Curable composition and cured product

Abstract

The present application provides a curable composition, and a cured product of the curable composition, which provides a cured product with a good balance of weather resistance and softness. In a curable composition comprising a polyoxyalkylene polymer (A) having a reactive silicon group, and a (meth)acrylate polymer (B) having a reactive silicon group and a structural unit derived from a (meth)acrylate, a (meth)acrylate polymer (B) is used, which has a number average molecular weight Mn, a ratio Mw / Mn of a weight average molecular weight Mw to Mn, a glass transition temperature, and a breaking strength of a cured product measured by a specific method, each within a given range.

Description

Technical Field

[0001] The present invention relates to a curable composition comprising a polyoxyethylene polymer (A) having a reactive silicon group and a (meth)acrylate polymer (B) having a reactive silicon group, and a cured product thereof. Background Technology

[0002] Organic polymers having at least one reactive silicon group in their molecule can crosslink even at room temperature by forming silicon-oxygen bonds through hydrolysis of the silane group caused by moisture absorption, etc. Organic polymers having reactive silicon groups are known to form rubber-like cured products through such crosslinking reactions.

[0003] Among organic polymers with reactive silicon groups, polyoxyethylene polymers with reactive silicon groups have been widely used in building sealants and industrial sealants. In these applications, there is a requirement for long-term excellent weather resistance of cured compositions containing polyoxyethylene polymers with reactive silicon groups.

[0004] As a method for improving the weather resistance of cured products, the following method is known: combining a (meth)acrylate polymer having a reactive silicon group and a polyoxyethylene polymer having a reactive silicon group into a curable composition (see Patent Document 1).

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: International Publication No. 2014 / 024963 Summary of the Invention

[0008] The problem that the invention aims to solve

[0009] Building sealants and industrial sealants typically require flexibility. However, as described in Patent Document 1, it is difficult to achieve both weather resistance and flexibility in existing curable compositions comprising reactive silicone-based polyoxyethylene polymers and reactive silicone-based (meth)acrylate polymers.

[0010] The present invention addresses the above-mentioned problems and aims to provide a curable composition and a cured product of the curable composition, wherein the curable composition provides a cured product with a good balance of weather resistance and flexibility.

[0011] Problem Solving Methods

[0012] The inventors discovered that, in a curable composition comprising a polyoxyethylene polymer (A) having reactive silicon groups and a (meth)acrylate polymer (B) having reactive silicon groups and structural units derived from (meth)acrylates, the above-mentioned problems can be solved by using a (meth)acrylate polymer (B) whose number-average molecular weight Mn, weight-average molecular weight Mw to Mn ratio Mw / Mn, glass transition temperature, and fracture strength of the cured product measured by a specific method are all within a given range, thereby completing the present invention.

[0013] More specifically, the present invention provides the following (1) to (4).

[0014] (1) A curable composition comprising a polyoxyethylene polymer (A) having reactive silicone groups and a (meth)acrylate polymer (B) having reactive silicone groups, wherein,

[0015] The molecular chain of (meth)acrylate polymer (B) contains structural units derived from (meth)acrylate.

[0016] The number-average molecular weight (Mn) of (meth)acrylate polymers (B), determined by gel permeation chromatography, is 10,000–20,000, based on the polystyrene equivalent.

[0017] The ratio of the polystyrene-converted weight-average molecular weight Mw to Mn of the (meth)acrylate polymer (B) determined by gel permeation chromatography (Mw / Mn) is greater than 1.6.

[0018] The glass transition temperature of (meth)acrylate polymer (B) is below 0°C.

[0019] The tensile strength of the cured (meth)acrylate polymer (B) is 0.020~0.300 N / mm. 2 ,

[0020] Fracture strength is determined by a method including the following operations:

[0021] A mixture was obtained by mixing 100 parts by weight of (meth)acrylate polymer (B) with 2 parts by weight of diacetylacetonyl dibutyltin;

[0022] The mixture is cured to produce a sheet with a thickness of 0.25±0.05mm;

[0023] Cut short strips, 5 mm wide, from the specimen; and

[0024] The test piece was used, and a tensile test was performed at a tensile speed of 10 mm / min.

[0025] (2) The curable composition according to (1), wherein,

[0026] The tensile strength is 0.050~0.300 N / mm. 2 .

[0027] (3) The curable composition according to (1) or (2), wherein,

[0028] The tensile strength is 0.050~0.200 N / mm. 2 .

[0029] (4) A cured product, which is a cured product of any one of (1) to (3).

[0030] The effects of the invention

[0031] According to the present invention, a curable composition can be provided that provides a cured product with excellent weather resistance and further flexibility, and a cured product of the curable composition can also be provided. Detailed Implementation

[0032] The present invention will now be described in detail.

[0033] Curing Compositions

[0034] The curable composition comprises a polyoxyethylene polymer (A) having reactive silicon groups and a (meth)acrylate polymer (B) having reactive silicon groups.

[0035] The molecular chain of (meth)acrylate polymer (B) contains structural units derived from (meth)acrylates.

[0036] The number-average molecular weight (Mn) of the (meth)acrylate polymer (B) as determined by gel permeation chromatography is 10,000 to 20,000, which is equivalent to polystyrene. The weight-average molecular weight (Mw) of the (meth)acrylate polymer (B) as determined by gel permeation chromatography is greater than 1.6, which is equivalent to Mn.

[0037] The glass transition temperature of (meth)acrylate polymer (B) is below 0°C.

[0038] The tensile strength of the cured (meth)acrylate polymer (B) is 0.020~0.300 N / mm. 2 .

[0039] The above-mentioned fracture strength was determined by a method including the following operations:

[0040] A mixture was obtained by mixing 100 parts by weight of (meth)acrylate polymer (B) with 2 parts by weight of diacetylacetonyl dibutyltin;

[0041] The mixture is cured to produce a sheet with a thickness of 0.25±0.05mm;

[0042] Cut short strips, 5 mm wide, from the specimen; and

[0043] The test piece was used, and a tensile test was conducted at a tensile speed of 10 mm / min.

[0044] The above-mentioned curable composition can form a cured product with excellent weather resistance and further flexibility.

[0045] The following describes the necessary or optional components contained in the curable composition.

[0046] <Polyoxyolefin polymers (A)>

[0047] Polyoxyolefin polymer (A) (hereinafter sometimes simply referred to as "polymer (A)") has reactive silicon groups.

[0048] The reactive silicon group can be any silicon-containing group that has a silanol group or can be generated by hydrolysis to a silanol group. There are no special limitations, and it can be any known reactive silicon group.

[0049] As a reactive silicon group, the group described in the following formula (1) is preferred.

[0050] -SiR 1 a X 3-a (1)

[0051] In equation (1), R 1 A hydrocarbon group with 1 to 20 carbon atoms, either substituted or unsubstituted, or R 0 The 3SiO- group represents a triorganosilyloxy group. In the triorganosilyloxy group, the three R groups... 0 It consists of a hydrocarbon group with 1 to 20 carbon atoms. (3 Rs) 0 They can be the same or different.

[0052] X is a hydroxyl group or a hydrolyzable group.

[0053] a can be 0, 1, or 2.

[0054] Regarding R 1 And X, when each of them exists in multiples, multiple R 1 Multiple X's can be the same or different.

[0055] Polymer (A) has a polymer backbone and polymer chain ends bonded to the polymer backbone. In the specification and claims of this application, the polymer backbone is also referred to as the "main chain structure." The polymer backbone is a structure formed by the continuous bonding of multiple structural units derived from monomers. The monomers can be one type or multiple types.

[0056] The terminus of a polymer chain refers to the end portion of polymer (A). When the main chain structure is linear, the number of polymer chain ends in polymer (A) is 2; when the polymer backbone is branched, it is 3 or more. When polymer (A) is a mixture of polymers with linear and branched main chain structures, the average number of polymer chain ends is between 2 and 3.

[0057] Reactive silicon groups can be present in the polymer backbone and at the ends of the polymer chains. Furthermore, two or more reactive silicon groups can be present at the ends of the polymer chains. When the curable composition is used in adhesives, sealants, elastic coatings, adhesives, etc., the reactive silicon groups in polymer (A) are preferably present at the ends of the polymer chains.

[0058] (Reactive silicon-based)

[0059] Reactive silane groups are groups containing silanol groups or groups that can generate silanol groups through hydrolysis. In the case where reactive silane groups generate silanol groups, polymer (A) is crosslinked through a condensation reaction between silanol groups.

[0060] As the reactive silicon group described above, the group represented by formula (1) is preferred.

[0061] As R in equation (1) 1 Specific examples include: alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-hexyl, 2-ethylhexyl, and n-dodecyl; unsaturated hydrocarbon groups such as vinyl, isopropenyl, and allyl; alkoxymethyl groups such as methoxymethyl; halomethyl groups such as chloromethyl; cycloalkyl groups such as cyclohexyl; aryl groups such as phenyl, tolyl, and 1-naphthyl; and aralkyl groups such as benzyl. Among these groups, alkyl and aryl are preferred, methyl, ethyl, and phenyl are more preferred, methyl and ethyl are even more preferred, and methyl is particularly preferred. Formula (1) contains multiple R groups. 1 In the case of multiple R 1 It can be the same group or a combination of two or more different groups.

[0062] In formula (1), X is a hydroxyl group or a hydrolyzable group. There is no particular limitation on the hydrolyzable group; any known hydrolyzable group may be used. Specific examples of hydrolyzable groups include: hydrogen atoms, halogen atoms, alkoxy groups, acyloxy groups, ketoximate groups, amino groups, amide groups, acid amide groups, aminooxy groups, mercapto groups, and alkenoxy groups. Among these, alkoxy groups, acyloxy groups, ketoximate groups, and alkenoxy groups are preferred, and alkoxy groups such as methoxy and ethoxy groups are more preferred due to their hydrolytic stability and ease of handling. From the viewpoint of facilitating the adjustment of the curability of the curable composition, methoxy groups are preferred.

[0063] The reactive silicon group represented by formula (1) is not particularly limited. Specific examples of the reactive silicon group represented by formula (1) include: dimethoxymethylsilyl, diethoxymethylsilyl, trimethoxysilyl, triethoxysilyl, dimethoxyphenylsilyl, methoxymethyldimethoxysilyl, methoxymethyldiethoxysilyl, triisopropoxysilyl, and triacetoxysilyl. Among these, dimethoxymethylsilyl and trimethoxysilyl are preferred from the viewpoint of ease of synthesis of polymer (A). Trimethoxysilyl and methoxymethyldimethoxysilyl are preferred from the viewpoint of excellent curability. Dimethoxymethylsilyl is particularly preferred from the viewpoint of excellent stability.

[0064] (Regarding the main chain structure of polymer (A))

[0065] Polymer (A) is a polyoxyethylene polymer. Therefore, the main chain structure of the polymer contains polyoxyethylene polymers. Specifically, examples of polyoxyethylene polymers that can be used as the main chain structure of polymer (A) include: polyoxyethylene polymers, polyoxypropylene polymers, polyoxybutene polymers, polyoxytetramethylene polymers, polyoxyethylene-polyoxypropylene copolymers, polyoxypropylene-polyoxybutene copolymers, and other polyoxyethylene polymers.

[0066] From the viewpoint that it has excellent deep curing properties as a single-component composition, as well as excellent adhesion, polyoxypropylene is preferred as the main chain structure among polyoxyolefin polymers.

[0067] Polyoxyalkylene polymers are those with -R 3 -O- indicates the polymer of repeating units. R 3 It is a straight-chain or branched alkylene group having 1 to 14 carbon atoms. As R 3 More preferably, it is a straight-chain or branched alkylene group having 2 to 4 carbon atoms. As -R 3Specific examples of the repeating unit indicated by -O- include: -CH2O-, -CH2CH2O-, -CH2CH(CH3)O-, -CH2CH(C2H5)O-, -CH2C(CH3)(CH3)O-, and -CH2CH2CH2CH2O-, etc. The main chain structure of the polyoxypropylene polymer can be formed by only one repeating unit or by two or more repeating units. In particular, when the curable composition is used in sealants, adhesives, etc., a polyoxypropylene polymer having 50% or more, preferably 80% or more, of propylene oxide repeating units in the polymer main chain structure is preferred as a polyoxypropylene polymer. This is because such polyoxypropylene polymers are amorphous and have relatively low viscosity.

[0068] The main chain structure of polyoxyethylene polymers can be linear or branched.

[0069] The preferred polymers are those obtained by using a polymerization catalyst in the presence of an initiator and through a ring-opening polymerization reaction of a cyclic ether compound.

[0070] Examples of cyclic ether compounds include: ethylene oxide, propylene oxide, butane oxide, and tetramethylene oxide. These cyclic ether compounds include tetrahydrofuran, etc. Only one of these cyclic ether compounds may be used, or two or more may be used in combination. Among these cyclic ether compounds, propylene oxide is particularly preferred from the viewpoint of obtaining amorphous polyether polymers with relatively low viscosity.

[0071] Specific examples of initiators include: butanol, ethylene glycol, propylene glycol, propylene glycol monoalkyl ethers, butanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, triethylene glycol, glycerol, trimethylolpropane, pentaerythritol, and sorbitol; and polyoxypropylene glycol, polyoxypropylene triol, polyoxyethylene glycol, and polyoxyethylene triol, etc.

[0072] There are no particular limitations on the synthesis methods of polyoxyethylene polymers. Examples of synthesis methods for polyoxyethylene polymers include: polymerization methods based on base catalysts such as KOH; polymerization methods based on transition metal compound-porphyrin complex catalysts, such as those shown in Japanese Patent Application Publication No. 61-215623, which involve reacting an organoaluminum compound with a porphyrin to obtain a complex; and polymerization methods based on Japanese Patent Application Publication Nos. 46-27250, 59-15336, US Patent No. 3278457, and US Patent No. Polymerization methods using composite metal cyanide complex catalysts, as shown in US Patent Nos. 3278458, 3278459, 3427256, 3427334, and 3427335; polymerization methods using catalysts formed from polyphosphazene salts, as exemplified in Japanese Patent Application Publication No. 10-273512; and polymerization methods using catalysts formed from phosphazene compounds, as exemplified in Japanese Patent Application Publication No. 11-060722, etc. Polymerization methods based on composite metal cyanide complex catalysts are more preferred because they can produce polymers with low manufacturing costs and narrow molecular weight distributions.

[0073] Polyoxyolefin polymers whose main chain structure includes bonds other than ether bonds, such as urethane bonds and urea bonds, can be used without significantly impairing the desired effect. Specific examples of polymers having such a main chain structure include polyurethane prepolymers and polyurea prepolymers.

[0074] Polyurethane prepolymers can be obtained by known methods such as reacting polyol compounds with polyisocyanate compounds. Polyurea prepolymers can be obtained by known methods such as reacting polyamine compounds with polyisocyanate compounds.

[0075] Prepolymers with a combination of urethane and urea bonds, obtained by reacting polyols and polyamines with polyisocyanates, can also have a main chain structure.

[0076] Specific examples of polyol compounds include: polyether polyols, polyester polyols, polycarbonate polyols, and polyether polyester polyols.

[0077] Specific examples of polyisocyanate compounds include: diphenylmethane diisocyanate, toluene diisocyanate, xylene diisocyanate, methylene-bis(cyclohexylisocyanate), isophorone diisocyanate, and hexamethylene diisocyanate.

[0078] The ends of the polyurethane prepolymer may optionally be hydroxyl and isocyanate groups. The ends of the polyurea prepolymer may optionally be amino and isocyanate groups.

[0079] As a polymer (A), in a cured product of a curable composition containing a polymer having one or more bonds selected from urethane bonds, urea bonds and ester bonds in the main chain structure, the strength of the cured product may decrease due to the breaking of urethane bonds, urea bonds or ester bonds in the main chain structure caused by heat or other factors.

[0080] When polymers containing amide bonds in their main chain structure are used as organic polymers, the curability of the curable composition is sometimes improved. The amide bond, for example, is via -NR... 4 -C(=O)- indicates R. 4 The amide atom can be a hydrogen atom or an organic group with optional substituents. If the amount of amide bonds in the main chain structure is within a suitable range, it is less likely to cause a decrease in polymer viscosity, a decrease in the strength of the cured product due to the breakage of amide bonds caused by heat, or an increase in the viscosity of the cured composition due to storage. The cured composition has good workability.

[0081] When the main chain structure of polymer (A) contains amide bonds, the number of amide bonds, on average per molecule, is preferably 1 to 10, more preferably 1.5 to 5, and even more preferably 2 to 3. If the number of amide bonds, on average per molecule, is within such a range, the curable composition has good curability, the polymer (A) has low viscosity, and both the polymer (A) and the curable composition are easy to handle.

[0082] From the viewpoint of obtaining a curable composition with excellent storage stability and workability, the polymer (A) described above is most preferably a polyoxyethylene polymer whose main chain structure does not contain urethane bonds, urea bonds, ester bonds and amide bonds.

[0083] As polymer (A), it is preferably a polymer obtained by introducing reactive silicon groups into the polymer through any of the methods described in (a) to (d) below.

[0084] (a) After converting the terminal hydroxyl groups of the hydroxyl-terminated organic polymer to carbon-carbon unsaturated groups, via HSiR 1 a X 3-a The method shown is for the hydrosilylation of carbon-carbon unsaturated groups by hydrosilanes. R 1 X and a are the same as those in equation (1).

[0085] (b) Make OCN-W-SiR 1 a X 3-a The method shown illustrates the reaction of isocyanate alkylsilane compounds with the terminal hydroxyl groups of hydroxyl-terminated organic polymers. W represents a divalent organic group. R 1 X and a are the same as those in equation (1).

[0086] (c) After converting the terminal hydroxyl groups of the hydroxyl-terminated organic polymer to carbon-carbon unsaturated groups, the carbon-carbon unsaturated groups are reacted with HS-W-SiR. 1 a X 3-a The method for the ene-thiol reaction of the shown mercaptoalkylsilane compound. W is a divalent organic group. R 1 X and a are the same as those in equation (1).

[0087] (d) Reacting a hydroxyl-terminated organic polymer with a polyisocyanate compound to synthesize an NCO-terminated organic polymer, then reacting the terminal NCO group with HNR 5 -W-SiR 1 a X 3-a or HS-W-SiR 1 a X 3-a The method for reacting silane compounds is shown. W represents a divalent organic group. R5 represents a hydrogen atom or an alkyl group. 1 X and a are the same as those in equation (1).

[0088] In the methods described in (a) and (c) above, examples of terminal carbon-carbon unsaturated groups include vinyl, allyl, methylallyl, propadienyl, and propargyl.

[0089] In any of the methods described in (b) to (d) above, the polymer (A) obtained using a silane compound with W as methylene exhibits very high curability.

[0090] From the viewpoint of easily obtaining a polymer (A) with good storage stability, method (a) is preferred. From the viewpoint of obtaining a high conversion rate with a relatively short reaction time, methods (b), (c), and (d) are preferred.

[0091] Examples of methods for introducing reactive silicon groups via method (a) include: Japanese Patent Publication Nos. 45-36319, 46-12154, 50-156599, 54-6096, 55-13767, 55-13468, 57-164123, Japanese Patent Publication No. 3-2450, US Patent Nos. 3,632,557, 4,345,053, 4,366,307, and US Patent Nos. The methods proposed in Japanese Patent No. 4960844 and others, or the methods proposed in Japanese Patent Application Publications Nos. 61-197631, 61-215622, 61-215623 and 61-218632, which introduce reactive silicon groups into isotropic number-average polyoxypropylene polymers with a molecular weight of 6000 or more and a Mw / Mn ratio of 1.6 or less, and the method proposed in Japanese Patent Application Publication No. 3-72527, are examples of methods for introducing more than one reactive silicon group to the molecule's end.

[0092] The number-average molecular weight (Mn) of polymer (A) is not particularly limited. As the equivalent molecular weight of polystyrene in gel permeation chromatography (GPC), the number-average molecular weight of polymer (A) is preferably 5,000 to 40,000, more preferably 6,000 to 30,000.

[0093] The molecular weight of polymer (A) can also be expressed as follows: by titration analysis based on the principles of the hydroxyl value determination method in JISK 1557 and the iodine value determination method specified in JISK 0070, the concentration of terminal groups in the polymer precursor before the introduction of reactive silicon groups is directly determined, and the terminal group-converted molecular weight is calculated considering the polymer structure (degree of branching determined by the polymerization initiator used). The terminal group-converted molecular weight of polymer (A) can also be determined by: preparing a standard curve of the number-average molecular weight of the polymer precursor obtained by conventional GPC determination and the aforementioned terminal group-converted molecular weight, and converting the number-average molecular weight obtained by GPC determination of polymer (A) to the terminal group-converted molecular weight.

[0094] The molecular weight distribution (Mw / Mn) of polymer (A) is not particularly limited. Preferably, polymer (A) has a narrow molecular weight distribution. Specifically, the molecular weight distribution is preferably 1.6 or less, more preferably 1.4 or less, even more preferably 1.3 or less, and particularly preferably 1.2 or less. The molecular weight distribution of polymer (A) can be determined by measuring the number-average molecular weight and weight-average molecular weight using GPC.

[0095] To obtain a good rubbery cured product, the reactive silicon groups of polymer (A) are preferably present at the ends of the polymer chains. The number of reactive silicon groups is preferably 0.5 or more and 3.0 or less per polymer chain end, more preferably 0.6 or more and 2.5 or less, even more preferably 0.7 or more and 2.2 or less, and particularly preferably 0.8 or more and 2.0 or less. If the number of reactive silicon groups is 0.5 or more, the polymer (A) and the curable composition have good curability, and the cured product of the curable composition has good rubber elasticity.

[0096] The number of reactive silicon groups in one molecule is preferably 1 to 7 on average, more preferably 1 to 4, and particularly preferably 1 to 3.

[0097] In addition, as described in WO2013 / 180203, organic polymers having two or more reactive silicon groups at the ends of their polymer chains can also be used as polymer (A). Such polymer (A) exhibits high curability, and the cured product is expected to have high strength and high resilience.

[0098] Specific examples of commercially available polymers (A) include various polyoxypropylene products containing reactive silicone groups, such as KANEKA MS Polymer (registered trademark) and KANEKA Silyl (registered trademark). These commercially available polymers (A) are all products of KANEKA Corporation. Additionally, products such as AGC Corporation's ExceStar (registered trademark), WACKER Corporation's GENIOSIL (registered trademark), and RISUNPOLYMER Corporation's STP can also be used.

[0099] <(Meth)acrylate polymers (B)>

[0100] (Meth)acrylate polymers (B) (hereinafter sometimes simply referred to as "polymer (B)") have reactive silicon groups.

[0101] The reactive silicon group is not particularly limited as long as it can form silicon-oxygen bonds. The reactive silicon group shown in formula (1) above is preferred. The polymer (B) has a polymer backbone and polymer chain ends bonded to the polymer backbone. The polymer backbone is a structure formed by the continuous bonding of multiple structural units derived from monomers. The monomers can be one type or multiple types.

[0102] The polymer chain terminus refers to the end portion of polymer (B). When the main chain structure is linear, the number of polymer chain termini in polymer (B) is 2.

[0103] Reactive silicone groups can be present in the polymer backbone and at the ends of the polymer chains. When the curable composition is used in adhesives, sealants, elastic coatings, adhesives, etc., the reactive silicone groups in polymer (B) are preferably present at the ends of the polymer chains.

[0104] The reactive silicon groups in polymer (B) may be the same as or different from those in polymer (A).

[0105] (Regarding the main chain structure of polymer (B))

[0106] Polymer (B) contains structural units derived from (meth)acrylates.

[0107] (Meth)alkyl acrylates refer to alkyl acrylates and / or alkyl methacrylates.

[0108] Specific examples of alkyl acrylates include: methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-decyl acrylate, n-undecyl acrylate, lauryl acrylate, n-tridecyl acrylate, myristyl acrylate, cetyl acrylate, stearyl acrylate, and methyl acrylate. Esters, etc.

[0109] Specific examples of alkyl methacrylates include: methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-decyl methacrylate, n-undecyl methacrylate, lauryl methacrylate, n-tridecyl methacrylate, myristyl methacrylate, cetyl methacrylate, stearyl methacrylate, and methyl methacrylate. Esters, etc.

[0110] The ratio of the weight of the structural units derived from (meth)acrylate relative to the weight of polymer (B) is preferably 50% by weight or more, more preferably 70% by weight or more, further preferably 80% by weight or more, and particularly preferably 90% by weight or more.

[0111] From the viewpoint of compatibility with polymer (A) and stability of polymer (B), the alkyl methacrylate used to prepare polymer (B) is preferably an alkyl methacrylate having an alkyl group having 1 to 30 carbon atoms.

[0112] Alkyl (meth)acrylates having alkyl groups having 1 to 30 carbon atoms are represented by the following formula (B1):

[0113] CH2=CR b1 COOR b2 (B1)

[0114] (In formula (B1), R) b1 It can be a hydrogen atom or a methyl group. R b2 It is an alkyl group having 1 to 30 carbon atoms.

[0115] As R in equation (B1) b2 Examples include alkyl groups with 1 to 30 carbon atoms, such as methyl, ethyl, n-propyl, n-butyl, tert-butyl, 2-ethylhexyl, lauryl, n-tetrazyl, cetyl, and stearyl.

[0116] As R b2 The alkyl group preferably has 1 to 20 carbon atoms.

[0117] The monomers used to manufacture polymer (B) may contain monomers other than alkyl (meth)acrylates.

[0118] Other monomers include: acrylic acid and methacrylic acid; (meth)acrylamides such as acrylamide, methacrylamide, N-hydroxymethylacrylamide and N-hydroxymethylmethacrylamide; epoxy-containing (meth)acrylates such as glycidyl acrylate and glycidyl methacrylate; amino-containing unsaturated compounds such as 2-(N,N-diethylamino)ethyl methacrylate and 2-aminoethyl vinyl ether; epoxy alkyl (meth)acrylates such as glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate and 6,7-epoxyheptyl (meth)acrylate; acrylonitrile and methacrylates; styrene and α-methylstyrene; alkyl vinyl ethers; vinyl chloride; and fatty acid vinyl esters such as vinyl acetate and vinyl propionate.

[0119] As the equivalent molecular weight of polystyrene in GPC, the number average molecular weight of polymer (B) is preferably 10,000 to 20,000, more preferably 12,000 to 18,000. As the equivalent molecular weight of polystyrene in GPC, the weight average molecular weight (Mw) of polymer (B) is preferably 16,000 to 80,000, more preferably 20,000 to 60,000.

[0120] The molecular weight distribution (Mw / Mn), which is the ratio of the weight-average molecular weight Mw to Mn of polymer (B), is not particularly limited. The molecular weight distribution of polymer (B) is preferably narrow. Specifically, the molecular weight distribution is preferably 1.6 or more, more preferably 2.0 or more, and even more preferably 2.4 or more. The upper limit of the molecular weight distribution (Mw / Mn) can be, for example, 4.0 or less, or 3.5 or less. The molecular weight distribution of polymer (B) can be determined by measuring the number-average molecular weight and weight-average molecular weight using GPC.

[0121] Polymer (B) can be manufactured by conventional vinyl polymerization. Examples of vinyl polymerization methods include, for example, solution polymerization based on free radical reactions and bulk polymerization. Vinyl polymerization is not limited to these methods.

[0122] Typically, the above polymerization reaction is carried out at 50–150 °C in the presence of monomers, free radical initiators, chain transfer agents, and solvents.

[0123] The conditions for polymerization reactions are not limited to those described above.

[0124] Specific examples of free radical initiators include: azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), and benzoyl peroxide.

[0125] Specific examples of chain transfer agents include thiols such as n-dodecyl mercaptan, tert-dodecyl mercaptan, and lauryl mercaptan, as well as halogenated compounds.

[0126] As a solvent, solvents that are inactive in the polymerization reaction, such as ethers, hydrocarbons, and esters, are preferred.

[0127] Various methods are known for introducing reactive silicon groups into (meth)acrylate polymers.

[0128] As a specific example, the following can be cited:

[0129] I) A method of copolymerizing a compound having vinyl unsaturated double bonds and reactive silicon groups with an alkyl methacrylate as shown in formula (B1);

[0130] II) A method of reacting reactive silicon and a compound capable of reacting with the reactive functional group (e.g., a reactive silicon-based isocyanate compound) with the reactive functional group in a copolymer obtained by copolymerizing a compound having vinyl unsaturated double bonds and reactive functional groups with an alkyl methacrylate as shown in formula (B1).

[0131] III) A method for polymerizing the alkyl methacrylate shown in formula (B1) in the presence of a reactive silyl thiol as a chain transfer agent;

[0132] IV) A method for polymerizing the alkyl methacrylate of formula (B1) using a reactive silicon-based azobisnitrile compound or a reactive silicon-based disulfide compound as an initiator; and

[0133] V) A method of introducing reactive silicon groups into the ends of the molecular chains of a polymer obtained by polymerizing an alkyl methacrylate of formula (B1) using living radical polymerization.

[0134] You can also combine at least two of the methods I), II), and III).

[0135] The method of introducing reactive silicon groups into (meth)acrylate polymers is not limited to the above methods, but is preferably a combination of I), II), III), I) and III), II) and III), and more preferably a combination of I), III), I) and III).

[0136] The compound having ethylene unsaturated double bonds and reactive silicon groups used in the method described in I) above is preferably a compound represented by the following formula (B2):

[0137] CH2=CR b5 COOR b6 -SiR 1 a X 3-a (B2)

[0138] (In formula (B2), R) 1 X and a are related to R in equation (1) 1 X and a are the same. R b5 It can be a hydrogen atom or a methyl group. R b6 It is an alkylene group having 1 to 6 carbon atoms.

[0139] In equation (B2), R is used as b6 The alkylene group is a alkylene group with 1 to 6 carbon atoms, such as methylene, ethane-1,2-diyl (vinyl) and propane-1,3-diyl (trimethylene), preferably a alkylene group with 1 to 4 carbon atoms.

[0140] Specific examples of compounds having vinyl unsaturated double bonds and reactive silicon groups include: γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, and γ-methacryloxypropyltriethoxysilane, etc.; γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, and γ-methacryloxypropyltriethoxysilane, etc.; vinylalkoxysilane, vinylmethyldimethoxysilane, and vinyltriethoxysilane, etc.

[0141] Examples of reactive functional groups in compounds having vinyl unsaturated double bonds and reactive functional groups used in method II) above include amino, hydroxyl, and carboxyl groups. Examples of groups capable of reacting with these reactive functional groups include isocyanate groups.

[0142] Furthermore, as other examples, such as those described in Japanese Patent Application Publication Nos. 54-36395, 01-272654, and 02-214759, allyl can be cited as a reactive functional group. Hydrogenated silicon (H-Si) can be cited as a group capable of reacting with allyl.

[0143] Examples of reactive silyl thiols used as chain transfer agents in the method described in III) above include γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, and γ-mercaptopropyltriethoxysilane.

[0144] Examples of reactive silicon-based azobisnitrile compounds and disulfide compounds used in the method described in the above IV) include azobisnitrile compounds and disulfide compounds containing alkoxysilyl groups, as disclosed in Japanese Patent Application Publication No. 60-23405 and Japanese Patent Application Publication No. 62-70405.

[0145] As an example of the method described in the above V), the method described in Japanese Patent Application Publication No. 09-272714, etc.

[0146] Other methods include those described in Japanese Patent Application Publication Nos. 59-168014 and 60-228516, which combine a reactive silicon-based thiol with a reactive silicon-based free radical polymerization initiator.

[0147] The tensile strength of the cured polymer (B) is 0.020~0.300 N / mm. 2 The preferred value is 0.050~0.300 N / mm. 2More preferably, it is 0.050~0.200 N / mm 2 The fracture strength of the cured polymer (B) is set to 0.020~0.300 N / mm. 2 The cured product of the mixture of polymer (B) and polymer (A) has high weather resistance and is also flexible.

[0148] It should be noted that if the breaking strength is too high, there is a tendency for things such as a decrease in elongation at break and a decrease in the softness of the cured product of the curing composition.

[0149] The fracture strength of the cured polymer (B) was determined by the following method.

[0150] Methods for determining the tensile strength of cured polymer (B) include:

[0151] A mixture was obtained by mixing 100 parts by weight of polymer (B) and 2 parts by weight of diacetylacetonyl dibutyltin.

[0152] The mixture is cured to produce a sheet with a thickness of 0.25±0.05mm;

[0153] Cut short strips, 5 mm wide, from the specimen; and

[0154] Tensile tests were conducted using test pieces at a tensile speed of 10 mm / min.

[0155] There are no particular limitations on the method for adjusting the fracture strength of the cured polymer (B) determined by the above method. For example, increasing the amount of reactive silicon-based structural units in polymer (B) tends to result in higher fracture strength. Additionally, increasing the Tg of polymer (B) also tends to result in higher fracture strength.

[0156] There is no particular limitation on the amount of polymer (B) used in the curable composition, provided that the desired effect is not compromised.

[0157] In the curable composition, the weight W of the polyoxyethylene polymer (A) A The weight W of (meth)acrylate polymer (B) B The ratio W A / W B Preferably, it is 95 / 5 to 5 / 95, more preferably 90 / 10 to 20 / 80, and even more preferably 80 / 20 to 30 / 70.

[0158] The glass transition temperature (Tg) of polymer (B) is below 0°C, more preferably -80 to -10°C, and even more preferably -60 to -20°C. It should be noted that Tg is determined using the following Fox equation.

[0159] Fox-style:

[0160] 1 / (Tg(K))=Σ(Mi / Tgi)

[0161] (Where, Mi is the weight fraction of monomer i constituting the polymer, and Tgi is the glass transition temperature (K) of the homopolymer of monomer i.)

[0162] <Other Additives>

[0163] Without compromising the desired effect, the curable composition may also contain additives other than polymers (A) and (B). Examples of such additives include: curing catalysts, fillers, tackifiers, plasticizers, solvents, diluents, thixotropic agents, antioxidants, light stabilizers, UV absorbers, property modifiers, tackifying resins, epoxy-containing compounds, photocurable substances, oxygen-curable substances, epoxy resins, other resins, surface modifiers, foaming agents, curing modifiers, flame retardants, silicates, free radical inhibitors, metal inactivators, phosphorus peroxide decomposers, lubricants, pigments, and fungicides.

[0164] (Catalyst solidification)

[0165] For the purpose of promoting the hydrolysis-condensation reaction between the reactive silicon groups of polymer (A) and polymer (B), and for extending or crosslinking the polymer chains, the curable composition preferably contains a curing catalyst.

[0166] Examples of curing catalysts include organotin compounds, metal salts of carboxylic acids, amine compounds, carboxylic acids, and alkoxy metals.

[0167] Specific examples of organotin compounds include: dibutyltin dilaurate, dibutyltin dioctanoate, bis(butylmaleic) dibutyltin, dibutyltin diacetate, dibutyltin oxide, diacetylacetonyl dibutyltin, diacetylacetonyl dioctyltin, dioctyltin dilaurate, dioctyltin distearate, dioctyltin diacetate, dioctyltin oxide, reactants of dibutyltin oxide with silicate compounds, reactants of dioctyltin oxide with silicate compounds, and reactants of dibutyltin oxide with phthalates, etc.

[0168] Specific examples of metal salts of carboxylic acids include tin carboxylic acid, bismuth carboxylic acid, titanium carboxylic acid, zirconium carboxylic acid, and iron carboxylic acid. Additionally, salts composed of the following carboxylic acids combined with various metals can also be used as metal salts of carboxylic acids.

[0169] Specific examples of amine compounds include: amines such as octylamine, 2-ethylhexylamine, laurylamine, and stearylamine; nitrogen-containing heterocyclic compounds such as pyridine, 1,8-diazabicyclo[5,4,0]undecene-7 (DBU), and 1,5-diazabicyclo[4,3,0]nonene-5 (DBN); guanidines such as guanidine, phenylguanidine, and diphenylguanidine; biguanides such as butylbiguanide, 1-o-tolylbiguanide, and 1-phenylbiguanide; aminosilane coupling agents; and ketimine compounds.

[0170] Specific examples of carboxylic acids include acetic acid, propionic acid, butyric acid, 2-ethylhexanoic acid, lauric acid, stearic acid, oleic acid, linoleic acid, neodecanoic acid, and 2-ethylhexanoic acid (versatic acid).

[0171] Specific examples of alkoxy metals include: titanium compounds such as tetrabutyl titanate, tetra(acetylacetone)titanium, and diisopropoxytitanium bis(ethyl acetoacetate); aluminum compounds such as tri(acetylacetone)aluminum and diisopropoxyaluminum ethyl acetoacetate; and zirconium compounds such as tetra(acetylacetone)zirconium.

[0172] Other silanol condensation catalysts can also include fluorinated anionic compounds, photoacid-producing agents, and photoalkali-producing agents.

[0173] Solidified catalysts can be used in combination of two or more different catalysts.

[0174] The amount of curing catalyst used is preferably 0.001 to 20 parts by weight, more preferably 0.01 to 15 parts by weight, and particularly preferably 0.01 to 10 parts by weight, relative to a total of 100 parts by weight of the polyoxyethylene polymer (A) and the (meth)acrylate polymer (B).

[0175] (filler)

[0176] Various fillers can be incorporated into the curing composition. Examples of fillers include: reinforcing fillers such as fumed silica, precipitated silica, crystalline silica, fused silica, dolomite, anhydrous silica, hydrated silica, and carbon black; fillers such as heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium dioxide, bentonite, organobentonite, iron oxide, aluminum powder, flint powder, zinc oxide, active zinc oxide, and resin powder; and fibrous fillers such as asbestos, glass fiber, and long fibers.

[0177] Examples of resin powders include PVC powder and PMMA powder.

[0178] When using a filler, the amount of filler used is preferably 1 to 300 parts by weight, more preferably 10 to 200 parts by weight, relative to 100 parts by weight of the total weight of the polyoxyethylene polymer (A) and the (meth)acrylate polymer (B).

[0179] When it is desirable to use these fillers to obtain a cured product with high strength, it is preferable to use fillers mainly selected from fumed silica, precipitated silica, crystalline silica, fused silica, dolomite, anhydrous silica, hydrated silica, carbon black, surface-treated fine calcium carbonate, calcined clay, clay and active zinc oxide.

[0180] From the viewpoint of the strength of the cured product, the preferred amount of these fillers is 1 to 200 parts by weight, relative to 100 parts by weight of the total weight of the polyoxyethylene polymer (A) and the (meth)acrylate polymer (B). Furthermore, when a cured product with low strength and high elongation at break is desired, fillers mainly selected from titanium dioxide, calcium carbonate, magnesium carbonate, talc, iron oxide, zinc oxide, and silica microspheres are preferred. From the viewpoint of the elongation at break of the cured product, the preferred amount of these fillers is 5 to 200 parts by weight, relative to 100 parts by weight of the total weight of the polyoxyethylene polymer (A) and the (meth)acrylate polymer (B).

[0181] For the purpose of making the cured product lighter (lower specific gravity), the curable composition may contain spherical hollow bodies such as hollow spheres.

[0182] Hollow spheres are spherical fillers with a hollow interior. Examples of materials for hollow spheres include inorganic materials such as glass, white sand, and silica; and organic materials such as phenolic resin, urea-formaldehyde resin, polystyrene, saline, and acrylonitrile. The materials for hollow spheres are not limited to these. Hollow spheres can be composite materials formed from inorganic and organic materials. Furthermore, multiple layers of materials can be stacked. Additionally, hollow spheres can be made using one type of material alone or in combination of two or more. The surface of hollow spheres can be surface-processed, coated, or treated with various surface treatment agents. For example, hollow spheres coated with organic materials such as calcium carbonate, talc, or titanium dioxide, or inorganic hollow spheres surface-treated with silane coupling agents can be used.

[0183] The amount of spherical hollow bodies (hollow spheres) used is preferably 0.01 to 30 parts by weight relative to 100 parts by weight of the total weight of the polyoxyethylene polymer (A) and the (meth)acrylate polymer (B). The lower limit is more preferably 0.1 parts by weight, and the upper limit is more preferably 20 parts by weight. Using an amount of spherical hollow bodies within the above range results in a curable composition with good properties, easily forming a cured product with excellent elongation and tensile strength.

[0184] (Thickening agent)

[0185] The curable composition may contain a tackifier. Examples of tackifiers include silane coupling agents.

[0186] Silane coupling agents are compounds containing hydrolyzable silicon groups and other functional groups within their molecules. By using silane coupling agents, significant improvements in adhesion are observed when applying curable compositions to various substrates, including inorganic substrates such as glass, aluminum, stainless steel, zinc, copper, and mortar, and organic substrates such as vinyl chloride, acrylic acid, polyester, polyethylene, polypropylene, and polycarbonate, under both non-priming and priming conditions. The improvement in adhesion to various substrates is particularly pronounced when using curable compositions under non-priming conditions.

[0187] The hydrolyzable groups in the hydrolyzable silicon group of the silane coupling agent are not particularly limited. Examples of hydrolyzable groups include hydrogen atoms, halogen atoms, alkoxy groups, aryloxy groups, alkenoxy groups, acyloxy groups, ketoximate groups, amino groups, amide groups, acid amide groups, aminooxy groups, and mercapto groups. Among these, halogen atoms, alkoxy groups, alkenoxy groups, and aryloxy groups are preferred from the viewpoint of high reactivity. Chlorine atoms and alkoxy groups are preferred from the viewpoint of easy introduction into the silane coupling agent. From the viewpoint of hydrolytic stability and ease of handling, alkoxy groups such as methoxy and ethoxy are more preferred, and methoxy and ethoxy groups are particularly preferred. In addition, the compounds that are released by reaction from ethoxy and isopropoxy are ethanol and acetone, respectively, which are preferred from the viewpoint of safety. To ensure good adhesion, the number of hydrolyzable groups bonded to the silicon atoms in the silane coupling agent is sometimes preferably three. In addition, to ensure the storage stability of the cured composition, two groups are sometimes preferred.

[0188] Specific examples of aminosilane coupling agents include: 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltriisopropoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propylmethyldimethoxysilane, 3-(2-aminoethylamino)propyltriethoxysilane, 3-(2-aminoethylamino)propylmethyldiethoxysilane, 3-(2-aminoethylamino)propyltriisopropoxysilane, 3-(2-(2-aminoethylamino)ethylamino)propyltrimethoxysilane, 3-(6-aminohexylamino)propyltrimethoxysilane, 3-ethylamino-2-methyl Aminosilanes including propyltrimethoxysilane, 3-ureapropylpropyltrimethoxysilane, 3-ureapropylpropyltriethoxysilane, 3-phenylaminopropyltrimethoxysilane, 3-benzylaminopropyltrimethoxysilane, 3-(vinylbenzylamino)propyltriethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, N-phenylaminomethyltrimethoxysilane, N-butylaminopropyltrimethoxysilane, (2-aminoethylamino)methyltrimethoxysilane, N,N'-bis[3-(trimethoxysilyl)propyl]ethylenediamine, and bis(trimethoxysilylpropyl)amine; and ketimine silanes such as N-(1,3-dimethylbutylene)-3-(triethoxysilyl)-1-propylamine.

[0189] Among these, 3-aminopropyltrimethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, and 3-(2-aminoethylamino)propylmethyldimethoxysilane are preferred from the viewpoint of good adhesion of the cured product. One aminosilane coupling agent can be used alone, or two or more can be used in combination. Compared with other aminosilanes, 3-(2-aminoethylamino)propyltrimethoxysilane has been shown to be irritating. The irritation can be mitigated by using 3-aminopropyltrimethoxysilane in combination instead of reducing the amount of 3-(2-aminoethylamino)propyltrimethoxysilane. Furthermore, silane coupling agents that have undergone oligomerization by condensation of hydrolyzable silicon groups can also be used appropriately from the viewpoint of safety and stability. One or more condensed silane coupling agents can be used. Examples of oligomerized silane coupling agents include Dynasylan 1146 from Evonik. From the viewpoint of good storage stability of the cured composition, 3-aminopropyltrimethoxysilane and 3-(2-aminoethylamino)propylmethyldimethoxysilane are preferred.

[0190] Specific examples of silane coupling agents other than aminosilane coupling agents include: epoxypropyltrimethoxysilane, 3-glycidyl etheroxypropyltriethoxysilane, 3-glycidyl etheroxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, etc., epoxy-containing silane coupling agents; 3-isocyanate propyltrimethoxysilane, 3-isocyanate propyltriethoxysilane, 3-isocyanate propylmethyldiethoxysilane, 3-isocyanate propylmethyldimethoxysilane, (isocyanate methyl)trimethoxysilane, and (isocyanate methyl)dimethoxymethylsilane, etc., isocyanate-containing silane coupling agents; 3-mercaptopropyltrimethoxysilane This includes coupling agents containing mercaptosilanes such as 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, and mercaptomethyltriethoxysilane; carboxylsilane coupling agents such as 2-carboxyethyltriethoxysilane, 2-carboxyethylphenylbis(2-methoxyethoxy)silane, and N-2-(carboxymethylamino)ethyl-3-aminopropyltrimethoxysilane; silane coupling agents containing vinyl-type unsaturated groups such as vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, and 3-acryloyloxypropylmethyltriethoxysilane; halogenated silane coupling agents such as 3-chloropropyltrimethoxysilane; and isocyanurate silane coupling agents such as tris(trimethoxysilyl)isocyanurate. Additionally, condensates formed by partially condensing the above-mentioned silane coupling agents can also be used. Examples of such condensates include, for instance, Dynasylan 6490 and Dynasylan 6498 from Evonik. Furthermore, derivatives of these modified compounds, such as amino-modified silyl polymers, silylated amino polymers, unsaturated amino silane complexes, phenylamino long-chain alkyl silanes, aminosilylated silicones, and silylated polyesters, can also be used as silane coupling agents.

[0191] Among these, from the viewpoint of good adhesion of the cured product, 3-glycidyl etheroxypropyltrimethoxysilane, 3-glycidyl etheroxypropyltriethoxysilane and 3-glycidyl etheroxypropylmethyldimethoxysilane are preferred.

[0192] The above-mentioned silane coupling agents can be used alone or in combination of two or more.

[0193] The amount of silane coupling agent used is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, relative to a total of 100 parts by weight of the polyoxyethylene polymer (A) and the (meth)acrylate polymer (B).

[0194] (Plasticizer)

[0195] Curing compositions may contain plasticizers. By adding plasticizers, the viscosity and slump properties of the curing composition, as well as the tensile strength and elongation of the cured product, can be adjusted.

[0196] Specific examples of plasticizers include: phthalate compounds such as dibutyl phthalate, diisononyl phthalate (DINP), diheptyl phthalate, di(2-ethylhexyl) phthalate, diisodecyl phthalate (DIDP), and butyl benzyl phthalate; terephthalate compounds such as bis(2-ethylhexyl)-1,4-benzenediacarboxylate; and hydrogenated compounds of phthalates such as diisononyl 1,2-cyclohexanedicarboxylate; Aliphatic polycarboxylic acid esters such as dioctyl diacidate, dioctyl sebacate, dibutyl sebacate, diisodecyl succinate, and acetylated tributyl citrate; unsaturated fatty acid esters such as butyl oleate and acetylated methyl castor oil; alkyl sulfonates; phosphate esters such as tricresyl phosphate and tributyl phosphate; trimellitic acid esters; chlorinated paraffins; hydrocarbon oils such as alkyl biphenyls and partially hydrogenated terphenyls; processing oils; epoxidized soybean oil, benzyl epoxidized stearate, and other epoxy plasticizers.

[0197] Specific examples of terephthalate compounds include EASTMAN 168 (trade name, manufactured by EASTMANCHEMICAL). Specific examples of non-phthalate compounds include Hexamoll DINCH (trade name, manufactured by BASF). Specific examples of alkyl sulfonates include Mesamoll (trade name, manufactured by LANXESS).

[0198] High molecular weight plasticizers can also be used. Compared with low molecular weight plasticizers, high molecular weight plasticizers can maintain the initial physical properties of the cured product for a longer period of time. In addition, when alkyd coatings are applied to the cured product, drying properties (coating properties) are improved.

[0199] Specific examples of polymeric plasticizers include: vinyl polymers that are polymers of vinyl monomers; esters of polyalkyl glycols and polyols such as diethylene glycol dibenzoate, triethylene glycol dibenzoate, and pentaerythritol ester; polyester plasticizers obtained by reacting dibasic acids such as sebacic acid, adipic acid, azelaic acid, and phthalic acid with dibasic alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, and dipropylene glycol; polyether polyols (polyoxyethylene compounds) such as polyethylene glycol, polypropylene glycol, and polytetrahydrofuran ether diol with a number average molecular weight of 500 or higher, and further 1000 or higher; derivatives of these polyether polyols whose hydroxyl groups are converted to ester groups, ether groups, etc.; polystyrene derivatives such as polystyrene and poly-α-methylstyrene; and polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, and polychloroprene. Polymer plasticizers are not limited to these.

[0200] The polymeric plasticizer is preferably compatible with the polyoxyethylene polymer (A) and / or the (meth)acrylate polymer (B). From this viewpoint, polyether-based and vinyl-based polymers are preferred. If a polyether-based plasticizer is used, surface curing and deep curing properties are improved, and post-storage curing delay does not occur. Among polyether-based plasticizers, polypropylene glycol is more preferred. Furthermore, from the viewpoint of compatibility with the polyoxyethylene polymer (A) and / or the (meth)acrylate polymer (B), as well as the weather resistance and heat resistance of the cured product, vinyl-based polymers are preferred. Among vinyl-based polymers, acrylic polymers and / or methacrylate polymers are preferred, and acrylic polymers such as alkyl polyacrylates are more preferred. As for the synthesis method of vinyl-based polymers, from the viewpoint of obtaining polymers with narrow molecular weight distribution and low viscosity, living radical polymerization is preferred, and atom transfer radical polymerization is more preferred. In addition, the so-called SGO process, which involves the continuous bulk polymerization of alkyl acrylate monomers under high temperature / high pressure as described in Japanese Patent Application Publication No. 2001-207157, is also preferred as a method for manufacturing vinyl polymers.

[0201] The number average molecular weight of the polymeric plasticizer is preferably 500-15000, more preferably 800-10000, further preferably 1000-8000, particularly preferably 1000-5000, and most preferably 1000-3000.

[0202] If the number average molecular weight of the polymeric plasticizer is within the above range, it can suppress the outflow of the plasticizer from the cured product over time due to heat, rainfall, etc., while maintaining the initial physical properties of the cured product for a long time. The cured composition has appropriate viscosity and good operability.

[0203] The number-average molecular weight of vinyl polymers was determined by GPC. The number-average molecular weight of polyether polymers was determined by end-group analysis.

[0204] Polymer plasticizers may or may not have reactive silicone groups. When a polymer plasticizer has reactive silicone groups, it functions as a reactive plasticizer, preventing the plasticizer from migrating from the cured product. When a polymer plasticizer has reactive silicone groups, the number of reactive silicone groups per molecule is preferably 1 or less on average, more preferably 0.8 or less. When using plasticizers with reactive silicone groups, particularly polyether polymers with reactive silicone groups, their number average molecular weight needs to be lower than that of polyoxyethylene polymers (A) and / or (meth)acrylate polymers (B).

[0205] Among the plasticizers described above, at least one is preferably selected from phthalates, hydrogenated phthalates, and polyoxyethylene compounds.

[0206] The amount of plasticizer used is preferably 5 to 150 parts by weight, more preferably 10 to 120 parts by weight, and even more preferably 20 to 100 parts by weight, relative to 100 parts by weight of the total weight of the polyoxyethylene polymer (A) and the (meth)acrylate polymer (B). If the amount of plasticizer used is within the above range, the desired effect resulting from the use of the plasticizer can be sufficiently obtained, and a cured product with excellent mechanical strength can be formed. The plasticizer can be used alone or in combination of two or more. Low-molecular-weight plasticizers and high-molecular-weight plasticizers can also be used in combination. These plasticizers can be incorporated into the polyoxyethylene polymer (A) or the (meth)acrylate polymer (B) during the manufacture of the polymer.

[0207] (Solvent, diluent)

[0208] The curable composition may contain a solvent or a diluent. There are no particular limitations on the solvent and diluent. Aliphatic hydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons, halogenated hydrocarbons, alcohols, esters, ketones, and ethers can be used as solvents and diluents. When using a solvent or diluent, considering the issue of air pollution when using the curable composition indoors, the boiling point of the solvent is preferably 150°C or higher, more preferably 200°C or higher, and particularly preferably 250°C or higher. The above-mentioned solvents or diluents can be used alone or in combination.

[0209] (Thixotropic agent)

[0210] As needed, to prevent sagging and ensure good workability, the curable composition may contain a thixotropic agent. There are no particular limitations on the thixotropic agent. Examples of thixotropic agents include, for instance, polyamide waxes and hydrogenated castor oil derivatives. These thixotropic agents can be used alone or in combination of two or more.

[0211] The amount of thixotropic agent used is preferably 0.1 to 20 parts by weight, relative to a total of 100 parts by weight of the polyoxyethylene polymer (A) and the (meth)acrylate polymer (B).

[0212] (Antioxidants)

[0213] The curing composition may contain antioxidants (anti-aging agents). Using antioxidants can improve the weather resistance of the cured product. Examples of antioxidants include hindered phenolic compounds, monophenolic compounds, bisphenolic compounds, and polyphenolic compounds.

[0214] For example, Irganox 245, Irganox 1010, Irganox 1035, Irganox 1076, Irganox 1135, Irganox 1330 and Irganox 1520 (all manufactured by BASF); SONGNOX 1076 (manufactured by SONGWON) and BHT are exemplified as suitable antioxidants.

[0215] Similarly, hindered amine light stabilizers such as Tinuvin 622LD, Tinuvin 144, Tinuvin 292, Chimassorb 944LD, and Chimassorb 119FL (all manufactured by BASF); ADEKA STAB LA-57, ADEKA STAB LA-62, ADEKA STAB LA-67, ADEKA STAB LA-63, and ADEKA STAB LA-68 (all manufactured by ADEKA Corporation); Sanol LS-2626, Sanol LS-1114, and Sanol LS-744 (all manufactured by Sankyo Lifetech Corporation); and NocRac CD (manufactured by Ouchi Shinsei Chemical Co., Ltd.) can also be used.

[0216] In addition, antioxidants such as SONGNOX4120, Naugard 445, and OKABEST CLX050 can also be used. Specific examples of antioxidants are described in Japanese Patent Application Publication Nos. 4-283259 and 9-194731.

[0217] The amount of antioxidant used is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, relative to a total of 100 parts by weight of the polyoxyethylene polymer (A) and the (meth)acrylate polymer (B).

[0218] (Light stabilizer)

[0219] The curable composition may contain a light stabilizer. Using a light stabilizer prevents photo-oxidative degradation of the cured product. Examples of light stabilizers include benzotriazole compounds, hindered amine compounds, and benzoate compounds.

[0220] The amount of light stabilizer used is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, relative to a total of 100 parts by weight of the polyoxyethylene polymer (A) and the (meth)acrylate polymer (B).

[0221] Specific examples of light stabilizers can be found in Japanese Patent Application Publication No. 9-194731.

[0222] (UV absorber)

[0223] The curing composition may contain a UV absorber. Using a UV absorber improves the surface weather resistance of the cured product. Examples of UV absorbers include benzophenone compounds, benzotriazole compounds, salicylate compounds, triazine compounds, substituted toluene compounds, and metal chelate compounds. Among these, benzotriazole compounds are particularly preferred. Specific examples of benzotriazole compounds include: Tinuvin 234, Tinuvin 326, Tinuvin 327, Tinuvin 328, Tinuvin 329, Tinuvin 350, Tinuvin 571, Tinuvin 900, Tinuvin 928, Tinuvin 1130, and Tinuvin 1600 (all manufactured by BASF); and SONGSORB 3290 (manufactured by SONGWON). Specific examples of triazine compounds include: Tinuvin 400, Tinuvin 405, Tinuvin 477, and Tinuvin 1577ED (all manufactured by BASF); and SONGSORBCS400 and SONGSORB1577 (manufactured by SONGWON). Specific examples of benzophenone compounds include SONGSORB8100 (manufactured by SONGWON).

[0224] The amount of ultraviolet absorber used is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, relative to 100 parts by weight of the total weight of the polyoxyethylene polymer (A) and the (meth)acrylate polymer (B). It is preferable to use a combination of phenolic antioxidants, hindered phenolic antioxidants, hindered amine light stabilizers, and benzotriazole ultraviolet absorbers.

[0225] Addworks IBC760 (manufactured by Clariant) can be used as a product that combines antioxidants, light stabilizers, and UV absorbers.

[0226] (Modifier)

[0227] As needed, the curable composition may contain a property modifier to adjust the tensile properties of the cured product. There are no particular limitations on the property modifier. Examples of property modifiers include: alkylalkoxysilanes such as methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and n-propyltrimethoxysilane; alkylisopropoxysilanes such as dimethyldiisopropoxysilane, methyltriisopropoxysilane, and 3-glycidyletheroxypropylmethyldiisopropoxysilane; alkoxysilanes with functional groups such as 3-glycidyletheroxypropylmethyldimethoxysilane, 3-glycidyletheroxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyldimethylmethoxysilane, 3-aminopropyltrimethoxysilane, N-2-aminoethyl-3-aminopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-mercaptopropylmethyldimethoxysilane; silicone varnishes; and polysiloxanes. By using property modifiers, the hardness of the cured material can be increased, or conversely, the hardness of the cured material can be decreased, thereby increasing the elongation at break. These property modifiers can be used alone or in combination of two or more.

[0228] In particular, compounds that generate intramolecularly monovalent silanol groups through hydrolysis have the effect of reducing the modulus of the cured product without causing the surface of the cured product to become sticky or deteriorate. Compounds that generate intramolecularly monovalent silanol groups through hydrolysis are particularly preferred. Examples of compounds that generate intramolecularly monovalent silanol groups through hydrolysis include those described in Japanese Patent Application Publication No. 5-117521. Additionally, examples include derivatives of alkyl alcohols such as hexanol, octanol, and decanol that generate trialkylsilanols such as trimethylsilanol through hydrolysis, and derivatives of polyols with 3 or more hydroxyl groups such as trimethylolpropane, glycerol, pentaerythritol, or sorbitol that generate trialkylsilanols such as trimethylsilanol through hydrolysis, as described in Japanese Patent Application Publication No. 11-241029.

[0229] Examples of derivatives of oxyalkylene polymers containing silicon compounds such as trimethylsilanol, which are produced by hydrolysis, can also be cited, as described in Japanese Patent Application Publication No. 7-258534. Furthermore, polymers containing silicon groups that are crosslinkable and hydrolyzable, and those that can be hydrolyzed to form monosilanol compounds, as described in Japanese Patent Application Publication No. 6-279693, can also be used.

[0230] The property modifier is used in the range of 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, relative to a total of 100 parts by weight of the polyoxyethylene polymer (A) and the (meth)acrylate polymer (B).

[0231] (Tackifying resin)

[0232] For purposes such as improving adhesion and bonding to the substrate of the cured product, the curing composition may also include a tackifying resin. There are no particular limitations on the tackifying resin used; any tackifying resin commonly used in various curing compositions may be used.

[0233] Specific examples of tackifying resins include: terpene resins, aromatic modified terpene resins, hydrogenated terpene resins, terpene-phenolic resins, phenolic resins, modified phenolic resins, xylene-phenolic resins, cyclopentadiene-phenolic resins, coumarone-indene resins, rosin resins, rosin ester resins, hydrogenated rosin ester resins, xylene resins, low molecular weight polystyrene resins, styrene copolymer resins, styrene block copolymers, hydrides of styrene block copolymers, petroleum resins, hydrogenated petroleum resins, and DCPD resins. Examples of petroleum resins include, for example, C5 hydrocarbon resins, C9 hydrocarbon resins, and C5C9 hydrocarbon copolymer resins. These can be used alone or in combination of two or more.

[0234] The amount of tackifying resin used is preferably 2 to 100 parts by weight relative to the total weight of the polyoxyethylene polymer (A) and the (meth)acrylate polymer (B). More preferably, it is 5 to 50 parts by weight, and even more preferably, it is 5 to 30 parts by weight. Using the tackifying resin in amounts within this range results in a cured product with good adhesion and bonding to the substrate. The cured composition has a suitable viscosity and good processability.

[0235] (Compounds containing epoxy groups)

[0236] Curable compositions may contain compounds containing epoxy groups. Using compounds with epoxy groups improves the reproducibility of the cured product. Examples of compounds with epoxy groups include: epoxidized unsaturated oils, epoxidized unsaturated fatty acid esters, alicyclic epoxy compounds, epichlorohydrin derivatives, and mixtures thereof. Specific examples of compounds with epoxy groups include: epoxidized soybean oil, epoxidized linseed oil, bis(2-ethylhexyl)-4,5-epoxycyclohexane-1,2-dicarboxylic acid ester (E-PS), octyl epoxy stearate, and butyl epoxy stearate.

[0237] The amount of the epoxy-containing compound used is preferably 0.5 to 50 parts by weight, relative to a total of 100 parts by weight of the polyoxyethylene polymer (A) and the (meth)acrylate polymer (B).

[0238] (Epoxy resin)

[0239] The curable composition may contain epoxy resin. Curable compositions containing epoxy resin are preferably used as adhesives, particularly as adhesives for exterior wall tiles. Examples of epoxy resins include bisphenol A type epoxy resins and phenolic varnish type epoxy resins.

[0240] The ratio of the total weight of the polyoxyethylene polymer (A) and the (meth)acrylate polymer (B) to the weight of the epoxy resin, expressed as a weight ratio (weight of polymer (A) and weight of polymer (B)) / (weight of epoxy resin), is preferably in the range of 100 / 1 to 100 / 100. Using polymer (A) and polymer (B) with epoxy resin in the above ratio readily yields a high-strength cured product with excellent impact strength and toughness.

[0241] When using epoxy resin, the curable composition may include a curing agent along with the epoxy resin. There are no particular limitations on the type of curing agent; commonly used curing agents can be used.

[0242] The amount of curing agent used is preferably 0.1 to 300 parts by weight relative to 100 parts by weight of epoxy resin.

[0243] (Photocurable substances)

[0244] Curable compositions may contain photocurable substances. When a photocurable substance is used, a film of the substance is formed on the surface of the cured material, improving its stickiness and weather resistance. Various compounds, such as organic monomers, oligomers, and resins, are known as photocurable substances. Furthermore, numerous compositions containing photocurable substances are known. Representative photocurable substances include unsaturated acrylic compounds, polyvinyl cinnamates, and azide resins. Examples of unsaturated acrylic compounds include monomers, oligomers, or mixtures thereof having one or more acrylic or methacrylic unsaturated groups.

[0245] The amount of photocurable material used is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, relative to 100 parts by weight of the total weight of the polyoxyethylene polymer (A) and the (meth)acrylate polymer (B). Using an amount of photocurable material within this range makes it easy to form a soft cured product with excellent weather resistance and that inhibits crack formation.

[0246] (Oxygen-curing substances)

[0247] The curing composition may contain an oxygen-curing substance. Examples of oxygen-curing substances include unsaturated compounds capable of reacting with oxygen in the air. If the curing substance contains an oxygen-curing substance, the oxygen-curing substance reacts with oxygen in the air to form a cured film near the surface of the cured material. By forming a cured film on the surface of the cured material, it is possible to prevent stickiness, dirt, and dust adhesion to the surface of the cured material. Specific examples of oxygen-curing substances include: drying oils such as tung oil and linseed oil; various alkyd resins obtained by modifying drying oils; acrylic polymers, epoxy resins, and silicone resins modified with drying oils; and liquid polymers such as 1,2-polybutadiene, 1,4-polybutadiene, or C5-C8 dienes obtained by polymerizing or copolymerizing diene compounds such as butadiene, chloroprene, isoprene, or 1,3-pentadiene. These can be used alone or in combination of two or more.

[0248] The amount of oxygen-curing agent used is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, relative to 100 parts by weight of the total weight of the polyoxyethylene polymer (A) and the (meth)acrylate polymer (B). Using an amount of oxygen-curing agent within this range facilitates the formation of a cured product with a surface that is not easily contaminated by dirt or dust, and exhibits excellent mechanical properties such as tensile strength. As described in Japanese Patent Application Publication No. 3-160053, the oxygen-curing agent is preferably used in combination with a light-curing agent.

[0249] Preparation of Curable Compositions

[0250] Curing compositions are prepared in a single-component form, where all components are pre-formulated and sealed, and then cured by moisture in the air after application.

[0251] Alternatively, a curing catalyst, filler, plasticizer, water, and other components can be separately pre-formulated as a curing agent, and the mixture can be prepared as a two-component formulation by mixing the pre-formulated material with a polymer composition containing a polyoxyethylene polymer (A) and a (meth)acrylate polymer before use. From an operability point of view, a single-component formulation is preferred.

[0252] When the curable composition is a single-component form, all compounding components are pre-formulated. Therefore, it is preferable to pre-dehydrate and dry the compounding components containing moisture before use, or to dehydrate them during compounding by means of reduced pressure or the like.

[0253] In addition to the dehydration and drying method, the storage stability of the cured composition can be further improved by adding alkoxysilane compounds such as methyltrimethoxysilane, phenyltrimethoxysilane, n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, and γ-glycidyl etheroxypropyltrimethoxysilane to the cured composition.

[0254] Uses of Curing Compositions

[0255] Curing compositions can be used as sealants, industrial adhesives, waterproof coatings, and adhesive raw materials. They can also be used as sealants for buildings, ships, automobiles, and roads. Furthermore, curing compositions can bond well with a wide range of substrates, including glass, ceramics, wood, metals, and resin molded products, either alone or with the aid of a primer. Therefore, curing compositions can be used as various types of sealing and adhesive compositions. In addition to conventional adhesives, curing compositions can also be used as contact adhesives. Moreover, curing compositions are useful as food packaging materials, casting rubber materials, molding materials, and coatings.

[0256] Example

[0257] The present invention will be further described in detail below through embodiments. It should be noted that the present invention is not limited to the following embodiments.

[0258] (molecular weight)

[0259] In the examples, the number-average molecular weight Mn and weight-average molecular weight Mw are GPC molecular weights determined under the following conditions.

[0260] Liquid delivery system: Tosoh HLC-8220GPC

[0261] Column: Tosoh TSKgel Super H series

[0262] Solvent: THF

[0263] Molecular weight: Polystyrene conversion

[0264] Measurement temperature: 40℃

[0265] (Average number of reactive silicon groups)

[0266] The average number of reactive silicon groups per molecule of the polymer shown in the examples was calculated by NMR determination.

[0267] (Glass transition temperature Tg)

[0268] The glass transition temperature Tg is determined using the following Fox equation.

[0269] Fox's formula: 1 / (Tg(K))=Σ(Mi / Tgi)

[0270] (In the formula, Mi represents the weight fraction of monomer i that constitutes the polymer, and Tgi represents the glass transition temperature (K) of the homopolymer of monomer i.)

[0271] [Synthesis example 1]

[0272] Polypropylene glycol with a number average molecular weight of approximately 4500 was used as an initiator, and propylene oxide was polymerized using a zinc hexacyanocobaltate ethylene glycol dimethyl ether complex catalyst to obtain polypropylene oxide (P-1) with two terminal hydroxyl groups, a number average molecular weight of 27900 (terminal group equivalent molecular weight 17700), and a molecular weight distribution Mw / Mn = 1.21. Next, 1.2 molar equivalents of sodium methoxide were added to the hydroxyl groups of the hydroxyl-terminated polypropylene oxide (P-1) in the form of a 28% methanol solution. After removing the methanol by vacuum devolatilization, 1.5 molar equivalents of allyl chloride were further added to the hydroxyl groups of the polymer (P-1) to convert the terminal hydroxyl groups to allyl groups. Unreacted allyl chloride was removed by vacuum devolatilization. The resulting unpurified polypropylene oxide was mixed with n-hexane and water, stirred, and the water was removed by centrifugation. Hexane was then devolatilized from the resulting hexane solution under reduced pressure, thereby removing the metal salt from the polymer. Through the above operations, polyoxypropylene (Q-1) with allyl groups at the ends was obtained. 50 μL of a divinyldisiloxane platinum complex solution (equivalent to 3% isopropanol solution in platinum equivalent) was added relative to 500 g of this polymer (Q-1), while stirring, 4.8 g of dimethoxymethylsilane was slowly added dropwise. After reacting the mixture at 100°C for 2 hours, the unreacted dimethoxymethylsilane was distilled off under reduced pressure, thus obtaining polyoxypropylene (A-1) with a number-average molecular weight of approximately 28,500 and dimethoxymethylsilyl groups at the ends. It can be seen that polymer (A-1) has an average of 0.8 dimethoxymethylsilyl groups at one end, and an average of 1.6 per molecule.

[0273] [Synthesis example 2]

[0274] Over 3.5 hours, the following solution was added dropwise to 81.4 g of isobutanol (IBA) heated to 105°C in the reaction vessel: a solution prepared by dissolving 6.2 g of azobis-2-methylbutyronitrile (ABR) as a polymerization initiator in a mixture of 34.3 g of methyl methacrylate, 188.7 g of butyl acrylate, 44.6 g of 2-ethylhexyl acrylate, 68.6 g of stearate methacrylate, 6.9 g of γ-methacryloyloxypropyl dimethoxymethylsilane, and 55.6 g of IBA. Next, over 1 hour, a solution prepared by dissolving 0.7 g of ABR as a polymerization initiator in 13.1 g of IBA was added dropwise to the reaction vessel. After polymerization for 2 hours, an isobutanol solution of a (meth)acrylate copolymer (B-1) with a solid content of 70% by weight, a number average molecular weight of 8700, and a weight average molecular weight of 18900 was obtained.

[0275] [Synthesis example 3]

[0276] Over 3.5 hours, the following solution was added dropwise to 90.3 g of isobutanol (IBA) heated to 105°C in the reaction vessel: 1.1 g of azobis-2-methylbutyronitrile (ABR), acting as a polymerization initiator, was dissolved in a mixture of 35.2 g of methyl methacrylate, 193.6 g of butyl acrylate, 45.8 g of 2-ethylhexyl acrylate, 70.4 g of stearate methacrylate, 3.5 g of γ-methacryloyloxypropyl dimethoxymethylsilane, and 43.9 g of IBA. Next, over 1 hour, a solution of 0.3 g of ABR dissolved in 15.7 g of IBA was added dropwise to the reaction vessel. After polymerization for 2 hours, an isobutanol solution of a (meth)acrylate polymer (B-2) with a solid content of 70% by weight, a number average molecular weight of 15,100, and a weight average molecular weight of 41,600 was obtained.

[0277] [Synthesis example 4]

[0278] Over 3.5 hours, the following solution was added dropwise to 90.9 g of isobutanol (IBA) heated to 105°C in the reaction vessel: 1.1 g of azobis-2-methylbutyronitrile (ABR), acting as a polymerization initiator, was dissolved in a solution formed from a mixture of 34.9 g of methyl methacrylate, 191.7 g of butyl acrylate, 45.3 g of 2-ethylhexyl acrylate, 69.7 g of stearate methacrylate, 7.0 g of γ-methacryloyloxypropyl dimethoxymethylsilane, and 43.5 g of IBA. Next, over 1 hour, a solution of 0.3 g of ABR, acting as a polymerization initiator, dissolved in 15.6 g of IBA, was added dropwise to the reaction vessel. After polymerization for 2 hours, an isobutanol solution of a (meth)acrylate polymer (B-3) with a solid content of 70% by weight, a number average molecular weight of 15,500, and a weight average molecular weight of 43,500 was obtained.

[0279] [Synthesis example 5]

[0280] Over 3.5 hours, the following solution was added dropwise to 91.5 g of isobutanol (IBA) heated to 105 °C in the reaction vessel: 1.1 g of azobis-2-methylbutyronitrile (ABR), acting as a polymerization initiator, was dissolved in a mixture of 34.5 g of methyl methacrylate, 189.8 g of butyl acrylate, 44.9 g of 2-ethylhexyl acrylate, 69.0 g of stearate methacrylate, 10.4 g of γ-methacryloyloxypropyl dimethoxymethylsilane, and 43.1 g of IBA. Next, over 1 hour, a solution of 0.3 g of ABR, acting as a polymerization initiator, dissolved in 15.5 g of IBA, was added dropwise to the reaction vessel. After polymerization for 2 hours, an isobutanol solution of a (meth)acrylate polymer (B-4) with a solid content of 70% by weight, a number average molecular weight of 14800, and a weight average molecular weight of 41000 was obtained.

[0281] [Synthesis Example 6]

[0282] Over 3.5 hours, the following solution was added dropwise to 91.5 g of isobutanol (IBA) heated to 105 °C in the reaction vessel: a solution of 1.1 g of azobis-2-methylbutyronitrile (ABR) as a polymerization initiator dissolved in a mixture of 103.5 g of methyl methacrylate, 131.2 g of butyl acrylate, 34.5 g of 2-ethylhexyl acrylate, 69.0 g of stearate methacrylate, 10.4 g of γ-methacryloyloxypropyl dimethoxymethylsilane, and 43.1 g of IBA was added dropwise to the reaction solution. Then, over 1 hour, a solution of 0.3 g of ABR dissolved in 15.5 g of IBA was added dropwise. After polymerization for 2 hours, an isobutanol solution of a (meth)acrylate polymer (B-5) with a solid content of 70% by weight, a number average molecular weight of 15800, and a weight average molecular weight of 39200 was obtained.

[0283] (Determination of physical properties of cured products)

[0284] 4 g of isobutanol solution (2.8 g solids) of the (meth)acrylate polymers (B-1) to (B-5) obtained in Synthetic Examples 2-6 was mixed with 0.056 g of NEOSTANN U-220H (manufactured by Nitto Kasei Corporation: diacetylacetonate dibutyltin), and air bubbles were removed using a centrifuge. The resulting mixture was coated onto a polytetrafluoroethylene sheet using a 10 mil applicator. The formed coating was cured at room temperature for 30 minutes, then cured at 105°C for 1 hour, 23°C for 3 days, and 50°C for 4 days to obtain cured sheets. Short strips (5 mm wide) were made from the obtained sheets, and tensile tests were conducted using an Autograph (AGS-J) instrument manufactured by Shimadzu Corporation at a tensile speed of 10 mm / min to determine the breaking strength TB (N / mm). 2 The results are shown in Table 1.

[0285]

[0286] [Comparative Example 1]

[0287] After mixing 60 parts by weight of polyoxypropylene (A-1) obtained in Synthesis Example 1 and an isobutanol solution containing 40 parts by weight of (meth)acrylate polymer (B-1) obtained in Synthesis Example 2 as a solid component, the isobutanol was heated to devolatilize. The resulting mixture was mixed with 160 parts by weight of Baiyanhua CCR (manufactured by Shiraishi Kogyo Co., Ltd.: precipitated calcium carbonate), 54 parts by weight of Whiton SB (manufactured by Shiraishi Calcium Co., Ltd.: heavy calcium carbonate), 5 parts by weight of TIPAQUE R820 (manufactured by Ishihara Sangyo Co., Ltd.: titanium dioxide), 90 parts by weight of DINP (manufactured by J-PLUS Co., Ltd.: diisodecyl phthalate), 2 parts by weight of DISPARLON 6500 (manufactured by Kusunoki Chemical Co., Ltd.: fatty acid amide wax), 1 part by weight of Tinuvin 326 (manufactured by BASF: benzotriazole UV absorber), and 1 part by weight of LS770 (manufactured by Ciba Specialty Chemicals: hindered amine light stabilizer), and then passed through a three-roll paint mill three times to ensure uniform dispersion. Subsequently, the resulting mixture was dehydrated under reduced pressure at 120°C for 2 hours. After cooling the dehydrated mixture to below 50°C, 3 parts by weight of A-171 (manufactured by Momentive: vinyltrimethoxysilane) and 3 parts by weight of A-1120 (manufactured by Momentive: N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane) were added to the mixture and mixed. Then, 2 parts by weight of NEOSTANN U-220H (manufactured by Nitto Chemical Co., Ltd.: diacetylacetonate dibutyltin) were added to the mixture and kneaded to obtain a curable composition. The obtained curable composition was sealed in a glue tube, which serves as a moisture-proof container, to obtain a single-component curable composition.

[0288] (Dumbbell stretching properties)

[0289] The obtained curable composition was filled into a mold and cured at 23°C and 50% relative humidity for 3 days, followed by curing at 50°C for 4 days to produce a sheet-like cured material with a thickness of approximately 3 mm. The sheet-like cured material was punched into a No. 3 dumbbell shape and subjected to tensile strength testing at 23°C and 50% relative humidity to determine the modulus (M100) at 100% elongation. In addition, the breaking strength TB (MPa) and elongation at break EB (%) were measured. The tests were conducted using an Autograph (AGS-J) instrument manufactured by Shimadzu Corporation at a tensile speed of 200 mm / min. The results are shown in Table 2.

[0290] (Weather resistance test)

[0291] The obtained curable composition was filled into a mold and cured at 23°C and 50% relative humidity for 3 days, followed by curing at 50°C for 4 days to produce a sheet-like cured material with a thickness of approximately 1 mm. The obtained sheet-like cured material was cut into 20 mm × 20 mm pieces to obtain test specimens. A Metal Weather weathering tester (manufactured by DAIPLA·WINTES Co., Ltd., trade name: DAIPLA·Metal Weather CW-R8PL-A) was used at an illuminance of 125 mW / cm². 2 Weather resistance tests were conducted on the test pieces under the conditions of a blackboard temperature of 63℃ and spraying pure water for 2 minutes every 2 hours. The surface of the cured material was observed every 70 hours of exposure. The time when cracks were confirmed on the surface of the test pieces is recorded in Table 2.

[0292] [Comparative Example 2 and Examples 1-3]

[0293] The (meth)acrylate polymer (B-1) was changed to a (meth)acrylate polymer of the type listed in Table 2, and otherwise a curable composition was obtained in the same manner as Comparative Example 1. Using the obtained curable composition, dumbbell tensile property tests and weathering resistance tests were performed according to the above method. The results are shown in Table 2.

[0294]

[0295] When using the curing compositions of Comparative Examples 1 and 2, which included either polymer (B-1) or polymer (B-2) whose cured property (TB) could not be determined individually, the crack initiation time in the weathering evaluation was shortened to 280 hours and 350 hours, respectively. In contrast, when using the cured product composition containing only (meth)acrylate polymer (B) with a cured property (TB) of 0.020 N / mm... 2 In the case of the curable compositions of polymers (B-3) to polymers (B-5) in Examples 1 to 3, the crack initiation time in the weathering test is more than 490 hours, and the elongation at break (EB) value is also a high value of more than 500%.

Claims

1. A curable composition comprising a polyoxyethylene polymer (A) having reactive silicone groups and a (meth)acrylate polymer (B) having reactive silicone groups, wherein, The molecular chain of the (meth)acrylate polymer (B) contains structural units derived from (meth)acrylates. The number-average molecular weight (Mn) of the (meth)acrylate polymer (B), as determined by gel permeation chromatography, is 10,000 to 20,000, based on the polystyrene equivalent. The ratio of the polystyrene-converted weight-average molecular weight Mw to Mn of the (meth)acrylate polymer (B), as determined by gel permeation chromatography, is 1.6 or higher (Mw / Mn). The glass transition temperature of the (meth)acrylate polymer (B) is below 0°C. The cured (meth)acrylate polymer (B) has a tensile strength of 0.020~0.300 N / mm. 2 , The fracture strength was determined by a method including the following operations: A mixture was obtained by mixing 100 parts by weight of the (meth)acrylate polymer (B) with 2 parts by weight of diacetylaceton-dibutyltin. The mixture is cured to produce a sheet with a thickness of 0.25 ± 0.05 mm; Cut short strips, 5 mm wide, from the sheet; and The test piece was used, and a tensile test was performed at a tensile speed of 10 mm / min.

2. The curable composition according to claim 1, wherein, The fracture strength is 0.050~0.300 N / mm. 2 .

3. The curable composition according to claim 1, wherein, The tensile strength is 0.050~0.200 N / mm. 2 .

4. A cured product, which is a cured product of the curable composition according to any one of claims 1 to 3.

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