WO2010008079A1 - Curable resin composition - Google Patents
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- 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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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
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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
- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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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Abstract
Description
また、トリブチルスズ誘導体に限らず、スズを含む重金属を中心とする触媒は毒性、環境への負荷が懸念されるため、使用に際してはその取り扱いや使用量に十分な注意が必要であるのは言うまでもない。
本発明が解決しようとする課題は、環境負荷の低減を達成し、安全性を確保しつつ必要十分な硬化速度を有する硬化性組成物を得ることにある。 Some organotin compounds have become problematic in recent years. In particular, among organic tin compounds, those containing highly toxic tributyltin derivatives are desired to be suppressed to 1000 ppm or less with respect to the composition.
In addition, 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.
分子内に式(1)で表される加水分解性珪素基を有する硬化性樹脂(A)と、
分子内に式(2)で表される加水分解性珪素基を有する硬化性樹脂(B)と、
式(3)で表される化合物、式(3)で表される化合物単独の縮合反応生成物、および式(3)で表される化合物と他のシラン化合物との縮合反応生成物から選ばれる少なくとも一種のアミノシラン化合物(C)と、
を含有する硬化性樹脂組成物であって、
硬化性樹脂(A)100質量部に対して硬化性樹脂(B)が15~900質量部含有されるとともに、硬化性樹脂(A)と硬化性樹脂(B)との総和100質量部に対して、アミノシラン化合物(C)が0.1~20質量部含有される硬化性樹脂組成物に関するものである。
-X-SiR1 a(OR2)3-a ・・・式(1)
(但し、Xは炭素数2以上の炭化水素基を、R1、R2は炭素数1~20個のアルキル基を、aは0、1又は2を、それぞれ示す。)
-A-CH2-SiR3 b(OR4)3-b ・・・式(2)
(但し、Aは加水分解性珪素基に含まれる珪素原子に結合するメチレン基に非共有電子対を有するヘテロ原子が結合している結合官能基を、R3、R4は炭素数1~20個のアルキル基を、bは0、1又は2を、それぞれ示す。)
R5R6N-R7-SiR8 c(OR9)3-c ・・・式(3)
(但し、R5、R6は有機基又は水素原子を、R7は加水分解性珪素原子に結合する炭素原子にヘテロ原子が結合していない有機基を、R8、R9は炭素数1~20個のアルキル基を、cは0、1又は2を、それぞれ示す。) That is, 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. In addition, 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 R 6 N—R 7 —SiR 8 c (OR 9 ) 3-c (3)
(However, 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, and R 8 and R 9 are each having 1 carbon atom. ˜20 alkyl groups, c represents 0, 1 or 2, respectively.)
また、第3の発明は、硬化性樹脂(A)の加水分解性珪素基がアルキルジアルコキシシリル基であることを特徴とする、第1又は第2の発明に係る硬化性樹脂組成物に関するものである。 Further, 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.
また、第5の発明は、硬化性樹脂(B)の主鎖が本質的にポリオキシアルキレンであることを特徴とする、第1~第4のいずれかの発明に係る硬化性樹脂組成物に関するものである。
また、第6の発明は、有機錫系触媒が0~1000ppm未満であることを特徴とする、第1~第5のいずれかの発明に係る硬化性樹脂組成物に関するものである。 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.
また、第8の発明は、第1~第6のいずれかの発明に係る硬化性組成物を硬化性成分の主体とする接着剤組成物に関するものである。 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.
本発明における硬化性樹脂(A)は、分子内に式(1)で表される加水分解性珪素基を有する硬化性樹脂である。
-X-SiR1 a(OR2)3-a ・・・式(1)
(但し、Xは炭素数2以上の炭化水素基を、R1、R2は炭素数1~20個のアルキル基を、aは0、1又は2を、それぞれ示す。) [About curable resin (A)]
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)
ここで、R1及びR2はそれぞれ炭素数1~20個のアルキル基である。アルコキシル基(OR2)としては、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基であるのが好ましく、さらに好ましくはメトキシ基又はエトキシ基である。珪素原子の残りの結合手に結合している炭化水素基(R1)としては、メチル基、エチル基、プロピル基、ブチル基であるのが好ましく、さらに好ましくはメチル基又はエチル基である。
また、硬化性樹脂(A)の加水分解性珪素基は、特にシーリング材に代表されるような比較的低モジュラス・高伸びの硬化物を希望する場合、アルキルジアルコキシシリル基(a=1)であることが硬化速度とモジュラスのバランスがとりやすい点から好ましい。
硬化性樹脂(A)の分子量は特に制限されないが、1,000~80,000が好ましく、1,500~60,000がより好ましく、2,000~40,000が特に好ましい。分子量が1,000を下回ると、架橋密度が高くなり過ぎることから脆い物性となる場合があり、分子量が80,000を上回ると、粘度が高くなり作業性が悪くなるため溶剤や可塑剤が多量に必要になるなど配合が制限される場合がある。 In the hydrolyzable silicon group, 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. In addition to the bond to the hydrocarbon group X, 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.
Here, 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.
In addition, the hydrolyzable silicon group of the curable resin (A) is preferably an alkyl dialkoxysilyl group (a = 1) when a cured product having a relatively low modulus and high elongation as typified by a sealing material is desired. It is preferable that it is easy to balance the curing rate and the modulus.
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.
硬化性樹脂(A)としては、特にシーリング材に代表されるような比較的低モジュラス・高伸びの硬化物を希望する場合、その分子内にウレタン結合又は尿素結合を含まないものであることが、モジュラスの調整がとりやすい等の点から好ましい。 Further, as the curable resin (A), a curable silicone resin containing a polar group such as a urethane bond or a urea bond in the molecule may be used. 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. 3343604, Japanese Patent Laid-Open No. 2005-54174, United States Patent 7208560, United States Patent 7230064, Japanese Patent Laid-Open No. 8-05528, Japanese Patent Laid-Open No. Can be easily synthesized by the method described in Japanese Patent No. 2-11879.
As 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.
本発明における硬化性樹脂(B)は、分子内に式(2)で表される加水分解性珪素基を有する硬化性樹脂である。
-A-CH2-SiR3 b(OR4)3-b ・・・式(2)
(但し、Aは加水分解性珪素基に含まれる珪素原子に結合するメチレン基に非共有電子対を有するヘテロ原子が結合している結合官能基を、R3、R4は炭素数1~20個のアルキル基を、bは0、1又は2を、それぞれ示す。)
[About curable resin (B)]
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.)
また、当該珪素原子についてはメチレン基との結合手以外に加水分解性基としてアルコキシ基(OR4)が1~3個結合すると共に、残りの結合手として炭化水素基(R3)が2~0個結合しているものである。
ここで、R3及びR4はそれぞれ炭素数1~20個のアルキル基である。アルコキシル基(OR4)としては、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基であるのが好ましく、さらに好ましくはメトキシ基又はエトキシ基である。珪素原子の残りの結合手に結合している炭化水素基(R3)としては、メチル基、エチル基、プロピル基、ブチル基であるのが好ましく、さらに好ましくはメチル基又はエチル基である。
また、硬化性樹脂(B)の加水分解性珪素基は、アルキルジアルコシキシリル基(b=1)又はトリアルコキシシリル基(b=0)であることが入手の容易さ、硬化物のモジュラス等の点から好ましい。
硬化性樹脂(B)の分子量は特に制限されないが、1,000~80,000が好ましく、1,500~60,000がより好ましく、2,000~40,000が特に好ましい。分子量が1,000を下回ると、架橋密度が高くなり過ぎることから脆い物性となる場合があり、分子量が80,000を上回ると、粘度が高くなり作業性が悪くなるため溶剤や可塑剤が多量に必要になるなど配合が制限される場合がある。 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. Further, the hydrolyzable silicon group is bonded to the main chain skeleton via this bonding functional group.
In addition to the bond with the methylene 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.
Here, 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 hydrolyzable silicon group of the curable resin (B) is easily an alkyldialkoxysilyl group (b = 1) or trialkoxysilyl group (b = 0), the modulus of the cured product, etc. From the point of view, it is preferable.
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. 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.
硬化性樹脂(A)と硬化性樹脂(B)の相溶性を向上させるために従来公知の技術を用いることができる。例えば一般的に相溶化剤として知られている化合物を添加することができる。また、硬化性樹脂(A)と硬化性樹脂(B)の主鎖骨格を相溶性が良好である組み合わせを選ぶことによって向上させることもできる。具体的には主鎖骨格の極性が比較的近いものを用いることで相溶性を向上することができる。例えば、双方ともに同じ主鎖骨格を選ぶと相溶性が非常に良好である。また同じではなくても、ポリオレフィン骨格同士、ポリエーテル骨格同士といった比較的構造が似通った骨格を選択することも好ましい。さらに、ポリオキシアルキレン骨格と特定構造のポリ(メタ)アクリレート骨格なども相溶性が良好であることが知られている。上記のように相溶性が良好である組み合わせの一例を例示したが、本発明はこれらに限定されるものではない。 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.
In order to improve the compatibility of the curable resin (A) and the curable resin (B), a conventionally known technique can be used. For example, a compound generally known as a compatibilizing agent can be added. Further, 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. For example, if the same main chain skeleton is selected for both, 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.
本発明における、アミノシラン化合物(C)は、分子内に1個以上のアミノ基と加水分解性珪素基を有する化合物であり、アミノ基と加水分解性珪素基との間に炭素原子が2つ以上結合しているアミノシラン化合物である。本発明におけるアミノシラン化合物(C)はα-シラン構造を有しないアミノシラン化合物である。α-シラン構造を有する低分子アミノシラン化合物は毒性が高いため適さない。 [Aminosilane compound (C)]
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 α-silane structure. A low molecular aminosilane compound having an α-silane structure is not suitable because of its high toxicity.
(但し、R5、R6は有機基又は水素原子を、R7は加水分解性珪素原子に結合する炭素原子にヘテロ原子が結合していない有機基を、R8、R9は炭素数1~20個のアルキル基を、cは0、1又は2を、それぞれ示す。) R 5 R 6 N—R 7 —SiR 8 c (OR 9 ) 3-c (3)
(However, 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, and R 8 and R 9 are each having 1 carbon atom. ˜20 alkyl groups, c represents 0, 1 or 2, respectively.)
(但し、式中、R10、R11、R12は、フェニル基、分子量500以下のアルキル基、メルカプトプロピル基、ウレイドプロピル基、フェノキシ基、及び、炭素数1~6のアルコキシ基に代表される分子量500以下の有機基から選ばれる一種以上の基をそれぞれ表し、R13は、フェニル基、及び、炭素数1~6のアルキル基から選ばれる一種以上の基をそれぞれ表す) Si (R 10 ) (R 11 ) (R 12 ) (OR 13 ) (4)
(In the formula, 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, and R 13 represents one or more groups selected from a phenyl group and an alkyl group having 1 to 6 carbon atoms.)
(但し、R5’、R6’は分子量500以下の有機基又は水素原子を、R7’は加水分解性珪素原子に結合する炭素原子にヘテロ原子が結合しておらず、さらに第2級アミノ基を含んでいてもよい分子量500以下の二価の有機基を、R8’、R9’は炭素数1~20個のアルキル基を、cは0、1又は2を、それぞれ示す。) R 5 ′ R 6 ′ NR 7 ′ -SiR 8 ′ c (OR 9 ′) 3-c Formula (3 ′)
(However, 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, A divalent organic group having a molecular weight of 500 or less that may contain an amino group, R 8 ′ and R 9 ′ each represent an alkyl group having 1 to 20 carbon atoms, and c represents 0, 1 or 2, respectively. )
上記アミノシラン化合物(c1)の具体例としては、3-アミノプロピルトリメトキシシラン、3-アミノプロピルメチルジメトキシシラン、3-アミノプロピルトリエトキシシラン、3-アミノプロピルメチルジエトキシシラン、N-(2-アミノエチル)-3-アミノプロピルトリメトキシシラン、N-(2-アミノエチル)-3-アミノプロピルメチルジメトキシシラン、N-(2-アミノエチル)-3-アミノプロピルトリエトキシシラン、N-(2-アミノエチル)-3-アミノプロピルメチルジエトキシシラン、4-アミノ-3-ジメチルブチルトリメトキシシラン、4-アミノ-3-ジメチルブチルメチルジメトキシシラン、4-アミノ-3-ジメチルブチルトリエトキシシラン、4-アミノ-3-ジメチルブチルメチルジエトキシシラン、ビス(3-トリメトキシプロピル)アミン、ビス(3-メチルジメトキシプロピル)アミン、N-フェニルアミノプロピルトリメトキシシラン、N-フェニルアミノプロピルメチルジメトキシシラン、N-エチルアミノイソブチルトリメトキシシラン、N-エチルアミノイソブチルメチルジメトキシシラン、N-ブチルアミノプロピルトリメトキシシラン、N-ブチルアミノプロピルメチルジメトキシシラン、ジエチレントリアミノプロピルトリメトキシシラン、N-(2-プロペニル)アミノプロピルトリメトキシシラン等のアミノシラン化合物が挙げられるが、これらに限定されるわけではない。また、3-トリエトキシシリル-N-(1,3-ジメチル-ブチリデン)プロピルアミン等のケチミンシラン化合物も、湿気により第1級アミノ基が生成するため、上記アミノシラン化合物(c1)のなかに実質的に含まれる。なかでも、3-アミノプロピルトリメトキシシラン、又は、N-(2-アミノエチル)-3-アミノプロピルトリメトキシシランを用いることが、入手が容易であるという点、及び、硬化促進効果高いという点から好ましい。また、アミノシラン化合物が配合された硬化物は一般的に熱や光によって黄色く変色しやすいことが知られている。このような黄変が好まれない用途に用いる時は、4-アミノ-3-ジメチルブチルトリメトキシシラン、4-アミノ-3-ジメチルブチルメチルジメトキシシラン、4-アミノ-3-ジメチルブチルトリエトキシシラン、4-アミノ-3-ジメチルブチルメチルジエトキシシラン、N-エチルアミノイソブチルトリメトキシシラン、N-エチルアミノイソブチルメチルジメトキシシラン等の窒素原子のβ位の炭素に結合する水素原子の数が少ないアミノシラン化合物を用いると黄変が低減されるため好ましい。 [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-dimethylbutyltriethoxysilane, 4-amino-3-dimethylbutylmethyldie Xysilane, bis (3-trimethoxypropyl) amine, bis (3-methyldimethoxypropyl) amine, N-phenylaminopropyltrimethoxysilane, N-phenylaminopropylmethyldimethoxysilane, N-ethylaminoisobutyltrimethoxysilane, N Aminosilane compounds such as ethylaminoisobutylmethyldimethoxysilane, N-butylaminopropyltrimethoxysilane, N-butylaminopropylmethyldimethoxysilane, diethylenetriaminopropyltrimethoxysilane, and N- (2-propenyl) aminopropyltrimethoxysilane; For example, but not limited to. In addition, 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). include. Among them, the use of 3-aminopropyltrimethoxysilane or N- (2-aminoethyl) -3-aminopropyltrimethoxysilane is easy to obtain and has a high curing acceleration effect. To preferred. Further, it is known that a cured product in which an aminosilane compound is blended is generally easily yellowed by heat or light. When used in applications where yellowing is not preferred, 4-amino-3-dimethylbutyltrimethoxysilane, 4-amino-3-dimethylbutylmethyldimethoxysilane, 4-amino-3-dimethylbutyltriethoxysilane 4-amino-3-dimethylbutylmethyldiethoxysilane, N-ethylaminoisobutyltrimethoxysilane, N-ethylaminoisobutylmethyldimethoxysilane, and other aminosilanes having a small number of hydrogen atoms bonded to the β-position carbon of the nitrogen atom Use of a compound is preferable because yellowing is reduced.
上記シラン化合物(c2)の具体例としては、メチルトリメトキシシラン、ジメチルジメトキシシラン、ヘキシルトリメトキシシラン、デシルトリメトキシシラン、フェニルトリメトキシシラン、メチルトリエトキシシラン、ジメチルジエトキシシラン、テトラエトキシシラン、ジメトキシジエトキシシラン、3-メルカプトプロピルトリメトキシシラン、3-ウレイドプロピルトリメトキシシラン等が例示される。なかでも、メチルトリメトキシシラン、ジメチルジメトキシシランを用いることが、アミノシラン化合物(c1)との縮合反応の容易性の観点から好ましい。 [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).
本発明においては、硬化性樹脂(A)100質量部に対して硬化性樹脂(B)が15~900質量部含有され、好ましくは硬化性樹脂(B)が18~800質量部、さらに好ましくは20~700質量部、特に好ましくは30~500質量部、最も好ましくは50~300質量部である。硬化性樹脂(B)の量が、15質量部を下回ると硬化性樹脂(B)による硬化促進の効果が十分発揮されない場合があり(即ち、硬化速度が充分にならず)、900質量部を上回ると、逆に硬化性樹脂(A)の配相対的な割合が少なくなり、接着強さや硬化後の物性などバランスが取りにくくなる(特に硬化皮膜物性が得られにくい)。
さらに、本発明においては、さらに硬化性樹脂(A)と硬化性樹脂(B)との総和100質量部に対して、アミノシラン化合物(C)が0.1~20質量部含有され、好ましくはアミノシラン化合物(C)が0.5~15質量部、さらに好ましくは1~10質量部である。アミノシラン化合物(C)の量が、0.1質量部を下回ると硬化促進硬化が十分でない場合があり(硬化速度という点で不具合を生じやすく)、20質量部を上回ると、相対的に硬化性樹脂(A)及び硬化性樹脂(B)の割合が減少するため、硬化物の皮膜物性の調整が困難になったり、硬化に多量の水分が必要になり内部硬化性が悪くなる等の不具合が生じやすい。 [About the amount]
In the present invention, 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. On the contrary, the relative proportion of the curable resin (A) decreases, making it difficult to achieve a balance such as adhesion strength and physical properties after curing (especially hardened film properties are difficult to obtain).
Further, in the present invention, 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.
通常、アミノシラン化合物(C)は硬化性樹脂(A)に対しては非常に弱い硬化触媒として作用するが、単独で硬化性樹脂(A)を完全に硬化させることはできない。しかし、硬化性樹脂(B)がここに介在することによって、硬化性樹脂(A)も硬化性樹脂(B)もともにアミノシラン化合物(C)の触媒効果により完全に硬化する。
これによって、従来は必須成分とされてきた、有機金属系触媒、特に有機錫系触媒を用いることなく、十分な硬化速度と硬化皮膜物性を得ることができる。このことにより、有機スズ系触媒を実質的に用いない、或いは用いたとしても1000ppm未満のごく少量の配合で済ませることができるのである。 In the present invention, the aminosilane compound (C) mainly functions as a curing catalyst.
Usually, 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).
As a result, 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. As a result, 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.
本発明に係る硬化性樹脂組成物中には、その他の成分として従来公知の任意の化合物乃至物質を配合することができる。たとえば、本発明で用いる硬化性樹脂以外の各種の樹脂、アミノシラン化合物(C)以外の非スズ系金属系触媒、アミン系触媒、酸性触媒、塩基性触媒等の硬化触媒、γ-アミノプロピルトリメトキシシラン等のシランカップリング剤、親水性又は疎水性シリカ系粉体等の充填剤、フェノール樹脂等の粘着付与剤、無水シリカ等の揺変剤、酸化カルシウム等の脱水剤、希釈剤、可塑剤、難燃剤、オリゴマー、老化防止剤、紫外線吸収剤、顔料、チタネートカップリング剤、アルミニウムカップリング剤、乾性油等を配合することができる。 [Other ingredients]
In the curable resin composition according to the present invention, any conventionally known compound or substance can be blended as other components. For example, 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, γ-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.
反応容器内で、N-(2-アミノエチル)-3-アミノプロピルトリメトキシシラン(222.4g、1.0mol)を窒素雰囲気下室温で撹拌しながら、アクリル酸メチル(172.2g、2.0mol)を1時間かけて滴下し、さらに80℃で10時間反応させることで、分子内にトリメトキシシリル基及び第二級アミノ基を有するシラン化合物SE-1を得た。
反応容器内で、「PML S 4012」(旭硝子ウレタン株式会社製、ポリオキシプロピレンポリオール、平均分子量10,000、950g)、「PR-3007」(旭電化工業株式会社製、プロピレンオキサイドとエチレンオキサイドの共重合型ポリオール、平均分子量3,000、50g)、イソホロンジイソシアネート(53.3g)及びジブチルスズジラウレート(50mg)を仕込み窒素雰囲気下にて撹拌混合しながら80℃で3時間反応させて、主鎖がオキシアルキレン重合体でありその分子内にイソシアネート基を有するウレタン樹脂U-1を得た。
さらに、上記シラン化合物SE-1(105.6g)を添加し、窒素雰囲気下にて撹拌混合しながら、80℃で1時間反応させることで、主鎖がオキシアルキレン重合体でありその分子内にウレタン結合、置換尿素結合、トリメトキシシリル基を有する架橋可能な反応性珪素基含有オキシアルキレン重合体SU-1を得た。SU-1の生成は、IR分析でイソシアネート基のピーク(2265cm-1)が観察されなかったことにより確認した。
反応容器に、上記架橋可能な反応性珪素基含有オキシアルキレン重合体SU-1を200g入れ、窒素雰囲気下、80℃まで昇温した。そこに、メタクリル酸メチル75g、メタクリル酸ラウリル50g、3-アクリロキシプロピルトリメトキシシラン14g、3-メルカプトプロピルトリメトキシシラン14g、及び2,2’-アゾビス(2,4-ジメチルバレロニトリル)1.53gを混合したモノマー混合液を90分かけて滴下し、重合反応を行った。さらに、80℃で120分重合反応を行った。その後、未反応の諸成分を減圧留去することで、架橋可能な反応性珪素基含有オキシアルキレン重合体SU-1と、架橋可能な反応性珪素基含有(メタ)アクリル酸エステル重合体とからなる加水分解性珪素基含有硬化性樹脂A-1を得た Synthesis Example 1 Synthesis of Curable Resin A-1 In a reaction vessel, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane (222.4 g, 1.0 mol) was stirred at room temperature in a nitrogen atmosphere. While adding methyl acrylate (172.2 g, 2.0 mol) dropwise over 1 hour and further reacting at 80 ° C. for 10 hours, a silane having a trimethoxysilyl group and a secondary amino group in the molecule Compound SE-1 was obtained.
In the reaction vessel, “PML S 4012” (Asahi Glass Urethane Co., Ltd., polyoxypropylene polyol, average molecular weight 10,000, 950 g), “PR-3007” (Asahi Denka Kogyo Co., Ltd., propylene oxide and ethylene oxide Copolymerized polyol, average molecular weight 3,000, 50 g), isophorone diisocyanate (53.3 g) and dibutyltin dilaurate (50 mg) were charged and reacted at 80 ° C. for 3 hours with stirring and mixing in a nitrogen atmosphere. A urethane resin U-1 which is an oxyalkylene polymer and has an isocyanate group in its molecule was obtained.
Further, the above 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.
In a reaction vessel, 200 g of the crosslinkable reactive silicon group-containing oxyalkylene polymer SU-1 was placed, and the temperature was raised to 80 ° C. in a nitrogen atmosphere. There, 75 g of methyl methacrylate, 50 g of lauryl methacrylate, 14 g of 3-acryloxypropyltrimethoxysilane, 14 g of 3-mercaptopropyltrimethoxysilane, and 2,2′-azobis (2,4-dimethylvaleronitrile) A monomer mixture mixed with 53 g was added dropwise over 90 minutes to carry out a polymerization reaction. Furthermore, a polymerization reaction was performed at 80 ° C. for 120 minutes. Thereafter, the unreacted components are distilled off under reduced pressure to form a crosslinkable reactive silicon group-containing oxyalkylene polymer SU-1 and a crosslinkable reactive silicon group-containing (meth) acrylic acid ester polymer. A hydrolyzable silicon group-containing curable resin A-1 was obtained.
[適切な配合量の検討]
硬化性樹脂(A)として、主鎖がポリオキシプロピレンであり末端に架橋性基としてメチルジメトキシシリル基を有する変成シリコーン樹脂「Excestar S2420」(旭硝子株式会社製)を、硬化性樹脂(B)として主鎖がポリオキシプロピレンであり、末端にメチルジメトキシシリル基型のα-シリル構造を有する「GENIOSIL STP-E30」(Wacker Chemie AG.製、メトキシ基等量から換算した分子量約16000、粘度約30000mPa・s/25℃)を、アミノシラン化合物(C)として3-アミノプロピルトリメトキシシランを用いて、表1に示す配合割合(数字は質量部を表す)で1分間速やかに混合して硬化性樹脂組成物を調製し、その皮張り時間を測定した。
皮張り時間は、硬化性樹脂組成物を、23±1℃及び相対湿度50±5%の雰囲気下に放置し、エタノールで脱脂した指先で表面を軽く触ってみて、表面の硬化性樹脂組成物が、指先に付着しなくなるまでの時間として求めた(JIS A 1439に準拠)。 (Examples 1 to 4 / Comparative Examples 1 and 2)
[Examination of appropriate amount]
As the 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 α-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 | required as time until it stops adhering to a fingertip (based on JISA1439).
[アミノシラン化合物(C)の効果]
変成シリコーン樹脂「Excestar S2420」(旭硝子株式会社製)(硬化性樹脂(A))、「GENIOSIL STP-E30」(Wacker Chemie AG.製)(硬化性樹脂(B))を、アミノシラン化合物(C)を用いずに、表1に示す配合割合で1分間速やかに混合して硬化性樹脂組成物を調製し、実施例1~4と同様に皮張り時間を測定した。 (Comparative Examples 3 and 4)
[Effect of aminosilane compound (C)]
Modified silicone resin “Excestar S2420” (manufactured by Asahi Glass Co., Ltd.) (curing resin (A)), “GENIOSIL STP-E30” (manufactured by Wacker Chemie AG.) (Curing resin (B)), aminosilane compound (C) The curable resin composition was prepared by rapidly mixing for 1 minute at the blending ratio shown in Table 1, and the skinning time was measured in the same manner as in Examples 1 to 4.
また、実施例1~4及び比較例3、4の結果から、アミノシラン化合物(C)を用いない場合硬化速度が充分ではないことがわかる。 From the results of Examples 1 to 4 and Comparative Examples 1 and 2, by using “Excestar S2420” that is a curable resin (A) and “GENIOSIL STP-E30” that is a curable resin (B), It can be seen that a sufficient curing rate can be obtained only with 3-aminopropyltrimethoxysilane, which is the aminosilane compound (C), even if no curing catalyst is added.
Further, the results of Examples 1 to 4 and Comparative Examples 3 and 4 indicate that the curing rate is not sufficient when the aminosilane compound (C) is not used.
各種の硬化性樹脂(A)70質量部と、硬化性樹脂(B)30質量部とを併用した場合の皮張り時間の測定を行った。触媒としてはアミノシラン化合物(C)のみを3質量部用いた。
硬化性樹脂(B)として「GENIOSIL STP-E30」(Wacker Chemie AG.製)を、アミノシラン化合物(C)として3-アミノプロピルトリメトキシシランを用いた。各種硬化性樹脂(A)、硬化性樹脂(B)及びアミノシラン化合物(C)を、表2に示す配合割合(数字は質量部を表す)で1分間速やかに混合し、実施例1~4と同様に皮張り時間を測定した。 (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). Various 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.
各種の硬化性樹脂(A)100質量部に、アミノシラン化合物(C)を3質量部配合した際の皮張り時間の測定を行った。
各種硬化性樹脂(A)及びアミノシラン化合物(C)を、表3に示す配合割合(数字は質量部)で1分間速やかに混合し、実施例1~4と同様に皮張り時間を測定した。 (Comparative Examples 5 to 9)
The skinning time was measured when 3 parts by mass of the aminosilane compound (C) was blended with 100 parts by mass of various curable resins (A).
Various curable resins (A) and aminosilane compounds (C) were rapidly mixed for 1 minute at the blending ratios (numbers are parts by mass) shown in Table 3, and the skinning time was measured in the same manner as in Examples 1 to 4.
・EXCESTAR G3440ST(*1)
主鎖がポリオキシプロピレン重合体であり架橋性基としてトリメトキシシリル基を有する変成シリコーン樹脂(旭硝子株式会社製)
・MA440(*2)
主鎖がポリオキシプロピレン重合体であり架橋性基としてメチルジメトキシシリル基を有する変成シリコーン樹脂と、分子内にアルコキシシリル基を有するポリ(メタ)アクリル重合体の混合物(株式会社カネカ製)
・SAT400(*3)
主鎖がポリオキシプロピレン重合体であり架橋性基としてメチルジメトキシシリル基を有する変成シリコーン樹脂(株式会社カネカ製)
・ARUFON US-6110(*4)
アルコキシシリル基含有ビニル重合体(東亞合成株式会社製)
・アクトフロー AS-301(*5)
アルコキシシリル基含有ビニル重合体(綜研化学株式会社製) The raw materials used are as follows.
・ EXCESTAR G3440ST (* 1)
Modified silicone resin whose main chain is a polyoxypropylene polymer and has a trimethoxysilyl group as a crosslinkable group (Asahi Glass Co., Ltd.)
・ MA440 (* 2)
A mixture of a modified silicone resin whose main chain is a polyoxypropylene polymer having a methyldimethoxysilyl group as a crosslinkable group and a poly (meth) acrylic polymer having an alkoxysilyl group in the molecule (manufactured by Kaneka Corporation)
・ SAT400 (* 3)
Modified silicone resin whose main chain is a polyoxypropylene polymer and has a methyldimethoxysilyl group as a crosslinkable group (manufactured by Kaneka Corporation)
・ ARUFON US-6110 (* 4)
Alkoxysilyl group-containing vinyl polymer (Toagosei Co., Ltd.)
・ ACT FLOW AS-301 (* 5)
Alkoxysilyl group-containing vinyl polymer (manufactured by Soken Chemical Co., Ltd.)
これに対し、比較例5~9の結果から、各種硬化性樹脂(A)に、アミノシラン化合物(C)を添加しただけでは皮張り時間が2日以上となり、硬化が非常に遅いことがわかる。 From the results of Examples 5 to 10, by using various curable resins (A) and curable resins (B) in combination, 3-aminopropyl, which is an aminosilane compound (C), can be used without adding any other curing catalyst. It can be seen that a sufficient curing rate can be obtained with only trimethoxysilane.
On the other hand, from the results of Comparative Examples 5 to 9, it can be seen that the addition of the aminosilane compound (C) to the various curable resins (A) results in a skinning time of 2 days or longer and the curing is very slow.
硬化性樹脂(A)として、主鎖がポリオキシプロピレンであり末端に架橋性基としてメチルジメトキシシリル基を有する変成シリコーン樹脂「カネカMSポリマーS203」(株式会社カネカ製)を、硬化性樹脂(B)として主鎖がポリオキシプロピレンであり、末端にメチルジメトキシシリル基型のα-シリル構造を有する「GENIOSIL STP-E10」(Wacker Chemie AG.製、メトキシ基等量から換算した分子量約10000、粘度約10000mPa・s/25℃)を、アミノシラン化合物(C)としてN-(2-アミノエチル)-3-アミノプロピルトリメトキシシランを用いて、表4及び表5に示す配合割合(質量部)で1分間速やかに混合して硬化性樹脂組成物を調製し、その皮張り時間を測定した。
皮張り時間は、硬化性樹脂組成物を、23±1℃及び相対湿度50±5%の雰囲気下に放置し、エタノールで脱脂した指先で表面を軽く触ってみて、表面の硬化性樹脂組成物が、指先に付着しなくなるまでの時間として求めた(JIS A 1439に準拠)。 (Examples 11 to 15, Comparative Examples 10 to 14)
As the 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 α-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.
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 | required as time until it stops adhering to a fingertip (based on JISA1439).
硬化性樹脂(A)として、主鎖がポリオキシプロピレンであり末端に架橋性基としてメチルジメトキシシリル基を有する変成シリコーン樹脂「カネカMSポリマーS203」(株式会社カネカ製)を、硬化性樹脂(B)として主鎖がポリオキシプロピレンであり、末端にメチルジメトキシシリル基型のα-シリル構造を有する「GENIOSIL STP-E10」(Wacker Chemie AG.製、メトキシ基等量から換算した分子量約10000、粘度約10000mPa・s/25℃)を、アミノシラン化合物(C)としてN-(2-アミノエチル)-3-アミノプロピルメチルジメトキシシランを用いて、表6及び表7に示す配合割合(質量部)で1分間速やかに混合して硬化性樹脂組成物を調製し、その皮張り時間を測定した。
皮張り時間は、硬化性樹脂組成物を、23±1℃及び相対湿度50±5%の雰囲気下に放置し、エタノールで脱脂した指先で表面を軽く触ってみて、表面の硬化性樹脂組成物が、指先に付着しなくなるまでの時間として求めた(JIS A 1439に準拠)。 (Examples 16 to 21, Comparative Examples 15 to 20)
As the 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 α-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.
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 | required as time until it stops adhering to a fingertip (based on JISA1439).
硬化性樹脂(A)として、主鎖がポリオキシプロピレンであり末端に架橋性基としてメチルジメトキシシリル基を有する変成シリコーン樹脂「カネカMSポリマーS203」(株式会社カネカ製)を、硬化性樹脂(B)として主鎖がポリオキシプロピレンであり、末端にメチルジメトキシシリル基型のα-シリル構造を有する「GENIOSIL STP-E10」(Wacker Chemie AG.製、メトキシ基等量から換算した分子量約10000、粘度約10000mPa・s/25℃)を、アミノシラン化合物(C)としてMS3301(チッソ株式会社製商品名、アミノ基及び加水分解性珪素基を有するを有するオリゴマー化合物)を用いて、表8に示す配合割合(質量部)で1分間速やかに混合して硬化性樹脂組成物を調製し、その皮張り時間を測定した。
皮張り時間は、硬化性樹脂組成物を、23±1℃及び相対湿度50±5%の雰囲気下に放置し、エタノールで脱脂した指先で表面を軽く触ってみて、表面の硬化性樹脂組成物が、指先に付着しなくなるまでの時間として求めた(JIS A 1439に準拠)。 (Examples 22 to 24, Comparative Examples 21 to 23)
As the 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 α-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 composition by quickly mixing (parts by weight) for 1 minute. And measured the skinning time.
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 | required as time until it stops adhering to a fingertip (based on JISA1439).
なお、本出願は、2008年7月18日付けで出願された日本特許出願(特願2008-187669)に基づいており、その全体が引用により援用される。また、ここに引用されるすべての参照は全体として取り込まれる。 Although the invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on a Japanese patent application (Japanese Patent Application No. 2008-187669) filed on July 18, 2008, which is incorporated by reference in its entirety. Also, all references cited herein are incorporated as a whole.
Claims (8)
- 分子内に式(1)で表される加水分解性珪素基を有する硬化性樹脂(A)と、
分子内に式(2)で表される加水分解性珪素基を有する硬化性樹脂(B)と、
式(3)で表される化合物、式(3)で表される化合物単独の縮合反応生成物、および式(3)で表される化合物と他のシラン化合物との縮合反応生成物から選ばれる少なくとも一種のアミノシラン化合物(C)と、
を含有する硬化性樹脂組成物であって、
硬化性樹脂(A)100質量部に対して硬化性樹脂(B)が15~900質量部含有されるとともに、硬化性樹脂(A)と硬化性樹脂(B)との総和100質量部に対して、アミノシラン化合物(C)が0.1~20質量部含有される硬化性樹脂組成物。
-X-SiR1 a(OR2)3-a ・・・式(1)
(但し、Xは炭素数2以上の炭化水素基を、R1、R2は炭素数1~20個のアルキル基を、aは0、1又は2を、それぞれ示す。)
-A-CH2-SiR3 b(OR4)3-b ・・・式(2)
(但し、Aは加水分解性珪素基に含まれる珪素原子に結合するメチレン基に非共有電子対を有するヘテロ原子が結合している結合官能基を、R3、R4は炭素数1~20個のアルキル基を、bは0、1又は2を、それぞれ示す。)
R5R6N-R7-SiR8 c(OR9)3-c ・・・式(3)
(但し、R5、R6は有機基又は水素原子を、R7は加水分解性珪素原子に結合する炭素原子にヘテロ原子が結合していない有機基を、R8、R9は炭素数1~20個のアルキル基を、cは0、1又は2を、それぞれ示す。)
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. 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 R 6 N—R 7 —SiR 8 c (OR 9 ) 3-c (3)
(However, 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, and R 8 and R 9 are each having 1 carbon atom. ˜20 alkyl groups, c represents 0, 1 or 2, respectively.)
- 硬化性樹脂(A)の主鎖が本質的にポリオキシアルキレン及び/又はポリ(メタ)アクリル酸エステルであることを特徴とする、請求項1に記載の硬化性樹脂組成物。 The curable resin composition according to claim 1, wherein the main chain of the curable resin (A) is essentially polyoxyalkylene and / or poly (meth) acrylate.
- 硬化性樹脂(A)の加水分解性珪素基がアルキルジアルコキシシリル基であることを特徴とする、請求項1又は2に記載の硬化性樹脂組成物。 The curable resin composition according to claim 1 or 2, wherein the hydrolyzable silicon group of the curable resin (A) is an alkyl dialkoxysilyl group.
- 硬化性樹脂(A)が、その分子内にウレタン結合又は尿素結合を含まないことを特徴とする、請求項1~3のいずれか一項に記載の硬化性樹脂組成物。 The curable resin composition according to any one of claims 1 to 3, wherein the curable resin (A) contains no urethane bond or urea bond in the molecule.
- 硬化性樹脂(B)の主鎖が本質的にポリオキシアルキレンであることを特徴とする、請求項1~4のいずれか一項に記載の硬化性樹脂組成物。 The curable resin composition according to any one of claims 1 to 4, wherein the main chain of the curable resin (B) is essentially polyoxyalkylene.
- 有機錫系触媒が0~1000ppm未満であることを特徴とする、請求項1~5のいずれか一項に記載の硬化性樹脂組成物。 The curable resin composition according to any one of claims 1 to 5, wherein the organotin catalyst is 0 to less than 1000 ppm.
- 請求項1~6のいずれか一項に記載の硬化性組成物を硬化性成分の主体とするシーラント組成物。 A sealant composition comprising the curable composition according to any one of claims 1 to 6 as a main component of a curable component.
- 請求項1~6のいずれか一項に記載の硬化性組成物を硬化性成分の主体とする接着剤組成物。
An adhesive composition mainly comprising the curable composition according to any one of claims 1 to 6 as a curable component.
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JP6000667B2 (en) * | 2012-06-07 | 2016-10-05 | コニシ株式会社 | Curable resin composition |
WO2014157247A1 (en) * | 2013-03-25 | 2014-10-02 | 積水フーラー株式会社 | Curable composition |
JP5901045B2 (en) * | 2013-11-26 | 2016-04-06 | リンテック株式会社 | Pressure-sensitive adhesive composition and method for producing pressure-sensitive adhesive sheet |
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JP2005501146A (en) * | 2001-08-28 | 2005-01-13 | 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 | Fast-curing one-component mixture containing alkoxysilane terminated polymer |
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JP2005535779A (en) * | 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 | Polymeric materials based on alkoxysilane-terminated polymers with controllable cure rate |
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JP2005501146A (en) * | 2001-08-28 | 2005-01-13 | 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 | Fast-curing one-component mixture containing alkoxysilane terminated polymer |
JP2005514504A (en) * | 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 | Crosslinkable polymer blends containing alkoxysilane-terminated polymers |
JP2005535779A (en) * | 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 | Polymeric materials based on alkoxysilane-terminated polymers with controllable cure rate |
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WO2020149269A1 (en) * | 2019-01-18 | 2020-07-23 | 日本化学塗料株式会社 | Curable water-swelling waterstop material, waterstop steel sheet pile, waterstop steel sheet pile production method, and water-stopping method |
JPWO2020149269A1 (en) * | 2019-01-18 | 2021-10-14 | 日本化学塗料株式会社 | Curable water expansion water stop material, water stop steel sheet pile, water stop steel sheet pile manufacturing method and water stop method |
EP3926097A4 (en) * | 2019-01-18 | 2022-10-12 | Nippon Chemical Paint Co., Ltd. | Curable water-swelling waterstop material, waterstop steel sheet pile, waterstop steel sheet pile production method, and water-stopping method |
JP7264509B2 (en) | 2019-01-18 | 2023-04-25 | 日本化学塗料株式会社 | Water-swelling water-stopping material hardening, water-stopping steel sheet pile, water-stopping steel sheet pile manufacturing method, and water-stopping construction method |
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