WO2010008079A1 - Composition de résine durcissable - Google Patents

Composition de résine durcissable Download PDF

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Publication number
WO2010008079A1
WO2010008079A1 PCT/JP2009/062994 JP2009062994W WO2010008079A1 WO 2010008079 A1 WO2010008079 A1 WO 2010008079A1 JP 2009062994 W JP2009062994 W JP 2009062994W WO 2010008079 A1 WO2010008079 A1 WO 2010008079A1
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Prior art keywords
curable resin
group
compound
curable
bonded
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PCT/JP2009/062994
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English (en)
Japanese (ja)
Inventor
孝治 楠木
純 乾
幸弘 野村
茂樹 杉山
慎一 佐藤
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コニシ株式会社
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Priority to CN2009801253902A priority Critical patent/CN102076777B/zh
Priority to JP2009545750A priority patent/JP4445584B2/ja
Publication of WO2010008079A1 publication Critical patent/WO2010008079A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C08L101/10—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing hydrolysable silane groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/544—Silicon-containing compounds containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—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
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C09J201/02—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C09J201/10—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing hydrolysable silane groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • 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
    • C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
    • C09K3/1018—Macromolecular compounds having one or more carbon-to-silicon linkages

Definitions

  • the present invention relates to a curable resin composition containing a hydrolyzable silicon group, which can be cured at room temperature, and more specifically, it is possible to reduce environmental burden and to ensure safety while ensuring safety.
  • the present invention relates to a curable composition having a high curing rate.
  • a curable resin having a hydrolyzable silicon group in the molecule is widely used as a base polymer for sealants, adhesives, adhesives, paints and the like.
  • This curable resin is also called a moisture curable polymer because the hydrolyzable silicon group is cured by hydrolysis and crosslinking with moisture in the atmosphere.
  • curable resins whose hydrolyzable silicon groups are alkoxysilanes are widely used because of their safety and low odor.
  • Patent Document 3 it has been proposed to use an amine compound, a carboxylic acid compound, or a bismuth compound or a titanium compound as a curing catalyst.
  • Patent Document 4 it has been proposed to use an amine compound, a carboxylic acid compound, or a bismuth compound or a titanium compound as a curing catalyst.
  • these catalyst systems have not been practically satisfactory in curing rate.
  • Japanese published patent JP-A-52-73998 Japanese published patent: Japanese Patent Laid-Open No. 63-112642 Japanese published patent: Japanese Patent No. 3793074 Japanese published patent: Japanese Patent No. 3768072 Japanese Patent: JP 2005-514504 Gazette
  • organotin compounds have become problematic in recent years.
  • those containing highly toxic tributyltin derivatives are desired to be suppressed to 1000 ppm or less with respect to the composition.
  • not only tributyltin derivatives but also catalysts with a focus on heavy metals containing tin are of concern for toxicity and environmental impact, so it is needless to say that sufficient handling and usage are required when using them.
  • the problem to be solved by the present invention is to obtain a curable composition having a necessary and sufficient curing speed while achieving reduction of environmental burden and ensuring safety.
  • the present inventors have conducted intensive research and found that a curable resin containing a hydrolyzable silicon group and a curable resin having an ⁇ -silane structure in the molecule within a certain range. It was found that a sufficient curing rate can be obtained at room temperature by mixing at a ratio and further adding an aminosilane compound having no ⁇ -silane structure as a catalyst, thereby completing the present invention.
  • the first invention is A curable resin (A) having a hydrolyzable silicon group represented by formula (1) in the molecule; A curable resin (B) having a hydrolyzable silicon group represented by the formula (2) in the molecule; The compound represented by the formula (3), the condensation reaction product of the compound represented by the formula (3) alone, and the condensation reaction product of the compound represented by the formula (3) and another silane compound are selected. At least one aminosilane compound (C); A curable resin composition containing The curable resin (B) is contained in an amount of 15 to 900 parts by mass with respect to 100 parts by mass of the curable resin (A), and the total amount of the curable resin (A) and the curable resin (B) is 100 parts by mass.
  • the present invention relates to a curable resin composition containing 0.1 to 20 parts by mass of the aminosilane compound (C).
  • —X—SiR 1 a (OR 2 ) 3-a Formula (1) (Wherein X represents a hydrocarbon group having 2 or more carbon atoms, R 1 and R 2 each represents an alkyl group having 1 to 20 carbon atoms, and a represents 0, 1 or 2) —A—CH 2 —SiR 3 b (OR 4 ) 3-b Formula (2) (However, A is a bonding functional group in which a hetero atom having an unshared electron pair is bonded to a methylene group bonded to a silicon atom contained in the hydrolyzable silicon group, and R 3 and R 4 are carbon atoms having 1 to 20 carbon atoms.
  • a plurality of alkyl groups, b represents 0, 1 or 2, respectively.
  • R 5 and R 6 are organic groups or hydrogen atoms
  • R 7 is an organic group in which a hetero atom is not bonded to a carbon atom bonded to a hydrolyzable silicon atom
  • R 8 and R 9 are each having 1 carbon atom.
  • ⁇ 20 alkyl groups, c represents 0, 1 or 2, respectively.
  • the aminosilane compound (C) acts as a very weak curing catalyst for the curable resin (A), but the curable resin (A) cannot be completely cured by itself. However, when the curable resin (B) intervenes here, both the curable resin (A) and the curable resin (B) are completely cured by the catalytic effect of the aminosilane compound (C).
  • the second invention is characterized in that the main chain of the curable resin (A) is essentially polyoxyalkylene and / or poly (meth) acrylic acid ester, and is curable according to the first invention.
  • the present invention relates to a resin composition.
  • the third invention relates to the curable resin composition according to the first or second invention, wherein the hydrolyzable silicon group of the curable resin (A) is an alkyl dialkoxysilyl group. It is.
  • the fourth invention provides the curable resin composition according to any one of the first to third inventions, wherein the curable resin (A) does not contain a urethane bond or a urea bond in its molecule. It is about things.
  • the fifth invention relates to the curable resin composition according to any one of the first to fourth inventions, wherein the main chain of the curable resin (B) is essentially polyoxyalkylene. Is.
  • the sixth invention relates to a curable resin composition according to any one of the first to fifth inventions, wherein the organotin catalyst is 0 to less than 1000 ppm.
  • the seventh invention relates to a sealant composition mainly comprising the curable composition according to any one of the first to sixth inventions as a curable component.
  • the eighth invention relates to an adhesive composition mainly comprising the curable composition according to any one of the first to sixth inventions as a curable component.
  • the curable resin composition according to the present invention has an effect of achieving a necessary and sufficient curing rate while achieving a reduction in environmental burden and ensuring safety.
  • the curable resin (A) in the present invention is a curable resin having a hydrolyzable silicon group represented by the formula (1) in the molecule.
  • -X-SiR 1 a (OR 2 ) 3-a Formula (1) wherein X represents a hydrocarbon group having 2 or more carbon atoms, R 1 and R 2 each represents an alkyl group having 1 to 20 carbon atoms, and a represents 0, 1 or 2)
  • a hydrocarbon group (X) having 2 or more carbon atoms is bonded to a silicon atom, and this is bonded to the main chain skeleton.
  • the silicon atom has 1 to 3 alkoxy groups (OR 2 ) as hydrolyzable groups, and the remaining bond is a hydrocarbon group (R 1 ). 2 to 0 are bonded.
  • R 1 and R 2 are each an alkyl group having 1 to 20 carbon atoms.
  • the alkoxyl group (OR 2 ) is preferably a methoxy group, an ethoxy group, a propoxy group or a butoxy group, more preferably a methoxy group or an ethoxy group.
  • the hydrocarbon group (R 1 ) bonded to the remaining bond of the silicon atom is preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and more preferably a methyl group or an ethyl group.
  • the molecular weight of the curable resin (A) is not particularly limited, but is preferably 1,000 to 80,000, more preferably 1,500 to 60,000, and particularly preferably 2,000 to 40,000. If the molecular weight is less than 1,000, the crosslink density becomes too high, which may result in brittle properties. If the molecular weight exceeds 80,000, the viscosity becomes high and the workability deteriorates, so a large amount of solvent or plasticizer is required. In some cases, blending may be limited.
  • Examples of the main chain skeleton of the curable resin (A) include polyoxyalkylene, vinyl polymer, saturated hydrocarbon polymer, unsaturated hydrocarbon polymer, polyester resin, polycarbonate, polydimethylsiloxane, and other silicone resins and modified silicone resins.
  • One or more kinds of skeletons selected from generally used main chain skeletons are adopted, and in particular, the polyoxyalkylene and / or the poly (meth) acrylate is essentially a cured product. It is preferable from the viewpoint of film properties.
  • “essentially” means that the structure is a main element of a repeating unit which is the main chain skeleton of the curable resin (A).
  • this structure may be contained independently, and 2 or more types may be contained.
  • acrylic acid and methacrylic acid are collectively referred to as “(meth) acrylic acid”.
  • curable resins are sold as silicone resins or modified silicone resins.
  • a curable silicone resin containing a polar group such as a urethane bond or a urea bond in the molecule may be used as the curable resin (A).
  • the curable resin (A) containing a polar group in the molecule may be synthesized by a conventionally known method. For example, a method of reacting an isocyanate group-terminated polymer with an amino group-containing alkoxysilane compound (or a mercapto group-containing alkoxysilane compound), a method of reacting a hydroxyl group-terminated polyol with an isocyanate group-containing alkoxysilane compound, and the like are known. More specifically, Japanese Patent No. 3030020, Japanese Patent No.
  • the curable resin (A) when a cured product having a relatively low modulus and high elongation, such as a sealing material, is desired, the resin may not contain urethane bonds or urea bonds in the molecule. From the viewpoint of easy adjustment of the modulus.
  • the curable resin (B) in the present invention is a curable resin having a hydrolyzable silicon group represented by the formula (2) in the molecule.
  • A—CH 2 —SiR 3 b (OR 4 ) 3-b Formula (2) (However, A is a bonding functional group in which a hetero atom having an unshared electron pair is bonded to a methylene group bonded to a silicon atom contained in the hydrolyzable silicon group, and R 3 and R 4 are carbon atoms having 1 to 20 carbon atoms.
  • a plurality of alkyl groups, b represents 0, 1 or 2, respectively.
  • a bonding functional group in which a hetero atom having an unshared electron pair is bonded to a silicon atom contained in the hydrolyzable silicon group via a methylene group is bonded to the hydrolyzable silicon group.
  • the bond functional group is a structure that connects the hydrolyzable silicon group and the main chain, especially if a heteroatom having an unshared electron pair is bonded to a methylene group bonded to a silicon atom contained in the hydrolyzable silicon group.
  • Specific examples include (thio) urethane bonds, (thio) urea bonds, (thio) substituted urea bonds, (thio) ester bonds, (thio) ether bonds, and the like.
  • the hydrolyzable silicon group is bonded to the main chain skeleton via this bonding functional group.
  • the silicon atom has 1 to 3 alkoxy groups (OR 4 ) bonded as hydrolyzable groups and 2 to 4 hydrocarbon groups (R 3 ) as the remaining bonds. 0 units are connected.
  • R 3 and R 4 are each an alkyl group having 1 to 20 carbon atoms.
  • the alkoxyl group (OR 4 ) is preferably a methoxy group, an ethoxy group, a propoxy group or a butoxy group, more preferably a methoxy group or an ethoxy group.
  • the hydrocarbon group (R 3 ) bonded to the remaining bond of the silicon atom is preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and more preferably a methyl group or an ethyl group.
  • the molecular weight of the curable resin (B) is not particularly limited, but is preferably 1,000 to 80,000, more preferably 1,500 to 60,000, and particularly preferably 2,000 to 40,000.
  • the molecular weight is less than 1,000, the crosslink density becomes too high, which may result in brittle properties. If the molecular weight exceeds 80,000, the viscosity becomes high and the workability deteriorates, so a large amount of solvent or plasticizer is required. In some cases, blending may be limited.
  • ⁇ -silane structure such a chemical structure is referred to as an “ ⁇ -silane structure”.
  • the moisture reactivity is much higher than that of a normal hydrolyzable silicon group, so that a sufficient curing rate can be obtained even when a tin catalyst is not used or a much smaller amount is used than usual. Obtainable.
  • main chain skeleton of the curable resin (B) examples include polyoxyalkylene, vinyl polymer, saturated hydrocarbon polymer, unsaturated hydrocarbon polymer, polyester, polycarbonate, polydimethylsiloxane, and other silicone resins and modified silicone resins.
  • One or more skeletons selected from main chain skeletons that are generally used are employed, and in particular, they are essentially polyoxyalkylenes from the viewpoints of availability, film properties of cured products, and the like. preferable.
  • “essentially” means that the structure is a main element of a repeating unit which is the main chain skeleton of the curable resin (B). Moreover, this structure may be contained independently in curable resin (B), and 2 or more types may be contained.
  • synthesis may be performed by a conventionally known method.
  • a method of reacting a compound having a hetero atom bonded thereto is known. More specifically, it can be easily synthesized by the methods described in JP-T-2004-518801, JP-T-2004-536957, JP-T-2005-501146, and the like.
  • curable resins (B) examples include GENIOSIL STP-E10 and GENIOSIL STP-E30 manufactured by Wacker Chemie AG.
  • the main chain skeleton of the curable resin (A) and the curable resin (B) may be the same or different. However, it is preferable that the curable resin (A) and the curable resin (B) are compatible since the effects of the present invention are more easily obtained.
  • a conventionally known technique can be used. For example, a compound generally known as a compatibilizing agent can be added.
  • the main chain skeleton of the curable resin (A) and the curable resin (B) can be improved by selecting a combination having good compatibility. Specifically, the compatibility can be improved by using a main chain skeleton having a relatively close polarity.
  • the compatibility is very good. Even if they are not the same, it is also preferable to select skeletons having relatively similar structures such as polyolefin skeletons or polyether skeletons. Furthermore, it is known that a polyoxyalkylene skeleton and a poly (meth) acrylate skeleton having a specific structure also have good compatibility. Examples of combinations having good compatibility as described above are exemplified, but the present invention is not limited to these.
  • the aminosilane compound (C) in the present invention is a compound having one or more amino groups and hydrolyzable silicon groups in the molecule, and two or more carbon atoms between the amino group and the hydrolyzable silicon group. It is a bonded aminosilane compound.
  • the aminosilane compound (C) in the present invention is an aminosilane compound having no ⁇ -silane structure. A low molecular aminosilane compound having an ⁇ -silane structure is not suitable because of its high toxicity.
  • Examples of the aminosilane compound (C) include an aminosilane compound (c1) represented by the following general formula (3), a condensation reaction product of the aminosilane compound (c1) alone, or an aminosilane compound (c1) and the following general formula (4). And a condensation reaction product with another silane compound as exemplified by the silane compound (c2).
  • the aminosilane compound (c1) or the condensation reaction product of the aminosilane compound (c1) alone is more preferable because the effect of the amino group in the aminosilane compound (C) can be expressed more easily.
  • the amino group contained in the aminosilane compound (C) may be any of primary, secondary, and tertiary amino groups, but the curable resin composition according to the present invention may be an adhesive, a sealing material, In applications that require adhesiveness such as pressure-sensitive adhesives, primary or secondary amino groups that are more likely to exhibit the adhesion-imparting effect are preferred, and primary amino groups are particularly preferred.
  • the amino group contained in the said aminosilane compound (C) may be one, and may be two or more.
  • the number of hydrolyzable silicon groups contained in the aminosilane compound (C) may be one, or two or more.
  • R 5 and R 6 are organic groups or hydrogen atoms
  • R 7 is an organic group in which a hetero atom is not bonded to a carbon atom bonded to a hydrolyzable silicon atom
  • R 8 and R 9 are each having 1 carbon atom. ⁇ 20 alkyl groups, c represents 0, 1 or 2, respectively.
  • R 10 , R 11 and R 12 are represented by a phenyl group, an alkyl group having a molecular weight of 500 or less, a mercaptopropyl group, a ureidopropyl group, a phenoxy group, and an alkoxy group having 1 to 6 carbon atoms.
  • Each represents one or more groups selected from organic groups having a molecular weight of 500 or less
  • R 13 represents one or more groups selected from a phenyl group and an alkyl group having 1 to 6 carbon atoms.
  • Formula (3) is preferably an aminosilane compound represented by the following general formula (3 ').
  • R 5 ′ R 6 ′ NR 7 ′ -SiR 8 ′ c OR 9 ′ 3-c Formula (3 ′)
  • R 5 ′ and R 6 ′ are organic groups or hydrogen atoms having a molecular weight of 500 or less
  • R 7 ′ is a hetero atom not bonded to a carbon atom bonded to a hydrolyzable silicon atom
  • R 8 ′ and R 9 ′ each represent an alkyl group having 1 to 20 carbon atoms
  • c represents 0, 1 or 2, respectively.
  • aminosilane compound (c1) Specific examples of the aminosilane compound (c1) include 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, N- (2- Aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, N- (2 -Aminoethyl) -3-aminopropylmethyldiethoxysilane, 4-amino-3-dimethylbutyltrimethoxysilane, 4-amino-3-dimethylbutylmethyldimethoxysilane, 4-amino-3-dimethylbutyltri
  • a ketimine silane compound such as 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine also generates a primary amino group by moisture, so that the aminosilane compound (c1) is substantially free from the aminosilane compound (c1).
  • the use of 3-aminopropyltrimethoxysilane or N- (2-aminoethyl) -3-aminopropyltrimethoxysilane is easy to obtain and has a high curing acceleration effect.
  • a cured product in which an aminosilane compound is blended is generally easily yellowed by heat or light.
  • Use of a compound is preferable because yellowing is reduced.
  • silane compound (c2) Specific examples of the silane compound (c2) include methyltrimethoxysilane, dimethyldimethoxysilane, hexyltrimethoxysilane, decyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, tetraethoxysilane, Examples include dimethoxydiethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-ureidopropyltrimethoxysilane. Of these, methyltrimethoxysilane and dimethyldimethoxysilane are preferably used from the viewpoint of easy condensation reaction with the aminosilane compound (c1).
  • the aminosilane compound (c1) alone or the condensation reaction product of the aminosilane compound (c1) and the silane compound (c2) may be synthesized by a conventionally known method. Specifically, a method of reacting the aminosilane compound (c1) with water or a method of reacting the aminosilane compound (c1) and the silane compound (c2) with water can be mentioned.
  • the aminosilane compound (c1) alone or the condensation reaction product of the aminosilane compound (c1) and the silane compound (c2) is commercially available, and these can be used in the present invention.
  • aminosilane silyl groups such as MS3301 (trade name, manufactured by Chisso Corporation), MS3302 (trade name, manufactured by Chisso Corporation), X-40-2651 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), etc. Examples thereof include compounds partially condensed with other alkoxysilane compounds.
  • the aminosilane compound (C) may be appropriately selected in order to obtain desired cured film properties and / or curing speed, and may be used alone or in combination of two or more.
  • the curable resin (B) is contained in an amount of 15 to 900 parts by weight, preferably 18 to 800 parts by weight, more preferably 100 parts by weight of the curable resin (A). It is 20 to 700 parts by mass, particularly preferably 30 to 500 parts by mass, and most preferably 50 to 300 parts by mass. If the amount of the curable resin (B) is less than 15 parts by mass, the effect of accelerating the curing by the curable resin (B) may not be sufficiently exhibited (that is, the curing rate is not sufficient), and 900 parts by mass is reduced.
  • the aminosilane compound (C) is further contained in an amount of 0.1 to 20 parts by weight, preferably 100% by weight of the total of the curable resin (A) and the curable resin (B).
  • the compound (C) is 0.5 to 15 parts by mass, more preferably 1 to 10 parts by mass. If the amount of the aminosilane compound (C) is less than 0.1 parts by mass, curing-accelerated curing may not be sufficient (prone to cause problems in terms of curing speed), and if it exceeds 20 parts by mass, it is relatively curable. Since the ratio of the resin (A) and the curable resin (B) is reduced, it is difficult to adjust the film properties of the cured product, or a large amount of moisture is required for curing, resulting in poor internal curability. Prone to occur.
  • the aminosilane compound (C) mainly functions as a curing catalyst.
  • the aminosilane compound (C) acts as a very weak curing catalyst for the curable resin (A), but the curable resin (A) cannot be completely cured by itself.
  • both the curable resin (A) and the curable resin (B) are completely cured by the catalytic effect of the aminosilane compound (C).
  • a sufficient curing rate and cured film physical properties can be obtained without using an organometallic catalyst, particularly an organotin catalyst, which has conventionally been regarded as an essential component.
  • the organotin-based catalyst is substantially not used, or even if it is used, it can be formulated with a very small amount of less than 1000 ppm.
  • any conventionally known compound or substance can be blended as other components.
  • various resins other than the curable resin used in the present invention non-tin based metal catalyst other than aminosilane compound (C), curing catalyst such as amine catalyst, acidic catalyst, basic catalyst, ⁇ -aminopropyltrimethoxy Silane coupling agents such as silane, fillers such as hydrophilic or hydrophobic silica powders, tackifiers such as phenol resins, thixotropic agents such as anhydrous silica, dehydrating agents such as calcium oxide, diluents, plasticizers , Flame retardants, oligomers, anti-aging agents, ultraviolet absorbers, pigments, titanate coupling agents, aluminum coupling agents, drying oils, and the like can be blended.
  • the curable resin composition according to the present invention is cured by condensation polymerization of hydrolyzable silicon groups in the presence of moisture. Therefore, when used as a one-component composition, it is handled in an airtightly sealed state so as not to come into contact with air (water in the air) during storage or transportation. And if it opens and uses it in arbitrary places at the time of use, it will contact with the water
  • the effects of the present invention are manifested when the above-described curable resin and the above-described aminosilane compound (C) are mixed.
  • the curable resin composition according to the present invention can be used for all applications to which a conventional curable resin has been applied.
  • it can be used as an adhesive, sealant, pressure-sensitive adhesive, paint, coating material, sealing material, casting material, coating material, and the like.
  • the curable resin composition according to the present invention as a main component, it is possible to provide a composition having a low environmental load, high safety, and a high curing rate, so that the working time can be shortened. It can be suitably used for applications such as sealants or adhesive compositions as required.
  • the “main body” means that in the crosslinked network structure when the composition is cured, the crosslinked network structure formed by condensation of hydrolyzable silicon groups of the curable resin composition is a main component.
  • silane compound SE-1 (105.6 g) was added and reacted at 80 ° C. for 1 hour with stirring and mixing in a nitrogen atmosphere, whereby the main chain was an oxyalkylene polymer and contained in the molecule.
  • a crosslinkable reactive silicon group-containing oxyalkylene polymer SU-1 having a urethane bond, a substituted urea bond and a trimethoxysilyl group was obtained.
  • the formation of SU-1 was confirmed by the absence of an isocyanate group peak (2265 cm ⁇ 1 ) observed by IR analysis.
  • 200 g of the crosslinkable reactive silicon group-containing oxyalkylene polymer SU-1 was placed, and the temperature was raised to 80 ° C.
  • curable resin (A) a modified silicone resin “Excestar S2420” (manufactured by Asahi Glass Co., Ltd.) having a main chain of polyoxypropylene and having a methyldimethoxysilyl group as a crosslinkable group at the terminal is used as the curable resin (B).
  • “GENIOSIL STP-E30” having a main chain of polyoxypropylene and having a methyldimethoxysilyl group-type ⁇ -silyl structure at the end (manufactured by Wacker Chemie AG., Molecular weight of about 16000 converted from equivalent amount of methoxy group, viscosity of about 30000 mPa S / 25 ° C.) was quickly mixed for 1 minute using 3-aminopropyltrimethoxysilane as the aminosilane compound (C) at the blending ratio shown in Table 1 (the numbers represent parts by mass).
  • a composition was prepared and its skinning time was measured. For the skinning time, the curable resin composition is left in an atmosphere of 23 ⁇ 1 ° C. and a relative humidity of 50 ⁇ 5%, and the surface is lightly touched with a fingertip degreased with ethanol. However, it calculated
  • Examples 5 to 10 The skinning time was measured when 70 parts by mass of various curable resins (A) and 30 parts by mass of curable resin (B) were used in combination. As a catalyst, only 3 parts by mass of the aminosilane compound (C) was used. “GENIOSIL STP-E30” (manufactured by Wacker Chemie AG.) was used as the curable resin (B), and 3-aminopropyltrimethoxysilane was used as the aminosilane compound (C).
  • curable resins (A), curable resins (B) and aminosilane compounds (C) were rapidly mixed for 1 minute at the blending ratios shown in Table 2 (numbers represent parts by mass), and Examples 1 to 4 Similarly, the skinning time was measured.
  • curable resin (A) a modified silicone resin “Kaneka MS Polymer S203” (manufactured by Kaneka Corporation) having a polyoxypropylene main chain and a methyldimethoxysilyl group as a crosslinkable group at the end is used as a curable resin (B ) “GENIOSIL STP-E10” (manufactured by Wacker Chemie AG.) Having a main chain of polyoxypropylene and having a methyldimethoxysilyl group-type ⁇ -silyl structure at the end, molecular weight of about 10,000 converted from methoxy group equivalent, viscosity About 10,000 mPa ⁇ s / 25 ° C.) using N- (2-aminoethyl) -3-aminopropyltrimethoxysilane as the aminosilane compound (C), and in the blending ratio (parts by mass) shown in Table 4 and Table 5.
  • the mixture was rapidly mixed for 1 minute to prepare a curable resin composition, and the skinning time was measured.
  • the curable resin composition is left in an atmosphere of 23 ⁇ 1 ° C. and a relative humidity of 50 ⁇ 5%, and the surface is lightly touched with a fingertip degreased with ethanol.
  • required as time until it stops adhering to a fingertip (based on JISA1439).
  • N- (2-amino) which is an aminosilane compound (C) can be obtained by using the curable resin (A) and the curable resin (B) in combination without adding other curing catalyst. It can be seen that a sufficient curing rate can be obtained with only ethyl) -3-aminopropyltrimethoxysilane. On the other hand, when N- (2-aminoethyl) -3-aminopropyltrimethoxysilane is not used, the skinning time is 2 days or more, and it can be seen that the curing is very slow.
  • curable resin (A) a modified silicone resin “Kaneka MS Polymer S203” (manufactured by Kaneka Corporation) having a polyoxypropylene main chain and a methyldimethoxysilyl group as a crosslinkable group at the end is used as a curable resin (B ) “GENIOSIL STP-E10” (manufactured by Wacker Chemie AG.) Having a main chain of polyoxypropylene and having a methyldimethoxysilyl group-type ⁇ -silyl structure at the end, molecular weight of about 10,000 converted from methoxy group equivalent, viscosity About 10,000 mPa ⁇ s / 25 ° C.) using N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane as the aminosilane compound (C), in the blending ratio (parts by mass) shown in Table 6 and Table 7.
  • the mixture was rapidly mixed for 1 minute to prepare a curable resin composition, and the skinning time was measured.
  • the curable resin composition is left in an atmosphere of 23 ⁇ 1 ° C. and a relative humidity of 50 ⁇ 5%, and the surface is lightly touched with a fingertip degreased with ethanol.
  • required as time until it stops adhering to a fingertip (based on JISA1439).
  • N- (2-amino) which is an aminosilane compound (C) can be obtained by using the curable resin (A) and the curable resin (B) in combination without adding another curing catalyst. It can be seen that a sufficient curing rate can be obtained with only ethyl) -3-aminopropylmethyldimethoxysilane. On the other hand, when N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane is not used, it can be seen that the skinning time is 2 days or more and the curing is very slow.
  • curable resin (A) a modified silicone resin “Kaneka MS Polymer S203” (manufactured by Kaneka Corporation) having a polyoxypropylene main chain and a methyldimethoxysilyl group as a crosslinkable group at the end is used as a curable resin (B ) “GENIOSIL STP-E10” (manufactured by Wacker Chemie AG.) Having a main chain of polyoxypropylene and having a methyldimethoxysilyl group-type ⁇ -silyl structure at the end, molecular weight of about 10,000 converted from methoxy group equivalent, viscosity About 10000 mPa ⁇ s / 25 ° C.), using MS3301 (an oligomer compound having an amino group and a hydrolyzable silicon group, manufactured by Chisso Corporation) as an aminosilane compound (C), the blending ratios shown in Table 8 Prepare a curable resin
  • the curable resin composition is left in an atmosphere of 23 ⁇ 1 ° C. and a relative humidity of 50 ⁇ 5%, and the surface is lightly touched with a fingertip degreased with ethanol. However, it calculated
  • the curable resin composition according to the present invention can be used for all applications to which a conventional curable resin has been applied.
  • it can be used as an adhesive, sealant, adhesive, paint, coating material, sealing material, casting material, coating material, etc.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention porte sur une composition de résine durcissable présentant une charge réduite pour l'environnement, qui est sans danger et offre une vitesse de durcissement suffisante. La composition contient une résine durcissable (A) comportant un groupe silicié hydrolysable (1) dans chaque molécule, une résine durcissable (B) comportant un groupe silicié hydrolysable (2) dans chaque molécule, et au moins une sorte d'un composé aminosilane (C) qui est un composé (3), un produit de condensation de composé (3) par lui-même ou un produit de condensation du composé (3) et un autre composé silane, dans un rapport spécifique. -X-SiR1 a(OR2)3-a (1) -A-CH2-SiR3 b(OR4)3-b (2) R5R6N-R7-SiR8 c(OR9)3-c (3) (Dans les formules, X représente un groupe hydrocarboné comportant 2 atomes de carbone ou plus ; A représente un groupe fonctionnel de liaison dans lequel un hétéroatome comportant une paire d'électrons non partagée est lié à CH2 qui est lié au Si contenu dans le groupe silicié hydrolysable ; R1, R2, R3, R4, R8 et R9 représentent chacun un groupe alkyle comportant de 1 à 20 atomes de carbone ; R5 et R6 représentent chacun un groupe organique ou un atome d'hydrogène ; R7 représente un groupe organique dans lequel un hétéroatome n'est pas lié à C qui est lié à un atome de silicium hydrolysable ; et a, b, c représentent chacun 0, 1 ou 2).
PCT/JP2009/062994 2008-07-18 2009-07-17 Composition de résine durcissable WO2010008079A1 (fr)

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WO2020149269A1 (fr) * 2019-01-18 2020-07-23 日本化学塗料株式会社 Matériau d'arrêt d'eau durcissable de type gonflant à l'eau, palplanche d'acier d'arrêt d'eau, procédé de production de palplanche d'acier d'arrêt d'eau et procédé d'arrêt d'eau

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JP6000667B2 (ja) * 2012-06-07 2016-10-05 コニシ株式会社 硬化性樹脂組成物
CN105073894B (zh) * 2013-03-25 2018-06-08 积水富乐株式会社 固化性组合物
JP5901045B2 (ja) * 2013-11-26 2016-04-06 リンテック株式会社 粘着剤組成物および粘着シートの製造方法

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JP2005514504A (ja) * 2002-01-17 2005-05-19 コンゾルテイウム フユール エレクトロケミツシエ インヅストリー ゲゼルシヤフト ミツト ベシユレンクテル ハフツング アルコキシシランを末端基とするポリマーを含有している架橋性ポリマーブレンド
JP2005535779A (ja) * 2002-08-14 2005-11-24 コンゾルテイウム　フユール　エレクトロケミツシエ　インヅストリー　ゲゼルシヤフト　ミツト　ベシユレンクテル　ハフツング 制御可能な硬化速度を有するアルコキシシラン末端ポリマーをベースとするポリマー材料

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WO2020149269A1 (fr) * 2019-01-18 2020-07-23 日本化学塗料株式会社 Matériau d'arrêt d'eau durcissable de type gonflant à l'eau, palplanche d'acier d'arrêt d'eau, procédé de production de palplanche d'acier d'arrêt d'eau et procédé d'arrêt d'eau
JPWO2020149269A1 (ja) * 2019-01-18 2021-10-14 日本化学塗料株式会社 硬化性水膨張止水材、止水鋼矢板、止水鋼矢板製造方法および止水工法
EP3926097A4 (fr) * 2019-01-18 2022-10-12 Nippon Chemical Paint Co., Ltd. Matériau d'arrêt d'eau durcissable de type gonflant à l'eau, palplanche d'acier d'arrêt d'eau, procédé de production de palplanche d'acier d'arrêt d'eau et procédé d'arrêt d'eau
JP7264509B2 (ja) 2019-01-18 2023-04-25 日本化学塗料株式会社 硬化性水膨張止水材、止水鋼矢板、止水鋼矢板製造方法および止水工法

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JPWO2010008079A1 (ja) 2012-01-05
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JP4445584B2 (ja) 2010-04-07
CN102076777A (zh) 2011-05-25

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