscosity of the polymer increases as the molecular weight distribution value generally increases to 2 or more. ing. Therefore, a low-V, (meth) acrylate polymer having a narrow molecular weight distribution and a low viscosity, and having a high proportion of (meth) acrylate polymers having a crosslinkable functional group at the molecular chain end. In order to obtain, it is preferable to use a living radical polymerization method.
- an organic halide is a halogenated sulfo.
- the atom transfer radical polymerization method which polymerizes a (meth) acrylate ester monomer using a carbonyl compound as an initiator and a transition metal complex as a catalyst, has the features of the above-mentioned ⁇ living radical polymerization method '' and a functional group. Since there is a halogen or the like at the terminal that is relatively advantageous for the conversion reaction and the degree of freedom in designing an initiator and a catalyst is large, a method for producing a (meth) acrylic acid ester-based polymer having a specific functional group has been considered. Even more preferred.
- the atom transfer radical polymerization method includes, for example, Matyjaszewski et al., J. Am. Chem. Soc. 1995, Vol. 117, p. 5614.
- Japanese Patent Publication No. 3-14068, Japanese Patent Publication No. 4-55444, and Japanese Patent Application Laid-Open No. Publications disclose a production method using a free radical polymerization method using a chain transfer agent.
- Japanese Patent Application Laid-Open No. 9-272714 discloses a method using an atom transfer radical polymerization method. The present invention is not particularly limited thereto.
- the above-mentioned (meth) acrylate polymer having a reactive silicon group may be used alone or in combination of two or more.
- organic polymers having a reactive silicon group may be used alone or in combination of two or more.
- a polyoxyalkylene polymer having a reactive silicon group a saturated hydrocarbon polymer having a reactive silicon group, a (meth) acrylate polymer having a reactive silicon group, Organic group
- An organic polymer obtained by blending two or more selected types can also be used.
- the method for producing an organic polymer obtained by blending a (meth) acrylate polymer is described in JP-A-59-122541, JP-A-63-112642, JP-A-6-172631, and JP-A-11-116763. Proposed in Japanese Unexamined Patent Publication (Kokai) No. H11-15064, and is not particularly limited thereto.
- a preferred example is a compound having a reactive silicon group and a molecular chain substantially having the following general formula (6): CH—C (R 9 ) (COOR 10 ) (6)
- R 9 represents a hydrogen atom or a methyl group
- R 1Q represents an alkyl group having 1 to 8 carbon atoms.
- R 9 is the same as described above, R 11 represents an alkyl group having 10 or more carbon atoms
- R 11 represents an alkyl group having 10 or more carbon atoms
- R 1Q in the general formula (6) for example, a methyl group, an ethyl group, a propyl group, an n-butyl group, a t-butyl group, a 2-ethylhexyl group, etc.
- R 1Q is 1 to 4, more preferably 1 to 2 alkyl groups.
- the alkyl group of R 1Q may be used alone or in combination of two or more.
- R 11 in the general formula (7) for example, lauryl group, tridecyl group, cetyl group, stearyl group, behyl group and the like have 10 or more carbon atoms, usually 10 to 30, and preferably 10 to 30 carbon atoms. Examples include long chain alkyl groups of 10 to 20. As in the case of R 1Q , the alkyl group of R 11 may be a single compound or a mixture of two or more compounds.
- the molecular chain of the (meth) acrylic acid ester-based copolymer substantially also has a monomer unit force represented by the formulas (6) and (7). It means that the sum of the monomer units of the formulas (6) and (7) present in the copolymer exceeds 50% by weight.
- the total of the monomer units of the formulas (6) and (7) is preferably at least 70% by weight.
- the abundance ratio of the monomer unit of the formula (6) and the monomer unit of the formula (7) is preferably 95: 5 to 40:60 by weight, and 90:10 to 60:40. Force is even more preferred.
- the monomer units other than those represented by the formulas (6) and (7) contained in the copolymer include, but are not limited to, ⁇ , ⁇ unsaturated such as acrylic acid and methacrylic acid.
- Monomers containing amino groups such as acrylate and aminoethyl vinyl ether; other monomer units derived from acrylonitrile, styrene, a-methylstyrene, alkyl vinyl ether, vinyl chloride, vinyl acetate, vinyl propionate, ethylene, etc. Is raised.
- a (meth) acrylate polymer having a reactive silicon functional group is blended.
- Another method for producing an organic polymer is to carry out the polymerization of a (meth) acrylate monomer in the presence of a polyoxypropylene polymer having a reactive silicon group. Available. This production method is not limited to those disclosed in JP-A-59-78223, JP-A-60-228516, and JP-A-60-228517.
- the main chain skeleton of the organic polymer of the present invention may contain other components such as a urethane binding component as long as the effects of the present invention are not significantly impaired.
- the urethane binding component is not particularly limited, and examples thereof include a group generated by a reaction between an isocyanate group and an active hydrogen group (hereinafter, also referred to as an amide segment).
- the amide segment has the general formula (8):
- R 12 represents a hydrogen atom or a substituted or unsubstituted organic group.
- the amide segment include a urethane group formed by a reaction between an isocyanate group and a hydroxyl group; a urea group formed by a reaction between an isocyanate group and an amino group; and an urea group formed by a reaction between an isocyanate group and a mercapto group. And a thiourethane group generated by the above reaction.
- the group represented by the general formula (8) also includes a group formed by the reaction of active hydrogen in the urethane group, urea group and thiourethane group with an isocyanate group.
- An example of an industrially easy method for producing an organic polymer having an amide segment and a reactive silicon group is as follows: An organic polymer having an active hydrogen-containing group at the terminal is added with an excess of polyisocyanate. After reacting to form a polymer having an isocyanate group at the terminal of the polyurethane-based main chain, or at the same time, all or a part of the isocyanate group has the general formula (9) WR 13 -SiR 7 X (9)
- R 13 is a divalent organic group, more preferably a substituted or unsubstituted divalent hydrocarbon having 1 to 20 carbon atoms.
- W is an active hydrogen-containing group selected from a hydroxyl group, a hydroxyl group, a mercapto group, and an amino group (unsubstituted or monosubstituted).
- Examples of known production methods for organic polymers related to this production method are described in JP-B-46-12154 (US Pat. No. 3,632,557) and JP-A-58-109. No. 529 (U.S. Pat.No. 4,374,237), Japanese Patent Application Laid-Open No.
- an organic polymer having an active hydrogen-containing group at a terminal is represented by the general formula (10)
- Examples of known production methods for organic polymers related to this production method include, for example, JP-A-11-279249 (US Pat. No. 5,990,257), JP-A-2000-119365 (US Pat. No. 6,046,270), and JP-A-58-29818. (US Patent No. 4345053), JP-A-3-47825 (US Pat. No.
- Examples of the organic polymer having an active hydrogen-containing group at a terminal include an oxyalkylene polymer (polyether polyol) having a hydroxyl group at a terminal and polyacryl polyol.
- polyether polyols are more preferable because the viscosity of the obtained organic polymer is low and the workability is good, and the adhesiveness and the deep curing property are good.
- polyacryl polyol is more preferable because the cured product of the obtained organic polymer has good weather resistance and heat resistance.
- any of those produced according to the above production method can be used, but those having at least 0.7 hydroxyl groups at the terminal per molecular terminal on the average of all molecules can be used. Is preferred.
- the initiator include an oxyalkylene polymer produced by reacting an alkylene oxide.
- a polymerization method using a double metal cyanide complex has a lower degree of unsaturation, a lower viscosity in which MwZMn is narrower, and a high acid resistance and high weather resistance oxyalkylene. It is preferable because a polymer can be obtained.
- Examples of the polyacryl polyol include polyols having a (meth) acrylic acid alkyl ester (co) polymer as a skeleton and having a hydroxyl group in the molecule.
- an atom transfer radical polymerization method is more preferable because a living radial polymerization method is preferable because a molecular weight distribution is narrow and a viscosity can be reduced.
- Specific examples include UH-2000 manufactured by Toagosei Co., Ltd.
- polyisocyanate conjugate examples include aromatic polyisocyanates such as toluene (tolylene) diisocyanate, diphenylmethane diisocyanate, and xylylene diisocyanate; Examples thereof include aliphatic polyisocyanates such as isocyanate and hexamethylene diisocyanate.
- Kei-containing compounds of the general formula (9) is not particularly limited as Kei-containing compounds of the general formula (9), specific examples, y ⁇ amino propyl trimethoxy silane, N-(beta-aminoethyl) I - ⁇ amino propyl trimetrexate Kishishiran , ⁇ - ( ⁇ phenyl) aminopropyltrimethoxysilane, ⁇ ⁇ ⁇ ethylaminoisobutyltrimethoxysilane, ( ⁇ cyclohexylaminomethyl) triethoxysilane, ( ⁇ -cyclohexylaminomethyl) diethoxymethylsilane, (( Silanes containing an amino group such as (4-phenylaminomethyl) trimethoxysilane; silanes containing a hydroxy group such as y-hydroxypropyltrimethoxysilane; silanes containing a mercapto group such as y-mercaptopropyltrimethoxysilane;
- JP-A-6- 211879 (U.S. Patent No. 5364955), JP-A-10-53637 (US Patent No. 5756751), JP-A-10-204144 (EP 0831108), JP-A-2000-169544, and JP-A-2000- No. 169545 [As described here!]
- Michael addition products of various a, j8 unsaturated carboyl compounds with primary amino group-containing silanes, or various (meth) atalyloyl group-containing silanes with primary A Michael addition reaction with an amino group-containing compound can also be used as the silicon compound of the general formula (9).
- the reactive silicon group-containing isocyanate compound of the general formula (10) is not particularly limited. Specifically, ⁇ -trimethoxysilylpropyl isocyanate, ⁇ -triki
- the amide segment When the amide segment is large in the main chain skeleton of the organic polymer of the present invention, the viscosity of the organic polymer increases, and a composition having poor workability may be obtained. On the other hand, the amide segment in the main chain skeleton of the organic polymer tends to improve the curability of the composition of the present invention.
- the composition in combination with the component ( ⁇ ) of the present invention has faster curability while using a non-organic tin catalyst.
- the number of amide segments per molecule is preferably 1 to 10, more preferably 1.5 to 7 more preferably 2 to 5 per molecule. Is particularly preferred. When the number is less than 1, the curability may not be sufficient, and when the number is more than 10, the organic polymer may have a high viscosity and the composition may have poor workability.
- a titanium chelate represented by the following general formula (1) or (2) is used as the component ( ⁇ ).
- ⁇ R 1 s are each independently a substituted or unsubstituted carbon atom having 1 to 20 carbon atoms. It is a hydrocarbon group.
- n R 2 s are each independently a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms.
- 4-n R 3 and 4-n R ' are each independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms.
- ⁇ is the deviation force of 0, 1, 2, and 3!
- R 5 is a substituted or unsubstituted divalent hydrocarbon group having 20 carbon atoms.
- This titanium chelate functions as a curing catalyst for the organic polymer as the component (A).
- organotin compounds such as dibutyltin dilaurate and dibutyltin bis (acetyl acetonate) have been used as a curing catalyst for an organic polymer having a reactive silicon group as the component (A).
- the titanium chelate (B) of the present invention it is possible to obtain a curable composition having practical curing characteristics while being a non-organic tin catalyst. Furthermore, the curability and storage stability are better as compared with the case where another titanium catalyst having no chelate ligand is used.
- titanium chelate (B) it is possible to obtain a composition that is less colored than other titanium chelates. Furthermore, compared to the case where another curing catalyst such as an organotin catalyst is used, the adhesion to a poorly adherent organic adherend such as acrylic resin can be improved.
- titanium chelate represented by the general formula (1) or the general formula (2) include titanium-dimethyldimethoxide bis (ethyl acetate acetate), titanium diethoxydobis (ethyl acetate acetate), Titanium diisopropoxide bis (ethyl acetate acetate), titanium diisopropoxide bis (methinolacetoacetate), titanium diisopropoxide bis (t-butyl acetate acetate), titanium diisopropoxide bis (methyl-3 —Oxo -4,4-dimethylhexanoate), titanium diisopropoxide bis (ethyl 3-oxo 4,4,4-trifluorobutanoate), titanium di-n-butoxide bis (ethyl acetate acetate), titanium Diisobutoxide bis (ethyl acetate acetate), titaium di-t-butoxide bis (ethyl acetate acetate), titanium di-2-
- the chelating reagent capable of forming the chelating ligand of the titanium chelate include methyl acetoacetate, ethyl acetoacetate, t-butyl acetoacetate, aryl acetoacetate, acetoacetate (2-methacrylic acid). J8-ketoesters such as loxoshetyl), methyl 3-oxo-4,4 dimethylhexanoate and ethyl 3-oxo4,4,4 trifluorobutanoate.
- methyl acetoacetate and ethyl acetoacetate are more preferable, in view of curability, storage stability and availability.
- each chelating ligand may be the same or different.
- the titanium chelate exemplified above is used as a method of adding the titanium chelate.
- a titanium conjugate which can react with a chelating reagent such as titanium tetraisopropoxide or titanium dichloride diisopropoxide, and a chelating reagent such as ethyl acetoacetate are added to the composition of the present invention, respectively.
- a method of chelating in the composition may also be applied.
- the titanium chelate of the component (B) can be used alone or in combination of two or more.
- Component (B) is used in an amount of preferably 0.1 to 20 parts by weight, more preferably 0.5 to 15 parts by weight, per 100 parts by weight of component (A). Particularly, 1 to: LO parts by weight are preferred.
- Component blending power S If the amount falls below this range, a practical curing speed may not be obtained, and the curing reaction may not sufficiently proceed. On the other hand, if the amount of the component (B) exceeds this range, the pot life tends to be too short and the workability tends to be poor.
- a titanium catalyst other than the component (B) can be used to the extent that the effects of the present invention are not impaired.
- Titanium dimethoxide bis (acetyl acetonate), titanium diethoxide bis (acetyl acetonate), titanium diisopropoxide bis (acetyl acetonate), titanium dimethyl diisopropoxide bis (2,2,6) 6-tetramethyl-3,5 heptanedionate), titanium-m- n -butoxide bis (acetyl acetate), titanium diisobutoxide (acetyl acetate), titanium di-butoxide bis (acetyla) Cetonate), titanium di-1-ethylhexoxide bis (acetyl acetate), titanium triisopropoxide (getyl malonate), titanium diisopropoxide bis (triethanol aminate), titanium tetrakis (acetyla) Titanium chelates, such as setonate); And the like; Taniumutorisu (di O Chi le phosphate) isopropoxide, titanium tris (de de iodos
- a light stabilizer is used as the component (C), and a light stabilizer (C1) having no benzotriazole ring is used as a main component thereof.
- Light stabilizers have the function of absorbing light at a wavelength in the ultraviolet region to suppress the generation of radicals, or of capturing radicals generated by light absorption and converting them into heat energy to render them harmless. It is a compound that enhances the stability to light and improves the weather resistance of the composition of the present invention.
- a light stabilizer (C-2) having a benzotriazole ring is commonly used in combination with an organotin catalyst.
- the present inventors have found that when combined with a titanium chelate, which is the component (B) of the present invention, there is a problem that the curability is reduced and the composition is significantly colored.
- the main component of the light stabilizer (C) of the present invention is a compound having no benzotriazole ring. ) Is essential.
- the light stabilizer (C-1) having no benzotriazole ring is specifically represented by the general formula (11):
- Ar 8 and Ar 9 are each independently a substituted or unsubstituted aryl group.
- a hindered amine light stabilizer included in the hindered amine-based light stabilizer.
- Specific examples of the hindered amine-based light stabilizer include general formula (15):
- R lb is a hydrogen atom or an organic group.
- a compound having a group represented by the formula (1) is preferred because of its high effect of improving weather resistance.
- a hindered amine having no —NH— group that is, R 15 in the general formula (15) is an organic group, is more effective than the hindered amine in which R 15 is a hydrogen atom.
- a composition having a small decrease in curability when combined with a titanium chelate as a component is preferable because it exhibits good curability.
- the organic group a substituted or unsubstituted alkyl group, an alkoxy group, an acyl group, an acyloxy group, etc. are mentioned.
- a point of availability A substituted or unsubstituted alkyl group is more preferred, and an unsubstituted alkyl group is more preferred. Most preferred are methyl groups, where the groups are particularly preferred.
- a benzoate-based ultraviolet absorber a triazine-based ultraviolet absorber, a cyanoacrylate-based ultraviolet absorber, and a hindered amine-based light stabilizer are used because a composition with less coloring is obtained. preferable. Also, from the viewpoint of the weather resistance of the obtained composition, benzoate-based ultraviolet absorbers, triazine-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, and hindered amine-based light stabilizers, which are preferred, are benzoate-based ultraviolet absorbers and triazine-based ultraviolet absorbers.
- Abinders and hindered amine light stabilizers are more preferred, and triazine ultraviolet absorbers and hindered amine light stabilizers are particularly preferred. Hindered amine light stabilizers are most preferred.
- Specific examples of the benzoate-based ultraviolet absorber include 4t-butylphenyl salicylate, 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, and phenyl salicylate.
- Examples of commercially available benzoate-based ultraviolet absorbents include Sumithorp 400 (manufactured by Sumitomo Iridaku), Seesorb 201, and Seesorb 202 (above V, the deviation is also manufactured by Cipro Kasei).
- triazine-based ultraviolet absorber examples include 2- (4,6 diphenyl-1,3,5 triazin-2-yl) -5- (hexyloxy) -phenol.
- examples of commercially available triazine-based ultraviolet absorbers include Tinuvin 1577FF (manufactured by Ciba Chemical Corporation).
- cyanoacrylate-based ultraviolet absorber examples include ethyl-2 cyano-3,3 diphenyl mono-arylate, 2-ethylhexyl 2-cyano 3,3 diphenyl-2-arytalylate, and the like.
- examples of commercially available cyanoacrylate-based ultraviolet absorbers include VIOSORB910 and VIOSORB930 (all of which are manufactured by Kyodo Yakuhin).
- benzophenone-based ultraviolet absorber examples include 2-hydroxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, and 2-hydroxy-4-n-otoxybenzo.
- benzophenone-based ultraviolet absorbers examples include VIOSORB100, VIOSORB105, VIOSORB110, VIOSORB130 (all manufactured by Kyodo Chemical), KEMISORB13, KEMISORB111, and KEMISORB1011 (all manufactured by Chemipro Kasei).
- hindered amine light stabilizer examples include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis (1,2,2,6,6, pentamethyl-4-propyl). Lysyl) sebacate, 1 ⁇ 2- (3- (3,5-ditert-butyl-4-hydroxyphenyl) propio-loxy] ethyl) -4 [3- (3,5-ditert-butyl-4-hydroxyphenyl) Propio-roxy] 2,2,6,6-tetramethylpiperidine, 4-benzo Yloxy-2,2,6,6-tetramethylpiperidine, 8 acetyl-3 dodecyl-7,7,9,9-tetramethyl-1,3,8 triazaspiro [4.5] decane-1,4 dione, Polymer of dimethyl methacrylate and 4-hydroxy 2,2,6,6-tetramethyl-1-piperidineethanol, bis (2,2,6,6-tetramethyl-1-oct
- Sanonore LS-770, LS-765, LS-292, LS-2626, LS-1114, LS-744, LS-440 (all manufactured by Sankyo); Tinuvin 6 22LD, Tinuvin 123S, Tinuvin 144, CHIMASSORB119FL ⁇ CHIMASSORB 2020FDL, CHIMASSORB944FDL (all made by Nippon Ciba Geigy Co., Ltd.); LA-82, LA-87 (all of these are manufactured by Adeka Gas Chemical Co., Ltd.) and the like.
- tinuvin 622LD tinuvin 144 which is a hindered amine light stabilizer having no NH group
- CHIMASSORB119FL ADK STAB LA-52, LA-62, LA-63, LA-82; LS-765 ,: LS- 292, LS-2626, LS-440, etc.
- the composition having a small decrease in curability when combined with the titanium chelate which is the component (B) shows good curability.
- the (C-1) component does not have a benzotriazole ring! / ⁇
- the light stabilizers can be used alone or in combination of two or more.
- the amount of the component (C-1) to be used is preferably 0.1 to 10 parts by weight, more preferably 0.3 to 5 parts by weight, per 100 parts by weight of the component (A). Particularly preferred is 0.5 to 2 parts by weight. If the amount of the component (C1) is below this range, a sufficient effect of improving weather resistance may not be obtained. On the other hand, when the amount of the component (C-1) exceeds this range, the composition tends to be colored and the curability tends to decrease.
- the light stabilizer (C-2) having a benzotriazole ring is most preferably not contained as the light stabilizer (C), but (C-2) benzotriazole is used as the light stabilizer (C).
- the content of (C 2) is preferably less than 0.1 part by weight based on 100 parts by weight of the polymer (A). More preferably, the amount is less than 0.01 part by weight.
- the light stabilizer (C 2) having a benzotriazole ring is contained in an amount of 0.1 part by weight or more, coloring and curability tend to be reduced.
- the light stabilizer (C-2) having a benzotriazole ring include 2- (2H-benzotriazole-2-yl) p-cresol and 2- (2Hbenzotriazole-2-yl).
- a filler can be added to the composition of the present invention.
- fillers include reinforcing fillers such as fume silicic acid, precipitated silica, crystalline silica, fused silica, dolomite, carboxylic anhydride, hydrous carboxylic acid, and carbon black; heavy calcium carbonate, colloidal calcium carbonate, Magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide, aluminum fine powder, flint powder, zinc oxide, activated zinc white, shirasu balloon, glass micro balloon, phenol And fillers such as fat powder such as organic microballoons of fat and salt, and resin, PVC powder and PMMA powder; and fibrous fillers such as asbestos, glass fiber and filament.
- the amount is 1 to 250 parts by weight, preferably 10 to 200 parts by weight, per 100 parts by weight of the polymer of component (A).
- the filler is uniformly mixed with a dehydrating agent such as calcium oxide, and then sealed in a bag made of an airtight material. It is also possible to preliminarily dehydrate and dry by leaving it to stand for an appropriate time. By using this low water content filler, storage stability can be improved, especially when a one-part composition is used.
- a polymer powder using a polymer such as methyl methacrylate as a raw material, Amorphous silica or the like can be used as a filler.
- hydrophobic silica or the like which is a fine powder of silicon dioxide having a hydrophobic group bonded to the surface thereof, as a filler makes it possible to increase the transparency.
- a high composition can be obtained.
- the surface of the silicon dioxide fine powder generally has a silanol group (—SiOH).
- —SiOH silanol group
- dimethylsiloxane, hexamethyldisilazane, dimethyldichlorosilane, trimethoxyoctylsilane, trimethylsilane, and the like are reactively bonded to silanol groups present on the surface of silicon dioxide fine powder.
- the silicon dioxide fine powder whose surface is formed of silanol groups (—SiOH) is called hydrophilic silica fine powder.
- calcium carbonate such as titanium oxide and heavy calcium carbonate, magnesium carbonate, talc, ferric oxide, zinc oxide, and shirasu balloon.
- a filler selected from the above is used in an amount of 5 to 200 parts by weight based on 100 parts by weight of the organic polymer (A) having a reactive silicon group, preferable results can be obtained.
- the greater the specific surface area of calcium carbonate the greater the effect of improving the strength at break, elongation at break, and adhesiveness of the cured product.
- these fillers may be used alone or in combination of two or more.
- the particle size of the surface-treated fine calcium carbonate is preferably 0.5 m or less.
- the surface treatment is preferably performed with a fatty acid or a fatty acid salt.
- the particle size of calcium carbonate having a large particle size is preferably 1 ⁇ m or more. Those that have been surface-treated can be used.
- the composition such as sharpness
- the surface of the cured product matte it is preferable to use organic and inorganic balloons. These fillers can be surface-treated, and may be used alone or in combination of two or more.
- the particle size of the balloon is preferably 0.1 mm or less.
- the thickness is preferably 5 to 300 m.
- the composition of the present invention has a cured product having good chemical resistance, etc., and is used for sizing boards, especially ceramic sizing boards, etc., for joints of exterior walls of houses, adhesives for exterior wall tiles, and adhesion of exterior wall tiles.
- the adhesive is preferably used for adhesives that remain on joints, but it is desirable that the design of the outer wall and the design of the sealing material be in harmony.
- high-quality exterior walls are being used as the exterior walls by spatter coating, coloring aggregates, and the like.
- the composition of the present invention contains a scale-like or granular substance having a diameter of 0.1 mm or more, preferably about 0.1 to 5.Omm, the cured product will have such a high-grade outer wall.
- this cured product is an excellent composition that lasts for a long time.
- the surface has a sanding-like or sandstone-like roughness, and when a flaky substance is used, the surface becomes uneven due to the scale.
- Preferable diameters, compounding amounts, materials, and the like of the scaly or granular substance are as follows, as described in JP-A-953063.
- the diameter is 0.1 mm or more, preferably about 0.1 to 5.0 mm, and an appropriate size is used according to the material, pattern, and the like of the outer wall. It is also possible to use those with a thickness of about 0.2 mm to 5. Omm or about 0.5 mm to 5. Omm. In the case of a scale-like substance, the thickness is as thin as about 1Z10 to 1Z5 in diameter (0.01 to about L00mm).
- the scaly or granular substance is premixed in the main sealing material and transferred to the construction site as a sealing material, and is mixed into the main sealing material at the construction site when used.
- the scaly or granular substance is mixed in an amount of about 1 to 200 parts by weight with respect to 100 parts by weight of a composition such as a sealing material composition or an adhesive composition.
- a composition such as a sealing material composition or an adhesive composition.
- the amount is appropriately selected depending on the size of the individual scale-like or granular material, the material of the outer wall, the pattern, and the like.
- Examples of the scaly or granular substance include natural substances such as ky sand, My power, synthetic rubber, and synthetic rubber. Inorganic substances such as fats and alumina are used. In order to enhance the design when filling the joints, it is colored in an appropriate color according to the material and pattern of the outer wall.
- a balloon preferably having an average particle size of 0.1 mm or more
- a sandy or sandstone-like surface with a rough feeling can be obtained, and a light-weight siding can be achieved.
- the preferred diameter, compounding amount, material and the like of the balloon are as follows, as described in JP-A-10-251618.
- the balloon is a spherical filler and has a hollow inside.
- Materials for the balloon include inorganic materials such as glass, shirasu, and silica, and organic materials such as phenolic resin, urea resin, polystyrene, and saran.
- the inorganic material and the organic material can be compounded, or a plurality of layers can be formed by lamination.
- Inorganic, organic, or composite balloons can be used.
- the same balloon may be used, or a plurality of types of balloons of different materials may be used in combination.
- the balloon one whose surface is processed or coated can be used, and that whose surface has been treated with various surface treatment agents can be used. For example, coating an organic balloon with calcium carbonate, talc, titanium oxide, or the like, or treating an inorganic nonane with a silane coupling agent for surface treatment may be mentioned.
- the balloon preferably has a particle size of 0.1 mm or more. It is also possible to use one with a thickness of about 0.2 mm to 5. Omm or about 0.5 mm to 5. Omm. If it is less than 0.1 mm, even if it is blended in a large amount, it may only increase the viscosity of the composition and may not exhibit a rough feeling.
- the blending amount of nolane can be easily determined according to the degree of roughness of the intended sanding tone or sandstone tone. In general, it is desirable to blend a composition having a particle size of 0.1 mm or more at a volume concentration in the composition of 5 to 25 vol%.
- volume concentration of the balloon is less than 5 vol%, the feeling of roughness is reduced, and if it exceeds 25 vol%, the viscosity of the sealing material / adhesive increases, the workability is poor, and the modulus of the cured product increases.
- the balance with the basic performance of the sealing material is particularly preferred, and the volume concentration is 8 to 22 vol%.
- the anti-slip agent described in JP-A-2000-154368 and the surface of the cured product described in JP-A-2001-164237 are made uneven.
- an amine compound for giving an opaque state in particular, primary and Z or secondary amine having a melting point of 35 ° C. or more can be added.
- the thermally expandable fine hollow particles described in JP-A-2004-51701 or JP-A-2004-66749 can be used.
- the heat-expandable fine-grained hollow body refers to a low-boiling compound such as a hydrocarbon having 1 to 5 carbon atoms, which is a polymer outer shell material (a salty vinylidene copolymer, an acrylonitrile copolymer, or a salty polymer). It is a plastic sphere wrapped in a spherical shape with a dani-lindene acrylonitrile copolymer).
- the composition of the present invention contains particles of cured sealing material, the cured product can form irregularities on the surface and improve the design.
- the preferred, diameter, compounding amount, material and the like of the cured sealing material particles are as follows as described in JP-A-2001-115142.
- the diameter is preferably from 0.1 mm to: Lmm, more preferably from about 0.2 to 0.5 mm.
- the amount is preferably 5 to: L00% by weight, more preferably 20 to 50% by weight in the curable composition.
- the material include urethane resin, silicone, modified silicone, polysulfide rubber, and the like. The material is not limited as long as it is used as a sealing material. A modified silicone-based sealing material is preferable.
- a tackifier may be added to the composition of the present invention.
- the tackifying resin is not particularly limited, but those commonly used at room temperature, whether solid or liquid, can be used. Specific examples include a styrene-based block copolymer, a hydrogenated product thereof, a phenol resin, a modified phenol resin (for example, a cash oil-modified phenol resin, a tall oil-modified phenol resin, etc.), a terpene phenol resin, Xylene phenol resin, cyclopentadiene phenol resin, coumarone indene resin, rosin resin, rosin ester resin, hydrogenated rosin ester resin, xylene resin, low molecular weight polystyrene resin, styrene copolymer Combined resin, petroleum resin (for example, C5 hydrocarbon resin, C9 hydrocarbon resin, C5C9 hydrocarbon copolymer resin, etc.), hydrogenated petroleum resin, terpene resin, DCPD resin petroleum
- Styrene-based block copolymers and their hydrogenated celluloses include styrene butagen-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), styrene-ethylene-butylene styrene block copolymer.
- SBS styrene butagen-styrene block copolymer
- SIS styrene-isoprene-styrene block copolymer
- SEBS styrene ethylene propylene styrene block copolymer
- SIBS styrene isobutylene styrene block copolymer
- the tackifying resin may be used alone or in combination of two or more.
- the tackifying resin is used in an amount of 5 to 1,000 parts by weight, preferably 10 to: L00 parts by weight based on 100 parts by weight of the organic polymer (A).
- a plasticizer can be added to the composition of the present invention.
- the viscosity and slump properties of the curable composition and the mechanical properties such as tensile strength and elongation of the cured product obtained by curing the composition can be adjusted by adding the plasticizer.
- plasticizer examples include phthalic acid esters such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate and butylbenzyl phthalate; dioctyl adipate, dioctyl sebacate, dibutyl sebacate, succinate
- Non-aromatic dibasic acid esters such as isodecyl acid; aliphatic esters such as butyl oleate and methyl acetyl ilicinoleate; phosphates such as tricresyl phosphate and tributyl phosphate; trimellitic esters Chlorinated paraffins; hydrocarbon-based oils such as alkyl diphenyls and partially hydrogenated terphenyls; process oils; epoxy plasticizers such as epoxidized soybean oil and benzyl epoxystearate; be able to.
- phthalic acid esters such as dibutyl phthalate, dih
- a polymer plasticizer can be used.
- the use of a high-molecular plasticizer maintains the initial physical properties for a long time as compared with the case of using a low-molecular plasticizer that is a plasticizer that does not contain a polymer component in the molecule.
- the drying property also referred to as coating property
- an alkyd paint is applied to the cured product can be improved.
- the polymer plasticizer include a vinyl polymer obtained by polymerizing a vinyl monomer by various methods; esters of polyalkylene glycol such as diethylene glycol dibenzoate, triethylene glycol dibenzoate, and pentaerythritol ester Polyester plasticizers obtained from dibasic acids such as sebacic acid, adipic acid, azelaic acid and phthalic acid and dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol and dipropylene glycol; Polyether polyols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc.
- esters of polyalkylene glycol such as diethylene glycol dibenzoate, triethylene glycol dibenzoate, and pentaerythritol ester Polyester plasticizers obtained from dibasic acids such as sebacic acid, adipic acid, azelaic acid and phthalic acid and dihydric alcohols such as ethylene
- Converted poly ethers such derivatives as etc., polystyrene and poly one a - poly styrene such as methyl styrene; polybutadiene, polybutene, polyisobutylene, butadiene Atarironitori Le, polyclonal port Puren like are limited to forces which may be mentioned Not something.
- polyethers and bullet polymers are preferred.
- polypropylene glycol is more preferable, because the surface hardening property and the deep-side hardening property are improved, and the hardening is not delayed after storage.
- a bullet polymer is preferred from the viewpoint of compatibility, weather resistance, and heat resistance.
- acrylic polymers such as alkyl acrylates, more preferably acrylic polymers and Z or methacrylic polymers, are more preferred.
- an atom transfer radical polymerization method is more preferable because a living radical polymerization method is preferable because a molecular weight distribution is narrow and a viscosity can be reduced. Also, it is described in Japanese Patent Application Laid-Open No. 2001-207157 that an alkyl acrylate-based monomer obtained by continuous bulk polymerization at high temperature and pressure is used. Like! / ,.
- the number average molecular weight of the polymeric plasticizer is preferably from 500 to 15,000, more preferably Pama is 800 to 10000, furthermore [Preferable ⁇ Pama 1000 to 8000, special [Preferred ⁇ Pama 1000 to 5000]. Most preferably, it is 1000-3000. If the molecular weight is too low, the plasticizer flows out over time due to heat or rainfall, and the initial physical properties cannot be maintained for a long time, and the alkyd paintability cannot be improved. On the other hand, if the molecular weight is too high, the viscosity increases, and the workability deteriorates.
- the molecular weight distribution of the high-molecular plasticizer is not particularly limited, but is preferably narrow, and preferably less than 1.80. 1. 70 or less is more preferred 1. 60 or less is still preferred 1. 50 or less is more preferred 1. 40 or less is particularly preferred 1. 30 or less is most preferred.
- the number average molecular weight is measured by a GPC method for a vinyl polymer and by a terminal group analysis method for a polyether polymer.
- the molecular weight distribution (MwZMn) is measured by the GPC method (polystyrene conversion).
- the polymer plasticizer may not have a reactive silicon group, but may have a reactive silicon group.
- it acts as a reactive plasticizer and can prevent migration of a plasticizer which is a cured product.
- the number is preferably 1 or less, more preferably 0.8 or less per molecule on average.
- a plasticizer having a reactive silicon group particularly an oxyalkylene polymer having a reactive silicon group, its number average molecular weight must be lower than that of the polymer of component (A). It is.
- the plasticizer may be used alone or in combination of two or more. Further, a low-molecular plasticizer and a high-molecular plasticizer may be used in combination. In addition, these plasticizers can be blended at the time of polymer production.
- the amount of the plasticizer to be used is 5 to 150 parts by weight, preferably 10 to 120 parts by weight, more preferably 20 to LOO parts by weight based on 100 parts by weight of the polymer of the component (A). If the amount is less than 5 parts by weight, the effect as a plasticizer will not be exhibited, and if it exceeds 150 parts by weight, the mechanical strength of the cured product will be insufficient.
- a compound that generates a compound having a monovalent silanol group in the molecule by hydrolysis may be added.
- This compound has the effect of lowering the modulus of the cured product without deteriorating the stickiness of the surface of the cured product.
- compounds that generate trimethylsilanol are preferred.
- JP-A-5-117521 discloses The compounds described in the publication can be mentioned. Also, compounds which are derivatives of alkyl alcohols such as hexanol, octanol and decanol and which produce silicon compounds which generate RSiOH such as trimethylsilanol by hydrolysis,
- the resulting compound can be mentioned.
- a derivative of an oxypropylene polymer as described in JP-A-7-258534, which forms an RSiOH such as trimethylsilanol by hydrolysis, may be used.
- the compound which forms a compound having a monovalent silanol group in the molecule by hydrolysis is 0.1 to 20 parts by weight based on 100 parts by weight of the organic polymer (A) having a reactive silicon group. , Preferably 0.5 to: used in the range of L0 parts by weight.
- a thixotropic agent may be added to the curable composition of the present invention to prevent sagging and improve workability.
- the anti-sagging agent is not particularly limited, and examples thereof include polyamide waxes; hydrogenated castor oil derivatives; and metal silicates such as calcium stearate, aluminum stearate, and barium stearate.
- a rubber powder having a particle diameter of 10 to 500 m as described in JP-A-11-349916 or an organic fiber as described in JP-A-2003-155389 is used, the thixotropic property is increased. And a composition with high workability is obtained.
- thixotropic agents anti-sagging agents
- the thixotropic agent is used in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the organic polymer (A) having a reactive silicon group.
- a compound containing an epoxy group in one molecule can be used.
- Epoxy group-containing compounds include epoxidized unsaturated fats, epoxidized unsaturated fats and the like. Examples thereof include acid esters, alicyclic epoxy conjugates, conjugates represented by epichlorohydrin derivatives, and mixtures thereof.
- E-PS epoxidized soybean oil, epoxidized ama-oil, bis (2-ethylhexyl) -4,5-epoxycyclohexane-1,2-dicarboxylate (E-PS), epoxy otatinol Stearate, epoxy butinolestearate and the like.
- E-PS is particularly preferred.
- the epoxy conjugate is preferably used in an amount of 0.5 to 50 parts by weight based on 100 parts by weight of the organic polymer (A) having a reactive silicon group.
- Photocurable substances can be used in the composition of the present invention.
- a photocurable material When a photocurable material is used, a film of the photocurable substance is formed on the surface of the cured product, and the tackiness and weather resistance of the cured product can be improved.
- a photo-curable substance is a substance which undergoes a chemical change in molecular structure in a short time by the action of light to produce physical changes such as curing.
- Many compounds of this kind are known, such as organic monomers, oligomers, resins and compositions containing them, and any commercially available compounds can be employed. Typical examples thereof include unsaturated acrylic compounds, polycaffeic acid burs, and azidhidani resin. As unsaturated acrylic compounds
- Aronix! All products are products of Toa Gosei Chemical Industry Co., Ltd.)
- polyvinyl cinnamate examples include a photosensitive resin having a cinnamoyl group as a photosensitive group, which is obtained by esterifying a poly (vinyl alcohol) with a cinnamate, and a number of polykai cinnamate derivatives.
- Azide resins are known as photosensitive resins with azide groups as photosensitive groups.
- photosensitive resin published on March 17, 1972, published by the Printing Society of Japan, pp. 93-106) , Page 117-
- a sensitizer may be added.
- the addition of a sensitizer such as ketones or nitro compounds, or an accelerator such as amines may enhance the effect in some cases.
- the photocurable substance is used in an amount of 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the organic polymer (A) having a reactive silicon group. If the amount is less than 0.1 part by weight, the effect of enhancing the weather resistance is not sufficient. If the amount is more than 20 parts by weight, the cured product becomes too hard and cracks tend to occur.
- An oxygen curable substance can be used in the composition of the present invention.
- oxygen-curable substance examples include unsaturated compounds that can react with oxygen in the air.They react with oxygen in the air to form a hardened film near the surface of the hardened material, and the surface becomes sticky or hardened. It acts to prevent the attachment of dust and dirt.
- Specific examples of the oxygen-curable substance include drying oils such as tung oil and linseed oil, and various alkyd resins obtained by modifying the compounds; acrylic polymers modified with the drying oil, epoxy resins and the like.
- NBR obtained by copolymerizing a liquid polymer such as a polymer of styrene, or a monomer such as Atari nitrile or styrene, which has copolymerizability with these gen-based compounds, so that the gen-based compounds are mainly used.
- liquid copolymers such as SBR and various modified products thereof (maleated modified product, boiled oil modified product, etc.). These may be used alone or in combination of two or more. Of these, tung oil and liquid gen-based polymers are particularly preferred.
- the effect may be enhanced by using a catalyst or a metal dryer that promotes the oxidative curing reaction.
- Examples of these catalysts and metal dryers include metal salts such as cobalt naphthenate, lead naphthenate, zirconium naphthenate, cobalt octoate, and zirconium octoate, and amine compounds.
- the amount of the oxygen-curable substance to be used is preferably in the range of 0.1 to 20 parts by weight, more preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the organic polymer (A) having a reactive silicon group. 5 to: L0 parts by weight. When the amount is less than 0.1 part by weight, the improvement of the contamination is not sufficient, and when the amount exceeds 20 parts by weight, the tensile properties of the cured product are reduced. Tend to be impaired.
- an oxygen-curable substance is preferably used in combination with a photocurable substance.
- An antioxidant can be used in the composition of the present invention.
- an antioxidant when an antioxidant is used, the heat resistance of the cured product can be increased.
- the antioxidant include hindered phenols, monophenols, bisphenols and polyphenols. Hindered phenols are particularly preferred. Specific examples of the antioxidant are also described in JP-A-4-283259-JP-A-9-194731.
- the amount of the antioxidant used is preferably in the range of 0.1 to 10 parts by weight, more preferably 0.2 to 10 parts by weight, per 100 parts by weight of the organic polymer (A) having a reactive silicon group. 5 parts by weight.
- An epoxy resin can be added to the composition of the present invention.
- the composition to which the epoxy resin is added is particularly preferable as an adhesive, particularly an adhesive for exterior wall tiles.
- Flame retardant epoxy resins such as epichlorohydrin-bisphenol A type epoxy resin, epichlorohydrin-bisphenol F type epoxy resin, and glycidyl ether of tetrabromobisphenol A , Novolak type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol A glycidyl ether type epoxy resin of kapsum with propylene oxide, p-oxybenzoic acid glycidyl ether ester type epoxy resin, m— Aminopheno mono-epoxy resin, diamino diphenyl methane epoxy resin, urethane-modified epoxy resin, various alicyclic epoxy resins, N, N-diglycidyl dilin, N, N-diglycidyl o-toluidine , Triglycidyl isocyanurate
- the used epoxy resin can be used.
- a resin containing at least two epoxy groups in a molecule is preferred because it has high reactivity upon curing and has a point force such that the cured product easily forms a three-dimensional network.
- More preferred are bisphenol A type epoxy resins and novolak type epoxy resins.
- the preferred ratio of use differs depending on the application of the curable resin composition and the like, but cannot be unconditionally determined. For example, the impact resistance, flexibility, toughness, and peel strength of the cured epoxy resin are improved. If you do
- the component (A) is used in an amount of 1 to 100 parts by weight of the epoxy resin, preferably from LOO parts by weight, more preferably from 5 to 100 parts by weight.
- epoxy resin curing agent for curing the epoxy resin
- an epoxy resin curing agent that is generally used without any particular limitation can be used.
- an epoxy resin curing agent When an epoxy resin curing agent is used, its amount is in the range of 0.1 to 300 parts by weight with respect to 100 parts by weight of the epoxy resin.
- Ketimine can be used as a curing agent for epoxy resins. Ketimine exists stably in the absence of moisture, and is decomposed into primary amines and ketones by moisture, and the resulting primary amines become room temperature curing agents for epoxy resins. When ketimine is used, a one-pack type composition can be obtained. Such ketimines include amine compounds and carbonyl compounds. Can be obtained by a condensation reaction of
- amine compounds include ethylenediamine, propylenediamine, trimethylenediamine and tetramethylenediamine.
- Diamines such as 1,3,3 diaminobutane, 2,3 diaminobutane, pentamethylenediamine, 2,4 diaminopentane, hexamethylenediamine, p-phenylenediamine, p, ⁇ '-biphenylenediamine
- Polyvalent amines such as 1,2,3 triaminopropane, triaminobenzene, tris (2-aminoethyl) amine and tetrakis (aminomethyl) methane; polyalkyls such as diethylenetriamine, triethylenetriamine and tetraethylenepentamine; Lenpolyamine; polyoxyanolylene-based polyamine; ⁇ -aminopropyltriethoxy Aminosilanes such as silane, ⁇ (monoaminoethyl) - ⁇ -aminopropyltrimethoxysilane, ⁇ - ( ⁇ -aminoethyl) y-amin
- Examples of the carbon compound include aldehydes such as acetaldehyde, propionaldehyde, ⁇ -butyraldehyde, isobutyraldehyde, getylacetaldehyde, glyoxal, and benzaldehyde; cyclopentanone, trimethylcyclopentanone, and cyclohexanone.
- aldehydes such as acetaldehyde, propionaldehyde, ⁇ -butyraldehyde, isobutyraldehyde, getylacetaldehyde, glyoxal, and benzaldehyde
- cyclopentanone trimethylcyclopentanone
- cyclohexanone cyclohexanone
- cyclic ketones such as trimethylcyclohexanone; aliphatic ketones such as acetone, methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, methyl ketone, dipropyl ketone, diisopropyl ketone, dibutyl ketone and diisobutyl ketone; 13 dicarbonitrile such as acetylacetone, methyl acetoacetate, ethyl acetoacetate, dimethyl malonate, getyl malonate, methylethyl malonate, dibenzoylmethane Compounds; and the like can be used.
- the imino group may be reacted with styrene oxide; glycidyl ether such as butyldaricidyl ether and arylglycidyl ether; and glycidyl ester.
- styrene oxide such as butyldaricidyl ether and arylglycidyl ether
- glycidyl ester such as butyldaricidyl ether and arylglycidyl ether
- glycidyl ester glycidyl ester
- the curable composition of the present invention includes a phosphorus-based plasticizer such as ammonium polyphosphate and tricresyl phosphate, aluminum hydroxide, magnesium hydroxide, and heat-expandable graphite. Flame retardants can be added. The above flame retardants can be used alone. Use it together.
- a phosphorus-based plasticizer such as ammonium polyphosphate and tricresyl phosphate, aluminum hydroxide, magnesium hydroxide, and heat-expandable graphite.
- Flame retardants can be added. The above flame retardants can be used alone. Use it together.
- the flame retardant is used in an amount of 5 to 200 parts by mass, preferably 10 to: LOO part by mass based on 100 parts by mass of the component (A).
- a solvent can be used for the purpose of reducing the viscosity of the composition, increasing the thixotropy, and improving the workability.
- various compounds can be used without particular limitation. Specific examples include hydrocarbon solvents such as toluene, xylene, heptane, hexane, petroleum solvents, halogen solvents such as trichloroethylene, ester solvents such as ethyl acetate and butyl acetate, acetone, methyl ethyl ketone, and the like.
- Ketone solvents such as methyl isobutyl ketone, ether solvents, alcohol solvents such as methanol, ethanol and isopropanol, and silicone solvents such as hexamethylcyclotrisiloxane, otatamethylcyclotetrasiloxane and decamethylcyclopentasiloxane.
- the boiling point of the solvent is preferably 150 ° C or higher, more preferably 200 ° C or higher, and more preferably 250 ° C or higher, due to the problem of air pollution when the composition is used indoors. Particularly preferred.
- These solvents may be used alone or in combination of two or more.
- the amount of the solvent is preferably 3 parts by weight or less, more preferably 1 part by weight or less, based on 100 parts by weight of the organic polymer as the component (A). It is most preferred that it is not included.
- additives may be added as necessary for the purpose of adjusting various physical properties of the curable composition or the cured product.
- additives include, for example, curability modifiers, radical inhibitors, metal deactivators, ozone deterioration inhibitors, phosphorus peroxide decomposers, lubricants, pigments, foaming agents, Ants, fungicides and the like. These various additives may be used alone or in combination of two or more.
- the curable composition of the present invention can be prepared as a one-component type in which all the components are premixed, sealed, and stored, and cured by the moisture in the air after application.
- Components such as a curing catalyst, a filler, a plasticizer, and water may be blended in advance, and the blended material and the polymer composition may be mixed before use to prepare a two-component type. From the viewpoint of workability, the one-component type is preferable.
- the curable composition is a one-component type, since all the components are preliminarily compounded, the components containing water are dehydrated and dried before use, or the pressure is reduced during mixing and kneading. It is preferred to dehydrate with water.
- the curable composition is of a two-component type, it is not necessary to blend a curing catalyst with a main ingredient containing a polymer having a reactive silicon group. Although there is little worry about gelling, it is preferable to dehydrate and dry when long-term storage stability is required.
- Dehydration and drying methods include heating and drying for powdered solids, and vacuum dehydration for liquids or dehydration using synthetic zeolite, activated alumina, silica gel, quicklime, magnesium oxide, etc. The method is preferred. Alternatively, a small amount of the isocyanate conjugate may be blended, and the isocyanate group may be reacted with water for dehydration. Further, an oxazolidinide compound such as 3-ethyl-2-methyl-2- (3-methylbutyl) 1,3 oxazolidine may be blended, reacted with water and dehydrated.
- an oxazolidinide compound such as 3-ethyl-2-methyl-2- (3-methylbutyl) 1,3 oxazolidine may be blended, reacted with water and dehydrated.
- Lower alcohols such as methanol and ethanol by vigorous dehydration drying; n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, methylsilicate, ethyl silicate, ⁇ -mercaptopropylmethyldimethoxysilane, Storage stability is further improved by adding an alkoxysilane conjugate such as ⁇ -mercaptopropylmethylethoxysilane or ⁇ -glycidoxypropyltrimethoxysilane.
- the amount of the dehydrating agent is 0.1 to 20 parts by weight based on 100 parts by weight of the organic polymer having a reactive silicon group ( ⁇ ). Parts by weight, preferably in the range of 0.5 to 10 parts by weight, are preferred.
- the method for preparing the curable composition of the present invention is not particularly limited.
- the above-mentioned components are mixed, and the mixture is kneaded at room temperature or under heat using a mixer, a roll, a kneader, or the like.
- Conventional methods such as dissolving and mixing the components using a small amount of a solvent can be employed.
- the curable composition of the present invention is three-dimensionally exposed to the atmosphere by the action of moisture. It forms a network and cures to a rubbery elastic solid.
- the curable composition of the present invention includes a pressure-sensitive adhesive, a sealant for roads such as buildings “vehicles” and “automobiles", an adhesive, a molding agent, a vibration-proof material, a vibration-proof material, a sound-proof material, a foam material, and a paint. It can be used for spraying materials.
- a cured product obtained by curing the curable composition of the present invention is excellent in flexibility and adhesiveness, and among these, it is more preferable to use the cured product as a sealing material or an adhesive.
- electric and electronic component materials such as sealing materials for backsides of solar cells, electric insulating materials such as insulating covering materials for electric wires and cables, elastic adhesives, outer contour adhesives, spray-type sealing materials, crack repairs Materials, adhesives for tiling, powder coatings, casting materials, rubber materials for medical use, medical adhesives, sealing materials for medical equipment, food packaging materials, sealing materials for joints of exterior materials such as sizing boards, coating materials, Primer, conductive material for electromagnetic wave shielding, heat conductive material, hot melt material, potting agent for electric and electronic materials, film, gasket, various molding materials, and prevention of the end face (cut part) of netted glass and laminated glass It can be used for various applications such as sealing materials for waterproofing, liquid sealants used in automobile parts, electric parts, various mechanical parts, etc.
- the curable composition of the present invention can be used as an adhesive for interior panels, an adhesive for exterior panels, an adhesive for tiles, an adhesive for stones, an adhesive for ceiling finishing, an adhesive for floor finishing, and an adhesive for wall finishing.
- Adhesives, adhesives for vehicle panels, adhesives for assembling electric / electronic / precision equipment, sealing materials for direct glazing, sealing materials for double glazing, sealing materials for the SSG method, or sealing materials for working joints in buildings Can also be used.
- polyoxypropylene triol having a molecular weight of about 3,000 as an initiator
- polymerization of propylene oxide was carried out using a zinc hexacyanocobaltate glyme complex catalyst, and the number average molecular weight was measured.
- Polypropylene oxide of about 26,000 (Tosoh HLC-8120GPC was used as the liquid sending system, TSK-GEL H type column was used as the column, and the polystyrene equivalent molecular weight was measured using THF as the solvent) was obtained. .
- component (A) 100 parts by weight of the reactive silicon group-containing polyoxyalkylene polymer (A-1) obtained in Synthesis Example 1 was used, and the surface-treated colloidal calcium carbonate (manufactured by Shiraishi Kogyo Co., Ltd.
- titanium diisopropoxide was added to the above-mentioned main ingredient according to the formulation shown in Table 1.
- Sidobis ethyl acetate acetate
- titanium diisopropoxide bis acetinoleacetonate
- isopropyl alcohol Matsumoto Trading
- ORGATICS TC-100 titanium diisopropoxide bis (acetinoleacetonate)
- dibutyltin bis acetyl acetate
- the number of titanium catalysts added was adjusted so that the number of moles of Ti atoms in the composition was the same.
- the color of the surface of the composition immediately after mixing was visually observed.
- the mixed composition was filled in a mold having a thickness of about 5 mm using a spatula, and the surface was flattened. This time was defined as the curing start time, the surface was touched with a spatula, and the time when the compound did not adhere to the spatula was measured as skinning time.
- the skinning time was measured under the conditions of 23 ° C and 50% RH.
- Table 1 shows the evaluation results of the composition, the color of the composition, and the skinning time.
- composition parts by weight
- compositions (Examples 1 to 5) are white and have good curability.
- composition using TC-100 as a titanium catalyst other than the component (B) (Comparative Example 3) is colored pale yellow and has poor curability.
- a 1Z1 (weight ratio) mixture of polyoxypropylene diol having a molecular weight of about 2,000 and polyoxypropylene triol having a molecular weight of about 3,000 is used as an initiator.
- a hydroxyl-terminated polypropylene oxide having a number average molecular weight of about 19,000 an aryl-terminated polypropylene oxide was obtained in the same procedure as in Synthesis Example 1.
- This aryl-terminated polypropylene oxide was reacted with 1.35 parts by weight of methyldimethoxysilane in the same procedure as in Synthesis Example 1 to obtain a polyoxypropylene-based polymer having an average of 1.7 methyldimethoxysilyl groups at the terminals. (A-3) was obtained.
- the polymer ( ⁇ -3) obtained in Synthesis Example 3 and the polymer ( ⁇ -4) obtained in Synthesis Example 4 were mixed at a solid content weight ratio of 80-20, and the solvent was distilled off to remove the solvent-free polymer ( ⁇ — 5) was obtained.
- a solution prepared by dissolving 2,2′-azobis (2-methylbutyro-tolyl) as a polymerization initiator was added dropwise to a 2-butanol solution of the following monomer mixture heated to 105 ° C. over 5 hours. Thereafter, “post-polymerization” was carried out for 1 hour to obtain a (meth) acrylate polymer (A-6).
- Each one-pack type curable composition was extruded from the cartridge, and the color of the surface of the composition was visually observed.
- the extruded curable composition was filled in a mold having a thickness of about 3 mm using a spatula, and the surface was adjusted to a flat shape.
- a cured sample of a 3 mm thick sheet obtained by curing at 23 ° C for 3 days + 50 ° C for 4 days was exposed for 300 hours with a SWOM weathering tester, taken out, and the surface of the cured product was observed.
- B indicates that an abnormality such as a surface crack was observed, and A indicates that no abnormality was observed.
- Table 2 shows the composition, the color of the composition, and the evaluation results of SWOM weather resistance.
- A- 2 100 100 100 100 100 100 100 100 100 Organic polymer A- 5 100
- composition containing the light stabilizer having a benzotriazole ring (Comparative Example 8) was colored yellow and contained no light stabilizer at all!
- the composition (Comparative Example 9) has poor weather resistance.
- the compositions containing the light stabilizer having no benzotriazole ring and containing the light stabilizer having no benzotriazole ring (Examples 6 to 12) are white and have good weather resistance.
- the following adhesive test was carried out using the one-component curable composition of Example 6.
- the curable composition was extruded from the cartridge so as to be in close contact with various adherends (polycarbonate and acrylic) to prepare samples. After curing the prepared sample at 23 ° C for 7 days, the adhesiveness was evaluated by a 90 degree hand peel test. As a result, all the adherends showed cohesive failure.
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/579,726 US7446158B2 (en) | 2004-05-07 | 2005-04-25 | Curable composition |
JP2006512950A JP4898430B2 (ja) | 2004-05-07 | 2005-04-25 | 硬化性組成物 |
EP05734516.7A EP1749858B1 (en) | 2004-05-07 | 2005-04-25 | Curable composition |
Applications Claiming Priority (14)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2004-139110 | 2004-05-07 | ||
JP2004139111 | 2004-05-07 | ||
JP2004-139111 | 2004-05-07 | ||
JP2004139110 | 2004-05-07 | ||
JP2004-146973 | 2004-05-17 | ||
JP2004146976 | 2004-05-17 | ||
JP2004146973 | 2004-05-17 | ||
JP2004146974 | 2004-05-17 | ||
JP2004-146977 | 2004-05-17 | ||
JP2004-146972 | 2004-05-17 | ||
JP2004146972 | 2004-05-17 | ||
JP2004-146974 | 2004-05-17 | ||
JP2004146977 | 2004-05-17 | ||
JP2004-146976 | 2004-05-17 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2005108494A1 true WO2005108494A1 (ja) | 2005-11-17 |
Family
ID=35320211
Family Applications (7)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2005/007799 WO2005108492A1 (ja) | 2004-05-07 | 2005-04-25 | 硬化性組成物 |
PCT/JP2005/007798 WO2005108491A1 (ja) | 2004-05-07 | 2005-04-25 | 硬化性組成物 |
PCT/JP2005/007804 WO2005108499A1 (ja) | 2004-05-07 | 2005-04-25 | 硬化性と接着性の改善された硬化性組成物 |
PCT/JP2005/007803 WO2005108494A1 (ja) | 2004-05-07 | 2005-04-25 | 硬化性組成物 |
PCT/JP2005/007800 WO2005108493A1 (ja) | 2004-05-07 | 2005-04-25 | 硬化性組成物 |
PCT/JP2005/007802 WO2005108498A1 (ja) | 2004-05-07 | 2005-04-25 | 硬化性組成物 |
PCT/JP2005/007805 WO2005108500A1 (ja) | 2004-05-07 | 2005-04-25 | 接着性の改善された硬化性組成物 |
Family Applications Before (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2005/007799 WO2005108492A1 (ja) | 2004-05-07 | 2005-04-25 | 硬化性組成物 |
PCT/JP2005/007798 WO2005108491A1 (ja) | 2004-05-07 | 2005-04-25 | 硬化性組成物 |
PCT/JP2005/007804 WO2005108499A1 (ja) | 2004-05-07 | 2005-04-25 | 硬化性と接着性の改善された硬化性組成物 |
Family Applications After (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2005/007800 WO2005108493A1 (ja) | 2004-05-07 | 2005-04-25 | 硬化性組成物 |
PCT/JP2005/007802 WO2005108498A1 (ja) | 2004-05-07 | 2005-04-25 | 硬化性組成物 |
PCT/JP2005/007805 WO2005108500A1 (ja) | 2004-05-07 | 2005-04-25 | 接着性の改善された硬化性組成物 |
Country Status (5)
Country | Link |
---|---|
US (7) | US7446158B2 (ja) |
EP (7) | EP1752496A4 (ja) |
JP (7) | JP5225580B2 (ja) |
CN (1) | CN1950459B (ja) |
WO (7) | WO2005108492A1 (ja) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008115281A (ja) * | 2006-11-06 | 2008-05-22 | Momentive Performance Materials Japan Kk | 硬化性組成物 |
JP2008303373A (ja) * | 2007-05-07 | 2008-12-18 | Momentive Performance Materials Japan Kk | 硬化性組成物 |
JP2010065102A (ja) * | 2008-09-09 | 2010-03-25 | Nitto Denko Corp | 光学フィルム用粘着剤組成物、光学フィルム用粘着剤層、粘着型光学フィルムおよび画像表示装置 |
Families Citing this family (119)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4101632B2 (ja) * | 2002-11-01 | 2008-06-18 | 株式会社カネカ | 硬化性組成物および復元性、クリープ性改善方法 |
US7446158B2 (en) * | 2004-05-07 | 2008-11-04 | Kaneka Corporation | Curable composition |
JP4480457B2 (ja) * | 2004-05-17 | 2010-06-16 | 株式会社カネカ | 硬化性組成物 |
DE102005042899A1 (de) * | 2005-09-08 | 2007-03-15 | Ewald Dörken Ag | Schweißbares Korrosionsschutzmittel und Bindemittel hierfür |
WO2007037483A1 (ja) * | 2005-09-30 | 2007-04-05 | Kaneka Corporation | 硬化性組成物 |
KR101354835B1 (ko) * | 2005-12-02 | 2014-01-22 | 모멘티브 파포만스 마테리아루즈 쟈판 고도가이샤 | 실온 경화성 규소기 함유 폴리머 조성물 |
JP5109147B2 (ja) * | 2005-12-21 | 2012-12-26 | 旭硝子株式会社 | 伸び増強剤及びそれを含む硬化性組成物 |
JP5335178B2 (ja) * | 2005-12-22 | 2013-11-06 | モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社 | 室温硬化性ケイ素基含有ポリマー組成物の調製方法 |
DE102006006975A1 (de) * | 2006-02-14 | 2007-08-30 | Bostik Gmbh | Einkomponentiger, lösemittelfreier Kontaktklebstoff |
CN101484499B (zh) * | 2006-07-03 | 2013-03-27 | 旭硝子株式会社 | 氧化烯聚合物的制造方法及固化性组合物 |
JP2008019361A (ja) * | 2006-07-14 | 2008-01-31 | Momentive Performance Materials Japan Kk | 反応性ケイ素基含有ポリマーの調製方法および室温硬化性ケイ素基含有ポリマー組成物 |
JP5040229B2 (ja) * | 2006-09-20 | 2012-10-03 | 住友化学株式会社 | 紫外線カットフィルム |
EP2302000B1 (en) * | 2006-11-22 | 2016-11-16 | Kaneka Corporation | Curable composition and catalyst composition |
EP2853245A1 (en) * | 2006-12-20 | 2015-04-01 | Coloplast A/S | A pressure sensitive adhesive composition comprising salt |
DE102006061458B4 (de) | 2006-12-23 | 2014-06-18 | Bostik Gmbh | Verwendung einer selbstverlaufenden, wasserfreien Beschichtungsmasse und Fußboden, mit Laminat- oder Parkettpaneelen |
CA2685747C (en) * | 2007-05-01 | 2013-06-18 | Akzo Nobel Coatings International B.V. | Antifouling coating composition based on curable polyorganosiloxane polyoxyalkylene copolymers |
JP5354511B2 (ja) * | 2007-07-12 | 2013-11-27 | 日東化成株式会社 | 有機重合体用硬化触媒およびそれを含有する湿気硬化型有機重合体組成物 |
GB0714257D0 (en) * | 2007-07-23 | 2007-08-29 | Dow Corning | Sealant for insulating glass unit |
WO2009014077A1 (ja) * | 2007-07-24 | 2009-01-29 | Kaneka Corporation | 硬化性組成物 |
JP4460591B2 (ja) | 2007-07-30 | 2010-05-12 | 信越化学工業株式会社 | 液状シリコーンゴムコーティング剤組成物、カーテンエアーバッグ及びその製造方法 |
DE102007038030B4 (de) * | 2007-08-10 | 2009-07-09 | Henkel Ag & Co. Kgaa | Härtbare Zusammensetzungen aus Dimethoxysilanen |
DE102007038661A1 (de) * | 2007-08-15 | 2009-02-19 | Henkel Ag & Co. Kgaa | Silanvernetzender Kleb- oder Dichtstoff mit N-Silylakylamiden und seine Verwendung |
US8101039B2 (en) | 2008-04-10 | 2012-01-24 | Cardinal Ig Company | Manufacturing of photovoltaic subassemblies |
DE502008000156D1 (de) * | 2008-03-05 | 2009-12-03 | Sika Technology Ag | Zusammensetzung mit verbesserter Haftung auf porösen Substraten |
KR20100138990A (ko) * | 2008-03-26 | 2010-12-31 | 아이카고교 가부시키가이샤 | 핫멜트 조성물, 시일재, 및 태양전지 |
DE102008047362A1 (de) | 2008-09-15 | 2010-04-15 | Henkel Ag & Co. Kgaa | Zusammensetzung zur Hautaufhellung |
JP2010100839A (ja) * | 2008-09-26 | 2010-05-06 | Kaneka Corp | 太陽電池モジュール用硬化性組成物および太陽電池モジュール |
JP2010111870A (ja) * | 2008-11-07 | 2010-05-20 | Kaneka Corp | 硬化性組成物および複層ガラス用シーリング材 |
EP2199351A1 (de) * | 2008-12-19 | 2010-06-23 | Sika Technology AG | Flüssigfolie auf Basis von silanterminierten Polymeren |
US9640396B2 (en) * | 2009-01-07 | 2017-05-02 | Brewer Science Inc. | Spin-on spacer materials for double- and triple-patterning lithography |
JP5717320B2 (ja) * | 2009-03-12 | 2015-05-13 | リンテック株式会社 | 再剥離型粘着シート |
DE102009026679A1 (de) * | 2009-06-03 | 2010-12-16 | Henkel Ag & Co. Kgaa | Kleb- und Dichtstoffe auf Basis silanterminierter Bindemittel zum Verkleben und Abdichten von flexiblen Solarfolien / Photovoltaikmodulen |
DE102009027357A1 (de) * | 2009-06-30 | 2011-01-05 | Wacker Chemie Ag | Alkoxysilanterminierte Polymere enthaltende Kleb- oder Dichtstoffmassen |
FR2948123B1 (fr) * | 2009-07-20 | 2011-12-16 | Bostik Sa | Colle de reparation ou de fixation sans organoetain |
US8952188B2 (en) | 2009-10-23 | 2015-02-10 | Air Products And Chemicals, Inc. | Group 4 metal precursors for metal-containing films |
WO2011072056A2 (en) | 2009-12-08 | 2011-06-16 | Dow Corning Coporation | Cure rate control for alkoxysilyl-end-blocked polymers |
EP2336210B1 (de) * | 2009-12-17 | 2014-03-12 | Sika Technology AG | Silanfunktionelle Polymere, welche bei der Vernetzung kein Methanol abspalten |
JP5789087B2 (ja) * | 2010-04-23 | 2015-10-07 | 株式会社カネカ | 内装用の非有機錫系接着剤組成物およびその硬化物 |
DE102010030096A1 (de) * | 2010-06-15 | 2011-12-15 | Wacker Chemie Ag | Silanvernetzende Zusammensetzungen |
DE102010041676A1 (de) * | 2010-09-29 | 2012-03-29 | Wacker Chemie Ag | Vernetzbare Organopolysiloxanzusammensetzung |
TWI529193B (zh) * | 2010-10-20 | 2016-04-11 | 可隆股份有限公司 | 可光聚合的組成物及光學片 |
JP5887786B2 (ja) * | 2010-10-27 | 2016-03-16 | セメダイン株式会社 | 硬化性組成物 |
JP6161103B2 (ja) * | 2010-10-27 | 2017-07-12 | セメダイン株式会社 | 硬化性組成物の製造方法 |
DE102010062186A1 (de) * | 2010-11-30 | 2012-05-31 | Henkel Ag & Co. Kgaa | Zweikomponentige härtbare Zusammensetzung |
FR2969638B1 (fr) * | 2010-12-22 | 2014-05-02 | Bostik Sa | Composition adhesive et procede correspondant de pose de parquet a stabilite dimensionnelle amelioree |
CN103328717B (zh) | 2011-01-18 | 2016-07-06 | 派特拉国际控股有限责任公司 | 用卤代硅烷处理基材的方法 |
DE102011003425B4 (de) * | 2011-02-01 | 2015-01-08 | Henkel Ag & Co. Kgaa | Verwendung einer härtbaren Zusammensetzung mit kombinierten Stabilisatoren |
JP5993367B2 (ja) * | 2011-04-15 | 2016-09-14 | 株式会社カネカ | 建築用外装材 |
KR101305438B1 (ko) | 2011-05-13 | 2013-09-06 | 현대자동차주식회사 | 폴리우레탄과 알루미늄의 접착을 위한 접착제 |
CN102140268B (zh) * | 2011-05-17 | 2013-04-10 | 欧美龙(南通)重防腐涂料有限公司 | 船舶压载舱防腐无溶剂环氧涂料改性添加剂及改性环氧涂料 |
TWI506110B (zh) | 2011-05-30 | 2015-11-01 | Cheil Ind Inc | 黏合劑組合物、光學元件和黏合劑片 |
JP2013032450A (ja) * | 2011-08-02 | 2013-02-14 | Kaneka Corp | 粘着剤組成物 |
CN103781823B (zh) | 2011-09-07 | 2016-08-17 | 道康宁公司 | 含钛络合物和缩合反应催化剂、制备该催化剂的方法以及包含该催化剂的组合物 |
US9228061B2 (en) | 2011-09-07 | 2016-01-05 | Dow Corning Corporation | Zirconium containing complex and condensation reaction catalysts, methods for preparing the catalysts, and compositions containing the catalysts |
JP2012036397A (ja) * | 2011-09-30 | 2012-02-23 | Matsumoto Fine Chemical Co Ltd | 硬化性組成物 |
US9139699B2 (en) | 2012-10-04 | 2015-09-22 | Dow Corning Corporation | Metal containing condensation reaction catalysts, methods for preparing the catalysts, and compositions containing the catalysts |
KR101738602B1 (ko) * | 2011-10-17 | 2017-06-08 | 신에쓰 가가꾸 고교 가부시끼가이샤 | 축합반응 경화형 실리콘 박리 코팅 조성물 |
JP5834755B2 (ja) * | 2011-10-17 | 2015-12-24 | 信越化学工業株式会社 | 剥離性硬化皮膜の形成方法 |
CN102505484B (zh) * | 2011-11-04 | 2013-11-06 | 西安康本材料有限公司 | 一种用于复丝拉伸性能测试的胶液 |
JP5810865B2 (ja) * | 2011-11-25 | 2015-11-11 | 信越化学工業株式会社 | シリコーン粘着剤用縮合反応硬化型プライマー組成物 |
US8481626B1 (en) | 2012-01-16 | 2013-07-09 | Itron, Inc. | Wax-based encapsulant/moisture barrier for use with electronics received in water meter pits |
US8728568B2 (en) * | 2012-01-16 | 2014-05-20 | Itron, Inc. | Method for encapsulation of electronics received in water meter pits with an improved wax-based encapsulant/moisture barrier |
DE102012201734A1 (de) | 2012-02-06 | 2013-08-08 | Wacker Chemie Ag | Massen auf Basis von organyloxysilanterminierten Polymeren |
EP2641935A1 (de) * | 2012-03-19 | 2013-09-25 | Sika Technology AG | Zusammensetzung auf Basis von silanterminierten Polymeren |
JP5480359B1 (ja) * | 2012-12-25 | 2014-04-23 | 古河電気工業株式会社 | 有機エレクトロルミネッセンス素子封止用透明樹脂組成物、有機エレクトロルミネッセンス素子封止用樹脂シート、及び画像表示装置 |
DE102013101993A1 (de) * | 2013-02-28 | 2014-08-28 | Gerd Hoffmann | Leckdichtung für einen insbesondere Öl oder eine ölhaltige Flüssigkeit enthaltenden Behälter |
CN104903414A (zh) * | 2013-03-11 | 2015-09-09 | 松下知识产权经营株式会社 | 抑制碎片飞散涂料 |
WO2014185276A1 (ja) * | 2013-05-16 | 2014-11-20 | 信越化学工業株式会社 | アルミニウムキレート化合物及びこれを含有する室温硬化性樹脂組成物 |
JP5636141B1 (ja) * | 2013-06-14 | 2014-12-03 | 積水フーラー株式会社 | 接着剤組成物 |
DE102013213655A1 (de) * | 2013-07-12 | 2015-01-15 | Evonik Industries Ag | Härtbare Silylgruppen enthaltende Zusammensetzungen mit verbesserter Lagerstabilität |
WO2015016010A1 (ja) * | 2013-07-31 | 2015-02-05 | スリーボンドファインケミカル株式会社 | 湿気硬化性組成物 |
DE102013216852A1 (de) * | 2013-08-23 | 2015-02-26 | Wacker Chemie Ag | Vernetzbare Massen auf Basis von organyloxysilanterminierten Polymeren |
JP6735668B2 (ja) * | 2013-11-26 | 2020-08-05 | モメンティブ パフォーマンス マテリアルズ インコーポレイテッドMomentive Performance Materials Inc. | 金属−アレーン錯体を有する湿気硬化型組成物 |
WO2015120773A1 (en) | 2014-02-13 | 2015-08-20 | Honeywell International Inc. | Compressible thermal interface materials |
JP5918908B2 (ja) * | 2014-04-01 | 2016-05-18 | 日東化成株式会社 | 有機重合体又はオルガノポリシロキサン用硬化触媒、湿気硬化型組成物、硬化物及びその製造方法 |
JP5937754B2 (ja) * | 2014-04-01 | 2016-06-22 | 日東化成株式会社 | 有機重合体又はオルガノポリシロキサン用硬化触媒、湿気硬化型組成物、硬化物及びその製造方法 |
CN103923583A (zh) * | 2014-04-11 | 2014-07-16 | 苏州之诺新材料科技有限公司 | 一种单组份端硅烷基聚丙烯酸酯胶粘剂及其制备方法 |
DE102014210309A1 (de) * | 2014-05-30 | 2015-12-03 | Wacker Chemie Ag | Vernetzbare Massen auf Basis von organyloxysilanterminierten Polymeren |
JP6377415B2 (ja) * | 2014-06-03 | 2018-08-22 | 宇部興産建材株式会社 | 表面含浸材及び構造物 |
DE102014212291A1 (de) | 2014-06-26 | 2015-12-31 | Henkel Ag & Co. Kgaa | Titankomplexe als Vulkanisationskatalysatoren |
JP2016020407A (ja) * | 2014-07-11 | 2016-02-04 | 信越化学工業株式会社 | 含フッ素有機ケイ素化合物の硬化方法、硬化皮膜の製造方法、含フッ素有機ケイ素化合物を含む組成物、及び該組成物の硬化物で表面処理された物品 |
WO2016061121A1 (en) | 2014-10-13 | 2016-04-21 | Avery Dennison Corporation | Weldable and vibration damping silicone adhesives |
EP3048141B1 (en) | 2015-01-26 | 2017-11-22 | Avery Dennison Corporation | Self adhesive fouling release coating composition |
BR112017015276B1 (pt) | 2015-01-28 | 2022-09-06 | Dow Corning Corporation | Gel, composição em gel curável por condensação, método de fabricação de um gel, e, uso de um gel |
JP6509650B2 (ja) * | 2015-04-02 | 2019-05-08 | アイカ工業株式会社 | 透明性接着剤組成物 |
ES2682598T3 (es) * | 2015-12-17 | 2018-09-21 | Henkel Ag & Co. Kgaa | Complejos de titanio como catalizadores de vulcanización |
KR102554661B1 (ko) | 2016-03-08 | 2023-07-13 | 허니웰 인터내셔널 인코포레이티드 | 상 변화 물질 |
GB201613397D0 (en) | 2016-08-03 | 2016-09-14 | Dow Corning | Cosmetic composition comprising silicone materials |
GB201613412D0 (en) | 2016-08-03 | 2016-09-14 | Dow Corning | Elastomeric compositions and their applications |
GB201613414D0 (en) * | 2016-08-03 | 2016-09-14 | Dow Corning | Elastomeric compositions and their applications |
GB201613399D0 (en) | 2016-08-03 | 2016-09-14 | Dow Corning | Cosmetic composition comprising silicone materials |
EP3323844A1 (en) | 2016-11-17 | 2018-05-23 | Henkel AG & Co. KGaA | Curable compositions based on silicon-containing polymers using phosphazenes as catalysts |
GB201707437D0 (en) | 2017-05-09 | 2017-06-21 | Dow Corning | Lamination adhesive compositions and their applications |
GB201707439D0 (en) | 2017-05-09 | 2017-06-21 | Dow Corning | Lamination Process |
US10800921B2 (en) | 2017-06-26 | 2020-10-13 | Dow Silicones Corporation | Isocyanate-functional silicone-polyether copolymer, silicone-polyether-urethane copolymer formed therewith, sealants comprising same, and related methods |
KR20190013091A (ko) * | 2017-07-31 | 2019-02-11 | 다우 실리콘즈 코포레이션 | 이중 경화성 수지 조성물, 그로부터 형성된 경화물, 및 그러한 경화물을 포함하는 전자 장치 |
CN107541170B (zh) * | 2017-09-06 | 2021-07-13 | 广州集泰化工股份有限公司 | 一种建筑用单组分硅烷改性聚醚密封胶及其制备方法 |
US11041103B2 (en) | 2017-09-08 | 2021-06-22 | Honeywell International Inc. | Silicone-free thermal gel |
CN108003804A (zh) * | 2017-12-20 | 2018-05-08 | 烟台德邦科技有限公司 | 一种快速固化环保粘合剂的制备方法 |
CN111511863B (zh) * | 2017-12-29 | 2022-06-14 | 汉高股份有限及两合公司 | 耐酸粘合剂组合物 |
US11072706B2 (en) | 2018-02-15 | 2021-07-27 | Honeywell International Inc. | Gel-type thermal interface material |
JP6991891B2 (ja) * | 2018-02-26 | 2022-01-13 | 日東電工株式会社 | 両面粘着テープ |
KR20200131228A (ko) * | 2018-03-12 | 2020-11-23 | 린텍 가부시키가이샤 | 경화성 조성물, 경화물, 경화물의 제조 방법, 및, 경화성 조성물의 사용 방법 |
CN108754861B (zh) * | 2018-04-27 | 2021-02-09 | 安徽索亚装饰材料有限公司 | 一种皮雕用无纺布的生产工艺 |
EP3898780A2 (en) | 2018-12-21 | 2021-10-27 | Dow Silicones Corporation | Silicone-organic copolymer, sealants comprising same, and related methods |
US11760841B2 (en) | 2018-12-21 | 2023-09-19 | Dow Silicones Corporation | Silicone-polycarbonate copolymer, sealants comprising same, and related methods |
CN109943271A (zh) * | 2019-04-10 | 2019-06-28 | 广东绿洲化工有限公司 | 一种无溶剂型免钉胶及其制备方法 |
US11373921B2 (en) | 2019-04-23 | 2022-06-28 | Honeywell International Inc. | Gel-type thermal interface material with low pre-curing viscosity and elastic properties post-curing |
TW202118833A (zh) * | 2019-11-13 | 2021-05-16 | 美商陶氏有機矽公司 | 室溫儲存穩定的uv/vis及濕氣可雙重固化聚矽氧烷組成物 |
WO2021106942A1 (ja) * | 2019-11-29 | 2021-06-03 | 日東化成株式会社 | 重合体の硬化に用いる硬化触媒、湿気硬化型組成物、硬化物の製造方法 |
CN110845989B (zh) * | 2019-12-02 | 2021-09-03 | 苏州太湖电工新材料股份有限公司 | 一种双组份有机硅灌封胶及其应用方法 |
KR20220118902A (ko) * | 2019-12-19 | 2022-08-26 | 헨켈 아게 운트 코. 카게아아 | 수분 경화성 폴리아크릴레이트 조성물 및 그의 용도 |
JP6919010B1 (ja) | 2020-03-18 | 2021-08-11 | 旭化成ワッカーシリコーン株式会社 | 湿気硬化型組成物、および該湿気硬化型組成物の製造方法 |
EP3889222A1 (en) * | 2020-03-30 | 2021-10-06 | Henkel AG & Co. KGaA | Curable potting composition free of substances of very high concern |
CN115698177A (zh) * | 2020-06-22 | 2023-02-03 | 株式会社钟化 | 加热固化型的固化性组合物及其固化物 |
CN112552703A (zh) * | 2020-11-27 | 2021-03-26 | 山东奥斯登房车有限公司 | 一种不透光玻璃钢复合材料制品及应用 |
AU2021410790A1 (en) | 2020-12-23 | 2023-07-27 | Kintra Fibers, Inc. | Polyester polymer nanocomposites |
CN115991875B (zh) * | 2023-02-15 | 2023-12-15 | 杭州之江有机硅化工有限公司 | 一种脱醇型室温硫化硅橡胶用钛酸酯催化剂及其制备方法 |
CN116786389B (zh) * | 2023-08-23 | 2023-10-27 | 淄博大洋阻燃制品有限公司 | 阻燃隔热复合材料及其制备方法 |
Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH05311063A (ja) * | 1992-05-07 | 1993-11-22 | Sekisui Chem Co Ltd | シーリング材組成物 |
JP2001302929A (ja) * | 2000-04-20 | 2001-10-31 | Dow Corning Asia Ltd | 硬化性組成物 |
JP2001302930A (ja) * | 2000-04-20 | 2001-10-31 | Dow Corning Asia Ltd | 硬化性組成物 |
JP2001302934A (ja) * | 2000-04-20 | 2001-10-31 | Dow Corning Asia Ltd | 室温硬化性に優れた硬化性組成物 |
JP2002249672A (ja) * | 2001-02-23 | 2002-09-06 | Nitto Kasei Co Ltd | 湿気硬化型組成物 |
JP2003327856A (ja) * | 2002-05-16 | 2003-11-19 | Auto Kagaku Kogyo Kk | 硬化性組成物及びシーリング材組成物 |
JP2004002757A (ja) * | 2002-03-28 | 2004-01-08 | Kanegafuchi Chem Ind Co Ltd | 湿気硬化性組成物 |
JP2004059870A (ja) * | 2002-07-31 | 2004-02-26 | Yokohama Rubber Co Ltd:The | 硬化性樹脂組成物 |
JP2004083895A (ja) * | 2002-07-05 | 2004-03-18 | Kanegafuchi Chem Ind Co Ltd | 硬化性組成物の製造方法 |
JP2004083606A (ja) * | 2001-08-14 | 2004-03-18 | Kanegafuchi Chem Ind Co Ltd | 硬化性樹脂組成物 |
Family Cites Families (47)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4439557A (en) * | 1981-05-08 | 1984-03-27 | Toray Industries, Incorporated | Coating compositions |
JPS62146959A (ja) * | 1985-12-19 | 1987-06-30 | Kanegafuchi Chem Ind Co Ltd | 粘着剤組成物 |
JPS62252456A (ja) * | 1986-04-24 | 1987-11-04 | Toray Silicone Co Ltd | 室温硬化性オルガノポリシロキサン組成物 |
JP2565333B2 (ja) * | 1987-04-28 | 1996-12-18 | 東レ・ダウコーニング・シリコーン株式会社 | 電気・電子機器用室温硬化性オルガノポリシロキサン組成物 |
JP2557444B2 (ja) * | 1988-02-03 | 1996-11-27 | 鐘淵化学工業株式会社 | アルキッド系塗料の乾燥性が改善された硬化性組成物 |
JP2835400B2 (ja) * | 1988-10-07 | 1998-12-14 | 鐘淵化学工業株式会社 | 硬化性組成物 |
JP2813801B2 (ja) * | 1989-02-01 | 1998-10-22 | 鐘淵化学工業株式会社 | 接着方法 |
ES2082203T3 (es) * | 1990-04-03 | 1996-03-16 | Kanegafuchi Chemical Ind | Composicion de resina curable. |
DE4019074C1 (ja) * | 1990-06-15 | 1991-07-18 | Teroson Gmbh, 6900 Heidelberg, De | |
JP3304954B2 (ja) * | 1991-03-11 | 2002-07-22 | 鐘淵化学工業株式会社 | シーラント用硬化性組成物 |
JP3725178B2 (ja) * | 1991-03-22 | 2005-12-07 | 東レ・ダウコーニング株式会社 | 室温硬化性オルガノポリシロキサン組成物 |
DE4110796A1 (de) | 1991-04-04 | 1992-10-08 | Bayer Ag | Provisorische befestigungsmaterialien |
US5703146A (en) | 1991-09-12 | 1997-12-30 | Kanegafuchi Kagaku Kogyo Kabushiki Kaisha | Curable composition containing an oxypropylene polymer and calcium carbonate which has been surface treated with a fatty acid |
JP3112753B2 (ja) * | 1991-09-12 | 2000-11-27 | 鐘淵化学工業株式会社 | 硬化性組成物 |
JPH05331063A (ja) * | 1992-05-25 | 1993-12-14 | Takeda Chem Ind Ltd | エンドセリン受容体拮抗剤 |
US5719249A (en) * | 1993-11-29 | 1998-02-17 | Kanegafuchi Kagaku Kogyo Kabushiki Kaisha | Reactive silicon group-containing polyoxyalkylene-polysiloxane copolymer |
JPH06166810A (ja) * | 1992-11-30 | 1994-06-14 | Toray Dow Corning Silicone Co Ltd | 室温硬化性組成物 |
DE4329244A1 (de) * | 1993-08-31 | 1995-03-02 | Sandoz Ag | Wässrige Wachs- und Silicon-Dispersionen, deren Herstellung und Verwendung |
JP3080835B2 (ja) * | 1994-04-05 | 2000-08-28 | 積水化学工業株式会社 | 室温硬化性組成物 |
TW325490B (en) * | 1995-06-23 | 1998-01-21 | Ciba Sc Holding Ag | Polysiloxane light stabilizers |
WO1997013820A1 (fr) * | 1995-10-12 | 1997-04-17 | Kaneka Corporation | Procede pour installer des elements vitres sur des vehicules |
JPH09124921A (ja) * | 1995-10-30 | 1997-05-13 | Sekisui Chem Co Ltd | 外壁用充填材 |
US5962074A (en) * | 1996-06-05 | 1999-10-05 | 3M Innovative Properties Company | Wax composition and method of use |
EP0909288B1 (en) * | 1996-07-02 | 2007-06-27 | Ciba SC Holding AG | Process for curing a polymerizable composition |
GB2327425B (en) * | 1996-08-15 | 2000-03-15 | Simson B V | Adhesive composition |
GB9721132D0 (en) * | 1997-10-07 | 1997-12-03 | Tioxide Specialties Ltd | Polymeric sealant compositions |
JP3903549B2 (ja) * | 1997-10-21 | 2007-04-11 | 旭硝子株式会社 | 室温硬化性組成物 |
US6080816A (en) * | 1997-11-10 | 2000-06-27 | E. I. Du Pont De Nemours And Company | Coatings that contain reactive silicon oligomers |
GB9724055D0 (en) * | 1997-11-15 | 1998-01-14 | Dow Corning Sa | Curable polysiloxane compositions |
JPH11209538A (ja) * | 1998-01-26 | 1999-08-03 | Kanegafuchi Chem Ind Co Ltd | 硬化性組成物 |
JP3636583B2 (ja) * | 1998-01-29 | 2005-04-06 | 株式会社カネカ | 複層ガラス用シーリング材 |
JP2000109676A (ja) | 1998-10-08 | 2000-04-18 | Asahi Glass Co Ltd | 硬化性組成物 |
DE60043697D1 (de) * | 1999-03-23 | 2010-03-04 | Kaneka Corp | Härtbare harzzusammensetzungen |
CA2397715C (en) | 2000-01-06 | 2008-11-25 | Dow Corning S.A. | Organosiloxane compositions |
AU2473401A (en) | 2000-01-06 | 2001-07-16 | Dow Corning Asia Limited | Organosiloxane compositions |
JP4400983B2 (ja) * | 2000-01-06 | 2010-01-20 | 東レ・ダウコーニング株式会社 | 硬化性組成物 |
EP1138732B1 (en) * | 2000-03-31 | 2005-08-31 | JSR Corporation | Coating composition and cured product |
US7176269B2 (en) * | 2000-07-25 | 2007-02-13 | Mitsui Chemicals, Inc. | Curable composition and its use |
AU2002224911A1 (en) * | 2000-12-12 | 2002-06-24 | Ciba Specialty Chemicals Holding Inc. | Benzophenone uv-absorbers with heterocyclic substituents |
US6642309B2 (en) * | 2001-08-14 | 2003-11-04 | Kaneka Corporation | Curable resin composition |
WO2003035755A1 (en) * | 2001-10-23 | 2003-05-01 | Kaneka Corporation | Curable resin composition |
ATE348862T1 (de) * | 2001-11-29 | 2007-01-15 | Kaneka Corp | Härtbare zusammensetzung |
JP4699897B2 (ja) * | 2002-10-02 | 2011-06-15 | 株式会社カネカ | 1液型硬化性組成物 |
JP4101632B2 (ja) * | 2002-11-01 | 2008-06-18 | 株式会社カネカ | 硬化性組成物および復元性、クリープ性改善方法 |
WO2005003230A1 (ja) * | 2003-07-08 | 2005-01-13 | Kaneka Corporation | 硬化性組成物 |
US7446158B2 (en) * | 2004-05-07 | 2008-11-04 | Kaneka Corporation | Curable composition |
JP4480457B2 (ja) * | 2004-05-17 | 2010-06-16 | 株式会社カネカ | 硬化性組成物 |
-
2005
- 2005-04-25 US US11/579,726 patent/US7446158B2/en not_active Expired - Fee Related
- 2005-04-25 US US11/579,587 patent/US7910681B2/en not_active Expired - Fee Related
- 2005-04-25 JP JP2006512949A patent/JP5225580B2/ja active Active
- 2005-04-25 JP JP2006512947A patent/JP4480719B2/ja not_active Expired - Fee Related
- 2005-04-25 CN CN2005800145584A patent/CN1950459B/zh not_active Expired - Fee Related
- 2005-04-25 US US11/579,635 patent/US20070287780A1/en not_active Abandoned
- 2005-04-25 JP JP2006512948A patent/JP4819675B2/ja active Active
- 2005-04-25 WO PCT/JP2005/007799 patent/WO2005108492A1/ja active Application Filing
- 2005-04-25 US US11/579,630 patent/US7625990B2/en not_active Expired - Fee Related
- 2005-04-25 US US11/579,405 patent/US7763673B2/en not_active Expired - Fee Related
- 2005-04-25 WO PCT/JP2005/007798 patent/WO2005108491A1/ja active Application Filing
- 2005-04-25 EP EP05734521.7A patent/EP1752496A4/en not_active Withdrawn
- 2005-04-25 EP EP05734604.1A patent/EP1749859B1/en active Active
- 2005-04-25 EP EP05734516.7A patent/EP1749858B1/en active Active
- 2005-04-25 JP JP2006512950A patent/JP4898430B2/ja active Active
- 2005-04-25 US US11/579,553 patent/US7973108B2/en not_active Expired - Fee Related
- 2005-04-25 EP EP05734518.3A patent/EP1746135B1/en active Active
- 2005-04-25 US US11/579,551 patent/US7893170B2/en not_active Expired - Fee Related
- 2005-04-25 JP JP2006512951A patent/JP5225581B2/ja active Active
- 2005-04-25 WO PCT/JP2005/007804 patent/WO2005108499A1/ja active Application Filing
- 2005-04-25 WO PCT/JP2005/007803 patent/WO2005108494A1/ja active Application Filing
- 2005-04-25 JP JP2006512952A patent/JP5225582B2/ja not_active Expired - Fee Related
- 2005-04-25 EP EP05734515.9A patent/EP1746134B1/en active Active
- 2005-04-25 WO PCT/JP2005/007800 patent/WO2005108493A1/ja active Application Filing
- 2005-04-25 JP JP2006512946A patent/JP5002262B2/ja active Active
- 2005-04-25 WO PCT/JP2005/007802 patent/WO2005108498A1/ja active Application Filing
- 2005-04-25 EP EP05734309.7A patent/EP1749857B1/en active Active
- 2005-04-25 EP EP05734513.4A patent/EP1746133B1/en not_active Not-in-force
- 2005-04-25 WO PCT/JP2005/007805 patent/WO2005108500A1/ja active Application Filing
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH05311063A (ja) * | 1992-05-07 | 1993-11-22 | Sekisui Chem Co Ltd | シーリング材組成物 |
JP2001302929A (ja) * | 2000-04-20 | 2001-10-31 | Dow Corning Asia Ltd | 硬化性組成物 |
JP2001302930A (ja) * | 2000-04-20 | 2001-10-31 | Dow Corning Asia Ltd | 硬化性組成物 |
JP2001302934A (ja) * | 2000-04-20 | 2001-10-31 | Dow Corning Asia Ltd | 室温硬化性に優れた硬化性組成物 |
JP2002249672A (ja) * | 2001-02-23 | 2002-09-06 | Nitto Kasei Co Ltd | 湿気硬化型組成物 |
JP2004083606A (ja) * | 2001-08-14 | 2004-03-18 | Kanegafuchi Chem Ind Co Ltd | 硬化性樹脂組成物 |
JP2004002757A (ja) * | 2002-03-28 | 2004-01-08 | Kanegafuchi Chem Ind Co Ltd | 湿気硬化性組成物 |
JP2003327856A (ja) * | 2002-05-16 | 2003-11-19 | Auto Kagaku Kogyo Kk | 硬化性組成物及びシーリング材組成物 |
JP2004083895A (ja) * | 2002-07-05 | 2004-03-18 | Kanegafuchi Chem Ind Co Ltd | 硬化性組成物の製造方法 |
JP2004059870A (ja) * | 2002-07-31 | 2004-02-26 | Yokohama Rubber Co Ltd:The | 硬化性樹脂組成物 |
Non-Patent Citations (1)
Title |
---|
See also references of EP1749858A4 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008115281A (ja) * | 2006-11-06 | 2008-05-22 | Momentive Performance Materials Japan Kk | 硬化性組成物 |
JP2008303373A (ja) * | 2007-05-07 | 2008-12-18 | Momentive Performance Materials Japan Kk | 硬化性組成物 |
JP2008303374A (ja) * | 2007-05-07 | 2008-12-18 | Momentive Performance Materials Japan Kk | 硬化性組成物 |
JP2010065102A (ja) * | 2008-09-09 | 2010-03-25 | Nitto Denko Corp | 光学フィルム用粘着剤組成物、光学フィルム用粘着剤層、粘着型光学フィルムおよび画像表示装置 |
Also Published As
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2005108494A1 (ja) | 硬化性組成物 | |
KR101838533B1 (ko) | 경화성 조성물 | |
JP5284797B2 (ja) | 硬化性組成物 | |
WO2005121255A1 (ja) | 硬化性組成物 | |
EP2894199B1 (en) | Curable composition | |
JP2015172119A (ja) | 硬化性組成物およびその硬化物 | |
JP5161578B2 (ja) | 1成分型硬化性組成物 | |
JP2023075949A (ja) | ワーキングジョイント用1成分型硬化性組成物の製造方法、目地構造体の製造方法および施工方法 | |
JP2007091931A (ja) | オルガノシロキサン変性ポリオキシアルキレン系重合体、および、該重合体を含有するパネル用接着剤 | |
WO2004035707A1 (ja) | 光触媒層を有する透明材料に用いるシーリング材 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KM KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SM SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LT LU MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWE | Wipo information: entry into national phase |
Ref document number: 2006512950 Country of ref document: JP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 11579726 Country of ref document: US Ref document number: 2007219299 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWW | Wipo information: withdrawn in national office |
Ref document number: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2005734516 Country of ref document: EP |
|
WWP | Wipo information: published in national office |
Ref document number: 2005734516 Country of ref document: EP |
|
WWP | Wipo information: published in national office |
Ref document number: 11579726 Country of ref document: US |