Method for producing curable composition and cured product

Abstract

To provide a method for producing a curable composition having low initial viscosity.SOLUTION: A curable composition according to one embodiment of the present invention comprises component A: a (meth)acrylic polymer having a silyl group, component B: an epoxy compound, component C: an epoxy curing agent that generates an amino group upon contact with moisture, and component D: a curing catalyst. Component A has a specific block structure. This curable composition is prepared by a production method comprising: Step 1: mixing component A and component E, Step 2: adding and mixing component D into the mixture prepared in Step 1, Step 3: further mixing component C into the mixture prepared in Step 2, and Step 4: further mixing component B into the mixture prepared in Step 3.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a method for producing a curable composition and a cured product. [Background technology]

[0002] Polymer molecules having silyl groups form siloxane bonds with other polymer molecules through hydrolysis of the silyl groups. This crosslinking reaction produces a rubber-like cured product. Curable compositions containing such polymer molecules are used in sealants, adhesives, paints, etc. (see, for example, Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent Publication No. 2021-066811 Summary of the Invention [Problem to be solved by the invention]

[0004] The above-mentioned conventional techniques leave room for improvement in terms of the viscosity of the resulting cured product.

[0005] An object of one aspect of the present invention is to provide a method for producing a curable composition having a low initial viscosity. [Means for solving the problem]

[0006] A method for producing a curable composition according to one embodiment of the present invention includes the following components A to D: Component A: a (meth)acrylic polymer having a silyl group; Component B: epoxy compound; Component C: An epoxy hardener that generates amino groups upon contact with moisture; Component D: Curing catalyst; Component E: Dehydrating agent; The method includes the following steps 1 to 4: Step 1: mixing the component A and the component E; Step 2: adding and mixing the component D to the mixture obtained in step 1; Step 3: further mixing component C with the mixture obtained in step 2; Step 4: further mixing component B into the mixture obtained in step 3; Here, the component A is The molecule has an XY diblock structure having an X block and a Y block, or an XYX triblock structure, The number of repeating units derived from the silyl group-containing (meth)acrylic acid ester monomer contained in the X block is more than 2.0 on average, the content of repeating units derived from silyl group-containing (meth)acrylic acid ester monomers contained in the Y block is 0% by weight or more and less than 5% by weight based on the weight of all repeating units contained in the Y block, The molecular weight distribution (Mw / Mn) is 1.8 or less. Effect of the Invention

[0007] According to one aspect of the present invention, there is provided a method for producing a curable composition having a low initial viscosity. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] An example of an embodiment of the present invention will be described in detail below, but the present invention is not limited to the following embodiments and may be modified in various ways within the scope of the claims. An embodiment that combines technical means described in different embodiments is also included in the technical scope of the present invention.

[0009] Unless otherwise specified in this specification, "A to B" representing a numerical range means "A or more and B or less." In this specification, "(meth)acrylic" means "acrylic and / or methacrylic." Unless otherwise specified in this specification, "silyl group" means "hydrolyzable silyl group." In one embodiment, the silyl group is an alkoxysilyl group.

[0010] 1. Method for producing curable composition A method for producing a curable composition according to one embodiment of the present invention includes the following steps: By mixing the components in this order, the initial viscosity can be reduced. Step 1: A step of mixing component A: a (meth)acrylic polymer having a silyl group, and component E: a dehydrating agent. Step 2: Adding component D, a curing catalyst, to the mixture obtained in step 1 and mixing. Step 3: A step of further mixing component C: an epoxy curing agent that generates an amino group upon contact with moisture, into the mixture obtained in step 2. Step 4: A step of further mixing component B: an epoxy compound into the mixture obtained in step 3.

[0011] In each step, the order of mixing the components is not particularly limited. For example, in step 1, component D may be added to component A and mixed, or component A may be added to component D and mixed. In each step, the components may be added in one batch or in multiple batches. For example, when component D is added to component A and mixed in step 1, the entire amount of component D may be added in one batch or in multiple batches.

[0012] [2. Curable composition] The curable composition according to one embodiment of the present invention includes component A: a (meth)acrylic polymer having a silyl group, component B: an epoxy compound, component C: an epoxy curing agent that generates an amino group upon contact with moisture, component D: a curing catalyst, and component E: a dehydrating agent. The curable composition may include additives other than those described above. Only one type of each component may be blended, or two or more types may be blended.

[0013] [2.1. Component A: (meth)acrylic polymer having silyl groups] Component A is a (meth)acrylic polymer A having a silyl group. Component A has a silyl group derived from a silyl group-containing (meth)acrylic ester monomer. Component A has an X block having a high frequency of silyl groups and a Y block having a low frequency of silyl groups. Component A can be polymerized, for example, by changing the monomer composition during polymerization.

[0014] [2.1.1. Structure of component A] Component A has an X block and a Y block, and contains an XY diblock structure or an XYX triblock structure in the molecule. The structure of the entire molecule of component A is not particularly limited as long as it contains an XY diblock structure or an XYX triblock structure, and may be, for example, an XYXY tetrablock structure.

[0015] Here, the term "XYX triblock structure" means the "ABA triblock structure" generally known among those skilled in the art. The ratio of X / Y in component A is preferably from (5 / 95) to (60 / 40), more preferably from (15 / 85) to (40 / 60).

[0016] In one embodiment, the molecule of component A has an XY diblock structure. In the molecule of the XY diblock structure, the X block can be a region of 40% or less, 30% or less, or 25% or less from one end of the molecule (all repeating units contained in the molecule are taken as 100%). Here, the X block is the block on the side where silyl groups are distributed in a relatively large amount.

[0017] In one embodiment, the molecule of component A has an XYX triblock structure. In the molecule of the XYX triblock structure, the X blocks can be 40% or less, 30% or less, or 25% or less of the region from the ends of the molecule (all repeat units contained in the molecule are taken as 100%). Here, the X blocks are blocks located at both ends of the molecule.

[0018] Component A has a repeating unit derived from a silyl group-containing (meth)acrylic acid ester monomer. The repeating unit derived from the silyl group-containing (meth)acrylic acid ester monomer is contained relatively more in the X block. The repeating units derived from the silyl group-containing (meth)acrylic acid ester monomer contained in the X block are more than 2.0 on average. When component A has two or more X blocks in one molecule, the total number of repeating units derived from the silyl group-containing (meth)acrylic acid ester monomer contained in the multiple X blocks is more than 2.0 on average. On the other hand, the repeating units derived from the silyl group-containing (meth)acrylic acid ester monomer contained in the Y block are 0% by weight or more and less than 5% by weight based on the weight of all repeating units contained in the Y block.

[0019] The repeating units derived from the silyl group-containing (meth)acrylic acid ester monomer contained in the X block are more than 2.0 on average, preferably 2.1 or more, more preferably 2.2 or more, even more preferably 2.3 or more, and particularly preferably 2.5 or more. Similarly, the repeating units derived from the silyl group-containing (meth)acrylic acid ester monomer contained in the X block are preferably 0.5% by weight or more, more preferably 2.0% by weight or more, and even more preferably 3.0% by weight or more, based on the weight of all repeating units contained in the X block. The upper limit of the repeating units derived from the silyl group-containing (meth)acrylic acid ester monomer contained in the X block is preferably 90% by weight or less, more preferably 60% by weight or less, and even more preferably 30% by weight or less.

[0020] The upper limit of the repeating units derived from the silyl group-containing (meth)acrylic acid ester monomer contained in the Y block is less than 5% by weight, preferably 4% by weight or less, more preferably 3% by weight or less, even more preferably 2% by weight or less, and particularly preferably 1% by weight or less, based on the weight of all repeating units contained in the Y block. The lower limit of the repeating units derived from the silyl group-containing (meth)acrylic acid ester monomer contained in the Y block is preferably 0% by weight or more, more preferably more than 0% by weight, based on the weight of all repeating units contained in the Y block.

[0021] The number of silyl groups introduced into component A is, on average, more than 2.0, preferably 2.2 or more, more preferably 2.6 or more, even more preferably 3.0 or more, and particularly preferably 3.4 or more, in the whole molecule. The upper limit of the number of silyl groups introduced into the (meth)acrylic polymer is preferably 10.0 or less, more preferably 8.0 or less, even more preferably 6.0 or less, and particularly preferably 5.0 or less. If the number of silyl groups is within the above range, a curable composition and a cured product with good physical properties can be obtained.

[0022] Specific examples of silyl group-containing (meth)acrylic acid ester monomers include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane.

[0023] Component A may contain a repeating unit derived from a (meth)acrylic monomer having a long side chain. In this specification, the term "(meth)acrylic monomer having a long side chain" refers to a repeating unit derived from a (meth)acrylic monomer having a long side chain, represented by the formula: CH2=C(R 1 )COOR 2 In the formula, R 1 is a hydrogen atom or a methyl group. 2 is a group having 9 or more carbon atoms.

[0024] The content of the repeating unit derived from the (meth)acrylic monomer having a long side chain is preferably 1% by weight or more of all the constitutional units contained in Component A. Component A containing such a repeating unit may improve the compatibility with the polyoxyalkylene polymer and improve the physical properties of the obtained cured product. The upper limit of the content of the repeating unit derived from the (meth)acrylic monomer having a long side chain is preferably 5% by weight or less, more preferably 3% by weight or less. If the content is within the above range, the production cost of Component A does not increase excessively.

[0025] Examples of (meth)acrylic monomers having a long side chain include nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, octadecyl (meth)acrylate, icosyl (meth)acrylate, docosyl (meth)acrylate, oleyl (meth)acrylate, linoleyl (meth)acrylate, and isobornyl (meth)acrylate.

[0026] Among the above-mentioned monomers, one or more selected from octadecyl (meth)acrylate, oleyl (meth)acrylate, and linoleyl (meth)acrylate are preferred. These monomers have the advantage of being liquid at room temperature and having high polymerization stability. In addition, by blending these monomers, a (meth)acrylic acid-based polymer having high compatibility with a polyoxyalkylene-based polymer can be obtained.

[0027] In this specification, the term "(meth)acrylic monomer having a non-long side chain" refers to a (meth)acrylic monomer having a non-long side chain in the above formula, R 2represents a monomer having 8 or less carbon atoms. Examples of such monomers include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, isopropoxyethyl (meth)acrylate, benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, glycidyl (meth)acrylate, 1-ethylcyclopentyl ether (meth)acrylate, and dimethylaminoethyl (meth)acrylate.

[0028] Among the above-mentioned monomers, one or more selected from methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate are preferred. These monomers have low procurement costs and are suitable for the purpose of reducing the production cost of component A.

[0029] Furthermore, from the viewpoint of glass transition point, one or more selected from n-butyl acrylate and 2-ethylhexyl acrylate are preferred. Component A obtained from these monomers has a low glass transition point and a low polymer viscosity. Therefore, a curable composition that is easy to use in a low temperature environment is obtained.

[0030] Component A may have a repeating unit derived from a monomer other than a (meth)acrylic acid ester monomer. The proportion of the repeating unit derived from a (meth)acrylic acid ester monomer in Component A is preferably 50% by weight or more, more preferably 70% by weight or more, and even more preferably 90% by weight or more of the total weight of Component A.

[0031] [2.1.2. Silyl groups possessed by (meth)acrylic copolymers] The silyl group contained in Component A may be derived from a silyl group-containing (meth)acrylic acid ester monomer. In one embodiment, the silyl group is represented by the following general formula: -[Si(R 3 ) 2-b (Y) b O] m -Si(R 4 ) 3-a (Y) a

[0032] In the formula, R 3 and R 4 are independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a methoxymethyl group, or a triorganosiloxy group represented by (R')3SiO-. R' is a monovalent hydrocarbon group having 1 to 20 carbon atoms. The three R's may be the same or different. R 3 or R 4 When two or more are present, they may be the same or different. Y represents a hydroxyl group or a hydrolyzable group. Examples of the hydrolyzable group include an alkoxy group, an acetoxy group, and an oxime group. In one embodiment, Y is a hydroxyl group, a methoxy group, an ethoxy group, or an isopropoxy group. When a single silyl group contains a plurality of X's, they may be the same or different. When a single molecule of component A contains a plurality of silyl groups, Y may be different for each silyl group. a is 0, 1, 2, or 3. b is 0, 1, or 2. m is an integer of 0 to 19. However, the relationship a+mb≧1 is satisfied.

[0033] The specific structure of the silyl group-containing (meth)acrylic acid ester monomer is not particularly limited. An example is a monomer represented by the following general formula: H2C=C(R 5 )C(=O)-O-(CH2) m -SiR 6n (OR 7 ) 3-n

[0034] In the formula, R 5 is hydrogen or a methyl group. 6 and R 7 R is at least one selected from the group consisting of hydrogen, a methyl group, and an ethyl group. 6 and / or R 7 When a plurality of are present, they may be the same or different. m is an integer of 0 to 10. n is an integer of 0 to 2.

[0035] Specific examples of silyl group-containing (meth)acrylic acid ester monomers include 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane.

[0036] [2.1.3. Physical properties of component A] In one embodiment, the lower limit of the number average molecular weight of component A is preferably 2,000 or more, more preferably 10,000 or more, and even more preferably 15,000 or more. The upper limit of the number average molecular weight of component A is preferably 50,000 or less, more preferably 30,000 or less, and even more preferably 20,000 or less. When the number average molecular weight of component A is within the above range, the viscosity of the curable composition does not become too high, and sufficient workability can be ensured.

[0037] In one embodiment, the molecular weight distribution of component A is 1.8 or less, preferably 1.5 or less, 1.4 or less, 1.3 or less, or 1.2 or less. If the molecular weight distribution is within the above range, the viscosity of the polymer tends to decrease and the workability tends to improve. The molecular weight distribution is a value given by "weight average molecular weight ÷ number average molecular weight".

[0038] The weight average molecular weight and number average molecular weight are measured by gel permeation chromatography (GPC). For GPC measurement, chloroform is used as the mobile phase and a polystyrene gel column is used as the stationary phase. The molecular weight obtained by measurement is the molecular weight converted into standard polystyrene.

[0039] [2.1.4. Manufacturing method of component A] The polymerization method of component A is not particularly limited, and known polymerization methods can be used (radical polymerization method, cationic polymerization method, anionic polymerization method, etc.). The polymerization method called SGO (Solid Grade Oligomer; high temperature continuous bulk polymerization) is preferred because it is a method that can obtain component A without using a polymerization solvent, a polymerization initiator, a chain transfer agent, etc. A living polymerization method is preferred because it can introduce a functional group near the end of the polymer molecule and can synthesize component A with a small molecular weight distribution. Examples of living polymerization methods include living radical polymerization method, living cationic polymerization method, and living anionic polymerization method, and among them, living radical polymerization method is suitable for polymerization of (meth)acrylic monomers. Examples of living radical polymerization methods include the following. Atom Transfer Radical Polymerization (ATRP) (see J. Am. Chem. Soc. 1995, 117, 5614; Macromolecules. 1995, 28, 1721) Single Electron Transfer Polymerization (SET-LRP (see J. Am. Chem. Soc. 2006, 128, 14156; JPSChem 2007, 45, 1607)) Reversible Chain Transfer Catalyzed Polymerization (RTCP) (see "Living Radical Polymerization Controlled by Organic Catalysts" Polymer Journal Vol. 68, 223-231 (2011); JP Patent Publication No. 2014-111798) Reversible addition-fragmentation chain transfer polymerization (RAFT polymerization) Nitroxy radical method (NMP method) Polymerization using organotellurium compounds (TERP method) ·Organoantimony Polymerization Method (SBRP Method) Polymerization method using organobismuth compounds (BIRP method) -Iodine transfer polymerization method

[0040] An example of a method for introducing a silyl group into component A is the method described in JP 2018-162394 A. The method disclosed in the document introduces a silyl group into component A by copolymerizing a (meth)acrylic acid ester monomer and a silyl group-containing (meth)acrylic acid ester monomer. More specifically, a silyl group is introduced near the terminal of the component A molecule by controlling the input amount of the silyl group-containing (meth)acrylic acid ester monomer according to the progress stage of the living polymerization. Component A obtained by these methods may have a silyl group locally at the terminal or near the terminal of the molecule.

[0041] [2.2. Component B: Epoxy compound] Component B is an epoxy compound. As component B, a resin having two or more epoxy groups in the molecule can be used without any particular limitation.

[0042] In one embodiment, Component B is preferably at least one selected from the group consisting of bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, aliphatic epoxy compounds, novolac type epoxy compounds, and glycidylamine type epoxy compounds.

[0043] Examples of bisphenol A type epoxy compounds include bisphenol A diglycidyl ether, halogenated bisphenol A diglycidyl ether, tetrachlorobisphenol A diglycidyl ether, bisphenol A polymeric diglycidyl ether, polycondensates of bisphenol A and epichlorohydrin, and hydrogenated products thereof.

[0044] Examples of the bisphenol F type epoxy compound include bisphenol F diglycidyl ether, bisphenol F polymeric diglycidyl ether, polycondensation products of bisphenol F and epichlorohydrin, and hydrogenated products thereof.

[0045] Examples of the aliphatic epoxy compound include linear aliphatic epoxy compounds (e.g., compounds having 6 to 50 carbon atoms and 2 to 6 epoxy groups); diglycidyl ethers of dihydric aliphatic alcohols (e.g., diglycidyl ethers of diols having 2 to 100 carbon atoms and molecular weights of 150 to 5000); polyglycidyl ethers of trihydric or higher aliphatic alcohols (e.g., glycidyl ethers of trihydric to hexahydric polyhydric alcohols having 3 to 50 carbon atoms and molecular weights of 92 to 10000); alicyclic epoxy compounds; and diglycidyl ethers having a polyethylene glycol skeleton, a polypropylene glycol skeleton, or a hexanediol skeleton.

[0046] Examples of the novolac type epoxy compound include phenol-modified novolac resin and cresol novolac resin.

[0047] Examples of the glycidyl amine type epoxy compound include glycidyl amines of aromatic amines (for example, glycidyl amines of aromatic amines having 6 to 20 carbon atoms and 2 to 10 active hydrogen atoms), glycidyl amines of alicyclic amines, glycidyl amines of heterocyclic amines, condensates of aliphatic amines and epichlorohydrin, and condensates of aromatic amines and epichlorohydrin.

[0048] [2.3. Component C: Epoxy curing agent that generates amino groups upon contact with moisture] Component C is an epoxy curing agent that generates amino groups upon contact with moisture. An example of such a curing agent is ketimine. Ketimine is an imine derived from ketone and has a partial structure of -N=C(R)R' (R and R' are not hydrogen atoms). Ketimine is stable in the absence of moisture, but generates amino groups upon contact with moisture, curing the epoxy cured material.

[0049] Commercially available products may be used as component C. Examples of ketimine-type curing agents include H3 and H30 (both manufactured by Mitsubishi Chemical Corporation), EH-235R-2 (ADEKA Corporation), and Daitoclar E-5493 (Daito Sangyo Co., Ltd.).

[0050] [2.4. Component D: Curing catalyst] Examples of the curing catalyst include tin-based curing catalysts. Specific examples of the tin-based curing catalyst include dialkyltin carboxylates (dibutyltin dilaurate, dibutyltin diacetate, dibutyltin diethylhexanolate, dibutyltin dioctate, dibutyltin dimethyl maleate, dibutyltin diethyl maleate, dibutyltin dibutyl maleate, dibutyltin diisooctyl maleate, dibutyltin ditridecyl maleate, dibutyltin dibenzyl maleate, dibutyltin maleate, dioctyltin diacetate, dioctyltin distearate, dioctyltin dilaurate, dioctyltin diethyl maleate, dioctyltin diisooctyl maleate, etc.); dialkyltin oxides (dibutyltin oxide, dioctyltin oxide, a mixture of dibutyltin oxide and phthalic acid ester, etc.); tetravalent tin compounds (dialkyltin oxide, dialkyltin diacetate, etc.) and silyl group-containing low molecular weight silicon divalent tin compounds (such as tin octoate, tin naphthenate, and tin stearate); monoalkyltin compounds (such as monobutyltin compounds (such as monobutyltin tris-octoate and monobutyltin triisopropoxide), and monooctyltin compounds); reaction products or mixtures of amine compounds and organic tin compounds (such as reaction products or mixtures of laurylamine and tin octoate); chelate compounds (such as dibutyltin bisacetylacetonate, dioctyltin bisacetylcetonate, dibutyltin bisethylacetonate, and dioctyltin bisethylacetonate); and tin alcoholates (such as dibutyltin dimethylate, dibutyltin diethylate, dioctyltin dimethylate, and dioctyltin diethylate).

[0051] Among these, chelate compounds (such as dibutyltin bisacetylacetonate) and tin alcoholates are preferred because they have high activity as silanol condensation catalysts, and dibutyltin dilaurate is preferred because it causes little coloring when added to a curable composition, is inexpensive, and is easily available.

[0052] [2.5. Component E: Dehydrating agent] Component E is a dehydrating agent. Examples of dehydrating agents include alkoxysilane compounds, synthetic zeolites, activated alumina, silica gel, quicklime, and magnesium oxide. Among these, alkoxysilane compounds are preferred, and vinylsilane compounds are more preferred. The reason for this is that vinylsilane compounds are highly volatile and do not participate in the crosslinking reaction of the curable composition. In addition, vinylsilane compounds are also highly safe. Examples of alkoxysilane compounds include n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, methylsilicate, ethylsilicate, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, and γ-glycidoxypropyltrimethoxysilane.

[0053] Component E may be a commercially available product or a synthetic product. Commercially available examples of component E include SilQUEST A-171 (Momentive), VTMO (Evonik), and KBM-1003 (Shin-Etsu Chemical Co., Ltd.).

[0054] [2.6. Other ingredients] The curable composition may contain various additives in addition to the above-mentioned components. By including these additives, it is possible to adjust various physical properties of the curable composition and the cured product. Examples of additives include the following. These additives may be used alone or in combination of two or more.

[0055] (Adhesion promoter) The curable composition may contain an adhesion promoter. By adding an adhesion promoter, the risk of the sealant peeling off from the adherend such as a siding board can be reduced (this peeling occurs when the joint width changes due to an external force). In addition, there may be cases where the need to use a primer to improve adhesion is eliminated. In this case, simplification of the construction work is expected.

[0056] An example of an adhesion promoter is a silane coupling agent. Specific examples of silane coupling agents include isocyanate group-containing silanes (γ-isocyanate propyl trimethoxysilane, γ-isocyanate propyl triethoxysilane, γ-isocyanate propyl methyl diethoxysilane, γ-isocyanate propyl methyl dimethoxysilane, etc.); amino group-containing silanes (γ-aminopropyl trimethoxysilane, γ-aminopropyl triethoxysilane, γ-aminopropyl methyl dimethoxysilane, γ-aminopropyl methyl diethoxysilane, N-(β-aminoethyl)-γ-aminopropyl trimethoxysilane, N-(β-aminoethyl)-γ-aminopropyl methyl dimethoxysilane, N-(β-aminoethyl)-γ-aminopropyl triethoxysilane, N-(β-aminoethyl)-γ-aminopropyl methyl diethoxysilane, γ-ureidopropyl trimethoxysilane, N-phenyl-γ-aminopropyl trimethoxysilane, N-benzyl-γ-aminopropyl trimethoxysilane, silane, N-vinylbenzyl-γ-aminopropyltriethoxysilane, etc.); mercapto group-containing silanes (γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, etc.); carboxysilanes (β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis(2-methoxyethoxy)silane, N-(β-carboxymethyl)aminoethyl-γ-aminopropyltrimethoxysilane, etc.); vinyl-type unsaturated group-containing silanes (vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-acroyloxypropylmethyltriethoxysilane, etc.); halogen-containing silanes (γ-chloropropyltrimethoxysilane, etc.); isocyanurate silanes (tris(trimethoxysilyl)isocyanurate, etc.).In addition, derivatives obtained by modifying silane coupling agents, such as amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, phenylamino long-chain alkylsilanes, aminosilylated silicones, and silylated polyesters, can also be used as silane coupling agents.

[0057] The content of the adhesion promoter is preferably 0.1 to 20 parts by weight, and more preferably 0.5 to 10 parts by weight, relative to 100 parts by weight of the total content of Components A and B.

[0058] (filling material) The curable composition may contain a filler. Examples of the filler include wood flour, reinforcing fillers (pulp, cotton chips, asbestos, mica, walnut shell powder, rice husk powder, graphite, white clay, silica (fumed silica, precipitated silica, crystalline silica, fused silica, dolomite, silicic anhydride, hydrated silicic acid, etc.), carbon black, etc.), fillers (heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide, red iron oxide, fine aluminum powder, flint powder, zinc oxide, activated zinc oxide, zinc powder, zinc carbonate, shirasu balloon, etc.), and fibrous fillers (asbestos, glass fiber and glass filament, carbon fiber, Kevlar fiber, polyethylene fiber, etc.).

[0059] The content of the filler is preferably from 5 to 5,000 parts by weight, more preferably from 10 to 2,500 parts by weight, and particularly preferably from 15 to 1,500 parts by weight, relative to 100 parts by weight of the total content of components A and B.

[0060] (Plasticizer) The curable composition may contain a plasticizer. The use of a plasticizer in combination with a filler increases the elongation of the cured product and allows the incorporation of a large amount of filler.

[0061] Examples of plasticizers include phthalates (dibutyl phthalate, diheptyl phthalate, di(2-ethylhexyl) phthalate, diisodecyl phthalate, butyl benzyl phthalate, etc.); non-aromatic dibasic acid esters (dioctyl adipate, dioctyl sebacate, dibutyl sebacate, isodecyl succinate, etc.); aliphatic esters (butyl oleate, methyl acetylricinoleate, etc.); esters of polyalkylene glycols (diethylene glycol dibenzoate, triethylene glycol dibenzoate, pentaerythritol esters, etc.); phosphate esters (tricresyl phosphate, tributyl phosphate, etc.); trimellitic acid esters, polystyrenes (polystyrene, poly-α-methylstyrene, etc.); polybutadiene; polybutene; polyisobutylene; butadiene-acrylonitrile; polychloroprene; chlorinated paraffins; hydrocarbon oils (alkyldiphenyls, partially hydrogenated terphenyls, etc.); process oils; polyethers (polyether polyols (polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc.), derivatives in which the hydroxyl groups of polyether polyols are converted to ester groups, ether groups, etc.); polyester plasticizers obtained from dibasic acids and dihydric alcohols (polyesters obtained from sebacic acid, adipic acid, azelaic acid, phthalic acid, etc., and ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, etc.); vinyl polymers (obtained by polymerizing vinyl monomers such as acrylic plasticizers by various methods).

[0062] Acrylic plasticizers can be produced by high-temperature continuous polymerization without using solvents and chain transfer agents (see U.S. Pat. No. 4,414,370, JP-A-59-6207, JP-B-5-58005, JP-A-1-313522, and U.S. Pat. No. 5,010,166). Specific examples of acrylic plasticizers include ARUFON UP-1000, UP-1020, and UP-1110 (all from Toagosei Co., Ltd.), JDX-P1000, JDX-P1010, and JDX-P1020 (all from Johnson Polymer Co., Ltd.).

[0063] The content of the plasticizer is preferably 5 to 800 parts by weight, more preferably 10 to 600 parts by weight, and further preferably 10 to 500 parts by weight, relative to 100 parts by weight of the total content of Components A and B.

[0064] (Physical property adjuster) The curable composition may contain a physical property modifier that adjusts the tensile properties of the cured product. By using the physical property modifier, it is possible to increase the hardness of the cured product, or conversely, to decrease the hardness of the cured product and increase the elongation.

[0065] Examples of physical property adjusters include alkylalkoxysilanes (methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, n-propyltrimethoxysilane, etc.); alkylisopropenoxysilanes (dimethyldiisopropenoxysilane, methyltriisopropenoxysilane, etc.); alkoxysilanes having functional groups (vinyldimethylmethoxysilane, γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)aminopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, etc.); silicone varnishes; and polysiloxanes.

[0066] The content of the physical property adjusting agent is preferably 0.1 to 80 parts by weight, and more preferably 0.1 to 50 parts by weight, relative to 100 parts by weight of the total content of Components A and B.

[0067] (Thixotropic agent (anti-sagging agent)) The curable composition may contain a thixotropic agent (anti-sagging agent) to prevent sagging and improve workability.

[0068] Examples of the thixotropic agent include polyamide waxes; hydrogenated castor oil derivatives; and metal soaps (calcium stearate, aluminum stearate, barium stearate, etc.).

[0069] The content of the thixotropy-imparting agent is preferably 0.1 to 50 parts by weight, and more preferably 0.2 to 25 parts by weight, relative to 100 parts by weight of the total content of Components A and B.

[0070] (light curing substance) The curable composition may contain a photocurable substance. A photocurable substance is a substance that undergoes a chemical change in a short time by the action of light, resulting in a change in physical properties (such as curing). By including a photocurable substance, the tackiness (residual tack) of the surface of the cured product can be reduced. A typical photocurable substance can be cured by leaving it at room temperature for one day in a sunny position indoors (such as near a window). Many photocurable substances are known, such as organic monomers, oligomers, resins, and compositions containing these, and the types are not particularly limited. Examples of photocurable substances include unsaturated acrylic compounds, polyvinyl cinnamates, and azido resins.

[0071] Specific examples of unsaturated acrylic compounds include (meth)acrylic acid esters of low molecular weight alcohols (ethylene glycol, glycerin, trimethylolpropane, pentaerythritol, neopentyl alcohol, etc.); (meth)acrylic acid esters of alcohols obtained by modifying acids (bisphenol A, isocyanuric acid) or low molecular weight alcohols with ethylene oxide, propylene oxide, etc.; (meth)acrylic acid esters (polyether polyols whose main chain is polyether and has hydroxyl groups at the terminals, polyols whose main chain is polyether, and polyols obtained by radical polymerization of vinyl monomers in polyols whose main chain is polyether). polymer polyols obtained by reacting an epoxy resin (such as bisphenol A type or novolak type) with (meth)acrylic acid, polyester polyols having a polyester main chain and hydroxyl groups at the terminals, and polyols having a vinyl or (meth)acrylic copolymer main chain and hydroxyl groups in the main chain; epoxy acrylate oligomers obtained by reacting an epoxy resin (such as bisphenol A type or novolak type) with (meth)acrylic acid; and urethane acrylate oligomers having urethane bonds and (meth)acrylic groups in the molecular chain obtained by reacting a polyol, a polyisocyanate, a hydroxyl group-containing (meth)acrylate, etc.

[0072] The content of the photocurable substance is preferably 0.01 to 30 parts by weight, assuming the total content of components A and B to be 100 parts by weight.

[0073] (Antioxidants and Light Stabilizers) The curable composition may contain an antioxidant and / or a light stabilizer. Various antioxidants and light stabilizers are known. For example, the substances described in [Kenichi Saruwatari et al., "Antioxidant Handbook," Taiseisha, 1976] and [Zenjiro Osawa, editor, "Deterioration and Stabilization of Polymer Materials," CMC, 1990, pp. 235-242] can be mentioned.

[0074] Examples of the antioxidant include thioether-based antioxidants such as ADK STAB PEP-36 and ADK STAB AO-23 (all manufactured by ADEKA Corporation); phosphorus-based antioxidants such as Irgafos38, Irgafos168, and IrgafosP-EPQ (all manufactured by Ciba Specialty Chemicals); and hindered phenol-based antioxidants. Among the above, hindered phenol-based antioxidants are preferred.

[0075] Specific examples of hindered phenol-based antioxidants include 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-4-ethylphenol, mono (or di or tri) (α-methylbenzyl)phenol, 2,2'-methylenebis(4-ethyl-6-t-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), 4,4'-butylidenebis(3-methyl-6-t-butylphenol), 4,4'-thiobis(3-methyl-6-t-butylphenol), and 2,5-di-t-butylhydroquinone. , 2,5-di-t-amylhydroquinone, triethylene glycol-bis-[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylene 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, bis(3,5-di-t-butyl-4-hydroxybenzyl)propionate, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 3,5-di-t-butyl-4-hydroxy-benzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, bis(3,5-di-t-butyl-4-hydroxybenzyl)propionate ethyl benzylphosphonate) calcium, tris-(3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 2,4-bis[(octylthio)methyl]o-cresol, N,N'-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyl]hydrazine, tris(2,4-di-t-butylphenyl)phosphite, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)-benzotriazole, methyl-3-[3-t-bu ethyl-5-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]propionate-polyethylene glycol (molecular weight about 300) condensate, hydroxyphenylbenzotriazole derivatives, 2-(3,5-di-t-butyl-4-hydroxybenzyl)-2-n-butylmalonic acid bis(1,2,2,6,6-pentamethyl-4-piperidyl), 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate.

[0076] Examples of commercially available antioxidants include Nocrac 200, Nocrac M-17, Nocrac SP, Nocrac SP-N, Nocrac NS-5, Nocrac NS-6, Nocrac NS-30, Nocrac 300, Nocrac NS-7, and Nocrac DAH (all manufactured by Ouchi Shinko Chemical Industry Co., Ltd.); ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO-616, ADK STAB AO-635, ADK STAB AO-658, ADK STAB AO-80, ADK STAB AO-15, ADK STAB AO-18, ADK STAB 328, and ADK STAB AO-37 (all manufactured by ADEKA Corporation); IRGANOX-245, IRGANOX-259, IRGANOX-565, IRGANOX-1010, IRGANOX-1024, IRGANOX-1035, IRGANOX-1076, IRGANOX-1081, IRGANOX-1098, IRGANOX-1222, IRGANOX-1330, IRGANOX-1425WL (all manufactured by Chiba Specialty Chemicals); Sumilizer GM, Sumilizer GA-80, Sumilizer GS (all manufactured by Sumitomo Chemical Co., Ltd.).

[0077] Examples of light stabilizers include ultraviolet absorbers (benzotriazole compounds such as Tinuvin P, Tinuvin 234, Tinuvin 320, Tinuvin 326, Tinuvin 327, Tinuvin 329, and Tinuvin 213 (all manufactured by Ciba Specialty Chemicals); triazine light stabilizers such as Tinuvin 1577; benzophenone compounds such as CHIMASSORB81; benzoate compounds such as Tinuvin 120 (manufactured by Ciba Specialty Chemicals); and hindered amine compounds). Of the above, hindered amine compounds are preferred.

[0078] Specific examples of the hindered amine compound include dimethyl succinate-1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, poly[{6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl}{(2,2,6,6-tetramethyl-4-piperidyl)imino}], N,N'-bis(3aminopropyl)ethylenediamine-2,4-bis[N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino]-6-chloro-1,3,5-triazine condensate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, and bis(2,2,6,6-tetramethyl-4-piperidinyl)succinate.

[0079] Examples of commercially available light stabilizers include Tinuvin 622LD, Tinuvin 144, CHIMASSORB944LD, and CHIMASSORB119FL (all manufactured by Chiba Specialty Chemicals), Adeka STAB LA-52, Adeka STAB LA-57, Adeka STAB LA-62, Adeka STAB LA-67, Adeka STAB LA-63, Adeka STAB LA-68, Adeka STAB LA-82, and Adeka STAB LA-87 (manufactured by ADEKA Corporation); Sanol LS-770, Sanol LS-765, Sanol LS-292, Sanol LS-2626, Sanol LS-1114, Sanol LS-744, and Sanol LS-440 (manufactured by Chiba Specialty Chemicals).

[0080] An antioxidant and a light stabilizer may be used in combination. By using them in combination, the effect of each agent may be further improved, and the heat resistance, weather resistance, etc. of the cured product may be improved. For example, in order to improve weather resistance, an ultraviolet absorber and a hindered amine compound (HALS) may be combined. This combination is preferable because it can further improve the effect of each agent.

[0081] The content of the antioxidant and / or light stabilizer is preferably 0.1 to 20 parts by weight, respectively, when the total content of Components A and B is 100 parts by weight.

[0082] 3. Composition of the Curable Composition In the curable composition, the content ratio (weight ratio) of Component A to Component B is preferably Component A:Component B=(1:99) to (99:1), more preferably (10:90) to (90:10), and even more preferably (20:80) to (80:20). By blending the two components in the above range, it is easy to obtain a cured product that has both strength and elongation.

[0083] In the curable composition, the content of Component C is preferably 0.01 to 10 parts by weight, relative to 100 parts by weight of the total content of Components A and B.

[0084] The content of component D is preferably 0.1 to 5 parts by weight, assuming that the total content of components A and B is 100 parts by weight.

[0085] The content of component E is preferably 0.1 to 10 parts by weight, assuming the total content of components A and B to be 100 parts by weight.

[0086] 4. Form of the curable composition The curable composition according to one embodiment of the present invention may be a one-component type or a multi-component type. A one-component type curable composition is a composition in which all the components are mixed in advance and then sealed and stored. The one-component type curable composition is cured by moisture in the air after use. In the multi-component type curable composition, each of the components A to E is prepared separately, and both are mixed at the time of use. The multi-component type curable composition may contain other optional agents (such as a colorant) in addition to the above components.

[0087] When the curable composition is prepared as a multi-component type, a colorant can be further added when mixing the respective components. The colorant is preferably a paste obtained by mixing, for example, a pigment, a plasticizer, and, if necessary, a filler, from the viewpoint of workability.

[0088] In addition, for multi-component curable compositions, a retarder can be added when mixing the base agent and the curing agent, allowing fine adjustment of the curing speed at the work site.

[0089] [5. Cured product] A cured product is obtained from the curable composition obtained by the above-mentioned manufacturing method by a known method. For example, the curable composition can absorb ambient moisture and spontaneously change into a cured product by the above-mentioned manufacturing method. The use of the cured product is not particularly limited. Examples include architectural and industrial sealants, electrical and electronic component materials (such as solar cell back sealants), electrical insulating materials (such as insulating coating materials for wires and cables), pressure sensitive adhesives, adhesives, elastic adhesives, contact adhesives, tile adhesives, paints, coating materials, sealing materials for can lids, etc., potting agents for electrical and electronic use, films, gaskets, casting materials, various molding materials, artificial marble, rust-proofing and waterproofing sealants for cut parts of wired glass or laminated glass, and waterproofing agents.

[0090] In one embodiment, the cured product is in the form of a film. The lower limit of the thickness of the film produced may be 0.1 mm or more, 0.5 mm or more, 1 mm or more, 5 mm or more, or 10 mm or more. The upper limit of the thickness of the film produced may be 100 mm or less, 90 mm or less, 80 mm or less, 70 mm or less, 60 mm or less, or 50 mm or less.

[0091] The film-like cured product can be produced, for example, by applying the curable composition to a substrate and then curing it. The film may be used in a state where it is peeled off from the substrate, or in a state where the substrate and the film are integrated. Examples of applications of the film-like cured product include sealing materials, coating agents, and adhesives.

[0092] [6. Summary] The present invention includes the following aspects. <1> A method for producing a curable composition comprising the following components A to D: Component A: a (meth)acrylic polymer having a silyl group; Component B: epoxy compound; Component C: An epoxy hardener that generates amino groups upon contact with moisture; Component D: Curing catalyst; Component E: Dehydrating agent; A production method comprising the following steps 1 to 4: Step 1: mixing the component A and the component E; Step 2: adding and mixing the component D to the mixture obtained in step 1; Step 3: further mixing component C with the mixture obtained in step 2; Step 4: further mixing component B into the mixture obtained in step 3; Here, the component A is The molecule has an XY diblock structure having an X block and a Y block, or an XYX triblock structure, The number of repeating units derived from the silyl group-containing (meth)acrylic acid ester monomer contained in the X block is more than 2.0 on average, the content of repeating units derived from silyl group-containing (meth)acrylic acid ester monomers contained in the Y block is 0% by weight or more and less than 5% by weight based on the weight of all repeating units contained in the Y block, The molecular weight distribution (Mw / Mn) is 1.8 or less. <2> The above component A is CH2=C(R 1 )COOR 2 (In the formula, R 1 is a hydrogen atom or a methyl group, and R 2 is a group having 9 or more carbon atoms), <1> The manufacturing method described in <3> The number average molecular weight of the component A is 2,000 to 50,000. <1> or <2> The manufacturing method described in <4> The component B is at least one selected from the group consisting of bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, aliphatic epoxy compounds, novolac type epoxy compounds, and glycidylamine type epoxy compounds. <1> ~ <3> 13. The method for producing a semiconductor device according to any one of the preceding claims. <5> The component C is a ketimine. <1> ~ <4> 13. The method for producing a semiconductor device according to any one of the preceding claims. <6> <1> ~ <5> 2. A cured product obtained by curing the curable composition obtained by the production method according to claim 1. EXAMPLES

[0093] [Measurement method] [Number average molecular weight] The following device was used to measure the number average molecular weight. The measured value is a polystyrene-equivalent molecular weight. Liquid delivery system: HLC-8120GPC (Tosoh Corporation) Column: TSK-GEL H type (Tosoh Corporation) Solvent: THF

[0094] [Terminal silyl group introduction rate] 1 The introduction rate of terminal silyl groups was calculated from the results of H-NMR measurement. 1 The following equipment was used for H-NMR measurements. Measuring instrument: JNM-LA400 (manufactured by JEOL Ltd.) Solvent: CDCl3

[0095] [Tensile properties] The tensile properties were measured by cutting No. 3 dumbbell-shaped test pieces from the cured products in accordance with JIS K 6251. The tensile properties were measured at 23°C and 55% RH using an autograph. The evaluation items were the stress at 100% elongation, the stress at break, and the elongation at break.

[0096] [Tear strength] A crescent-shaped test piece was obtained from the cured product, and the tear strength was measured in accordance with JIS K 6252. The tear strength was measured using an autograph at 23°C and 55% RH.

[0097] [viscosity] The viscosity of the curable composition immediately after production was measured using a viscometer (VISCOMETER TV-25, Toki Sangyo Co., Ltd.). The measurement was performed in accordance with JIS K 7117-2. The rotor used in the measurement was a 3°×R12 cone rotor. The rotation speed during the measurement was 1 rpm.

[0098] 〔material〕 The materials used in the examples and comparative examples are as follows. Ingredient A Silyl group-containing (meth)acrylic polymer (A-1) obtained in the production example ●Ingredient B Epoxy compound (B-1) (JER828, Mitsubishi Chemical Corporation, bisphenol A type liquid epoxy resin) Epoxy compound (B-2) (Epolite 4000, Kyoeisha Chemical Co., Ltd., hydrogenated bisphenol A diglycidyl ether) ●Component C Ketimine type epoxy hardener (H30, Mitsubishi Chemical Corporation) ●Component D Curing catalyst (Neostan U-220H, Nitto Kasei Co., Ltd., dibutyltin) ●Ingredient E Dehydrating agents (Silquest A-171, MOMENTIVE, vinyltrimethoxysilane) Component A' (a (meth)acrylic polymer having a silyl group other than Component A) Silyl group-containing (meth)acrylic polymer (A'-1) obtained in Comparative Production Example Adhesion enhancer N-2-(aminoethyl)-3-aminopropyltrimethoxysilane (KBM-603, Shin-Etsu Chemical Co., Ltd.)

[0099] [Production Example: Synthesis of (meth)acrylic polymer (A-1)] A (meth)acrylic polymer (A-1) having a silyl group was synthesized according to the following procedure. This polymer corresponds to component A. (preparation) 1. A 2000 mL three-neck flask was prepared. 108 g of ethyl acrylate, 707 g of n-butyl acrylate, and 186 g of octadecyl acrylate were charged into the flask and mixed. This mixture is referred to as "(meth)acrylic acid ester monomer mixture." 2. Another stirring vessel was prepared. 52.7 mg of cupric bromide (CuBr2), 54.4 mg of hexamethyltris(2-aminoethyl)amine (Me6TREN) and 1.82 g of methanol were charged into the stirring vessel and stirred under a nitrogen stream until a homogeneous solution was obtained. This homogeneous solution is referred to as the "copper solution." The amount of copper contained in the copper solution was equivalent to 15 ppm relative to the total amount of the (meth)acrylic acid ester monomer mixture. 3. Another stirring vessel was prepared. 30.8 mL of methanol, 1.0 g of ascorbic acid, and 1.6 mL of triethylamine were charged into the stirring vessel and stirred under a nitrogen stream to obtain a homogeneous solution. This homogeneous solution is called "ascorbic acid solution." [1st step] 4. 5.60g of ethyl α-bromobutyrate (initiator; 0.029 mol), 20% by weight of the total amount of (meth)acrylic acid ester monomer mixture, 10g of 3-methacryloxypropylmethyldimethoxysilane (0.045 mol; 1.5 molar equivalent to the initiator), 107.68g of methanol, and the total amount of copper solution were added to the stirrer, and stirred for 30 minutes under a nitrogen stream to obtain a homogeneous solution. The stirrer used at this time was a stirrer with a jacket temperature control, and the jacket temperature was set to 45°C. 5. When the temperature in the polymerization system reached 40°C or higher, the ascorbic acid solution was continuously dripped to start the polymerization reaction. The dripping rate of the ascorbic acid solution was set to a rate at which 144 mg of ascorbic acid was added to the polymerization system per hour. 6. The temperature in the polymerization system was monitored and it rose as soon as the dropping of ascorbic acid started, reached a maximum temperature, and then gradually decreased. When the temperature difference between the temperature in the polymerization system and the jacket temperature reached 1°C, a small amount of the reaction solution in the polymerization system was sampled and analyzed by gas chromatography. As a result, 90% by weight of the (meth)acrylic acid ester monomer mixture initially charged had been consumed. [Second process] 7. The remaining (meth)acrylic acid ester monomer mixture that was not added in the first step (80% by weight of the total amount) was continuously added dropwise to the polymerization system over a period of 90 minutes. The ascorbic acid solution was added dropwise at a rate of 48 mg of ascorbic acid per hour to the polymerization system. Sampling was also carried out sequentially and analyzed by gas chromatography. The polymerization was continued until 88% by weight of the total (meth)acrylic acid ester monomer mixture added to the polymerization system was consumed. [3rd step] 8. 11 g of 3-methacryloxypropylmethyldimethoxysilane (0.049 mol; 1.6 molar equivalents relative to the initiator) was added to the polymerization system. The ascorbic acid solution was continuously added dropwise until 98% by weight of the total amount of the (meth)acrylic acid ester monomer mixture added to the polymerization system was consumed. Thereafter, the addition of the ascorbic acid solution was stopped to terminate the polymerization. 9. The jacket temperature was changed to 80°C, and the solvent was then volatilized. A diaphragm pump was used first, and then a vacuum pump was used. After volatilization was completed, the jacket temperature was cooled to 60°C or less. [purification] 10. 1000g of butyl acetate was added to a jacket temperature-controlled stirring device and mixed with the polymer after devolatilization until a homogeneous solution was obtained. An adsorbent was added to this homogeneous solution and stirred for 1 hour. As the adsorbent, 10g of Kyoward 500SH (Kyowa Chemical Industry Co., Ltd.) and 10g of Kyoward 700SEN-S (Kyowa Chemical Industry Co., Ltd.) were used. 11. After the stirring was completed, the mixture was filtered through a filter equipped with a bag filter cloth. This resulted in a clear polymer solution. 1.5 g of an antioxidant (Sumilizer GS; Sumitomo Chemical Co., Ltd.) was added to the solution and mixed until homogenous. Thereafter, the solvent was removed from the solution using a diaphragm pump first and then a vacuum pump. In this way, a (meth)acrylic copolymer (A-1) was obtained.

[0100] The (meth)acrylic copolymer (A-1) is an XYX type block copolymer, with a number average molecular weight of 5,5000, a molecular weight distribution of 1.11, and a number of silyl groups introduced per molecule of 2.1. The X block of the (meth)acrylic copolymer (A-1) had an average of 2.1 repeating units derived from silyl group-containing (meth)acrylic acid ester monomers per copolymer molecule. The Y block of the (meth)acrylic copolymer (A-1) had 1.1% by weight of repeating units derived from silyl group-containing (meth)acrylic acid ester monomers (based on the weight of all repeating units contained in the Y block). The repeating units derived from silyl group-containing (meth)acrylic acid ester monomers contained in the Y block are extremely small. Therefore, when calculated with two significant digits, the repeating units derived from silyl group-containing (meth)acrylic acid ester monomers contained in the entire molecule and the repeating units derived from silyl group-containing (meth)acrylic acid ester monomers contained in the entire X block are both 2.1.

[0101] Comparative Production Example 1: Synthesis of Silyl Group-Containing (Meth)acrylic Polymer (A'-1) A (meth)acrylic polymer having a methyldimethoxysilyl group introduced at the molecular end was synthesized by the following procedure. The (meth)acrylic polymer does not fall under component A because the silyl group is located only at the molecular end and the whole molecule does not contain an X block. 1. The inside of a stainless steel reaction vessel equipped with a stirrer was deoxidized. 7.7 g of cuprous bromide and 200 g of butyl acrylate were charged into the reaction vessel and stirred while heating. 2. 90g of acetonitrile and 17.6g of diethyl 2,5-dibromoadipate (initiator) were added to a reaction vessel and mixed. The temperature of the mixture was adjusted to about 80°C, and then pentamethyldiethylenetriamine was added to initiate the polymerization reaction. 3. 800 g of butyl acrylate was gradually added to the reaction vessel to proceed with the polymerization reaction. During the polymerization, pentamethyldiethylenetriamine was appropriately added to adjust the polymerization rate. The total amount of pentamethyldiethylenetriamine used during the polymerization was 1.4 g. During the polymerization reaction, the internal temperature of the reaction vessel was adjusted to about 80 to about 90°C. 4. When the monomer conversion rate (polymerization reaction rate) reached about 95% or more, the volatile matter was removed by devolatilization under reduced pressure to obtain a concentrated (meth)acrylic polymer. 5. To the polymer concentrate obtained in step 4 was added 200 g of 1,7-octadiene, 260 g of acetonitrile and 3.1 g of pentamethyldiethylenetriamine. 6. The mixture was heated and stirred for several hours while adjusting the internal temperature of the reaction vessel to about 80 to about 90° C. This caused the polymer terminals to react with 1,7-octadiene, and introduced alkenyl groups into the polymer terminals. 7. Acetonitrile and unreacted 1,7-octadiene were removed by volatilization under reduced pressure to obtain a concentrated polymer having alkenyl groups at its terminals. 8. The concentrate obtained in step 7 was diluted with butyl acetate, and a filter aid and an adsorbent (Kyoward 700SEN and Kyoward 500SH, Kyowa Chemical Industry Co., Ltd.) were added. 9. The mixture obtained in step 8 was heated and stirred at about 80 to 100° C., and the solid components were filtered off. The filtrate was then concentrated to obtain a crude polymer. 10. A heat stabilizer (Sumilizer GS, Sumitomo Chemical Co., Ltd.) and an adsorbent (Kyoward 700SEN and Kyoward 500SH) were added to the crude polymer. 11. The temperature of the system was increased while removing volatilization under reduced pressure and heating with stirring, and the removal of volatilization under reduced pressure and heating with stirring were continued at about 170 to about 200° C. for several hours. 12. Adsorbents (Kyoward 700SEN and Kyoward 500SH) and butyl acetate in an amount about 10 times by weight relative to the crude polymer product were added, and the mixture was heated and stirred at about 170 to about 200° C. for several hours. 13. The treated liquid obtained in step 12 was further diluted with butyl acetate, and the adsorbent was filtered off. The filtrate was concentrated to obtain a polymer having alkenyl groups at both ends. 14. 500 g of the polymer obtained in step 13 was mixed with 7.7 g of methyldimethoxysilane, 2.5 g of methyl orthoformate, and 50 mg of platinum catalyst, and heated and stirred at about 100° C. for about 1 hour. As the platinum catalyst, an isopropanol solution of bis(1,3-divinyl-1,1,3,3-tetramethyldisiloxane) platinum complex catalyst was used. 15. Volatile components (unreacted methyldimethoxysilane, etc.) were distilled off under reduced pressure to obtain a (meth)acrylic polymer (A'-1) having methyldimethoxysilyl groups introduced at the molecular ends. The (meth)acrylic polymer (A'-1) had a number average molecular weight of 27,000, a molecular weight distribution of 1.2, and the number of silyl groups introduced per molecule was 2.0.

[0102] [Examples 1-2] A cured product was prepared according to the following procedure. 1. Prepare each component in the amount (unit: g) shown in Table 1. 2. Components A and E were placed in a 150 cc plastic cup and mixed using a spoon. 3. Ingredient D was added to the cup and further mixed using a spoon. 4. The tackifier was added to the cup and further mixed using a spoon. 5. Ingredient C was added to the cup and further mixed using a spoon. 6. Ingredient B was added to the cup and further mixed using a spoon. 7. Using a planetary stirring and defoaming device (ARE-310, Thinky Corporation), the mixture was stirred (1600 rpm x 90 seconds) and defoamed (2200 rpm x 300 seconds) to obtain a curable composition. The viscosity of the obtained curable composition was measured immediately after production and after storage. 8. The obtained curable composition was cured under conditions of 23°C and 55% RH to obtain a cured product. The obtained cured product was subjected to a tensile test and a tear test.

[0103] [Comparative Examples 1-2, Reference Examples] A cured product was prepared according to the following procedure. 1. Prepare each component in the amount (unit: g) shown in Table 1. 2. These ingredients were placed in a 150cc plastic cup and mixed using a spoon. Mixing was started after all ingredients were placed in the cup. 3. Using a planetary stirring and defoaming device (ARE-310, Thinky Corporation), the mixture was stirred (1600 rpm x 90 seconds) and defoamed (2200 rpm x 300 seconds) to obtain a curable composition. The viscosity of the obtained curable composition was measured immediately after production and after storage. 4. The obtained curable composition was cured under conditions of 23°C and 55% RH to obtain a cured product. The obtained cured product was subjected to a tensile test and a tear test.

[0104] 〔result〕 The results are shown in Table 1. [Table 1]

[0105] As can be seen from Table 1, the curable compositions according to Example 1 and Comparative Example 1 have the same composition, and the curable compositions according to Example 2 and Comparative Example 2 have the same composition. The only difference between the Examples and Comparative Examples is the mixing order of each component. However, the initial viscosity of the curable composition according to the Examples was significantly lower than that of the curable composition according to the Comparative Example, and was comparable to that of the Reference Example. Although component A tends to have a higher viscosity than component A', the initial viscosity of the curable composition according to the Examples was comparable to that of the curable composition containing component A', despite containing component A. From this, it was found that the initial viscosity of the curable composition can be reduced by the manufacturing method according to one aspect of the present invention.

[0106] The cured products of the Examples and the cured products of the Comparative Examples had similar tensile properties and tear strengths. [Industrial Applicability]

[0107] The curable composition produced by the method according to one embodiment of the present invention can be suitably used for pressure sensitive adhesives, sealing materials, adhesives, mold release agents, vibration isolators, vibration dampers, soundproofing materials, foaming materials, paints, spray materials, etc.

Claims

1. A method for producing a curable composition comprising the following components A to D: Component A: a (meth)acrylic polymer having a silyl group; Component B: epoxy compound; Component C: an epoxy curing agent that generates an amino group upon contact with moisture; Component D: curing catalyst; Component E: Dehydrating agent; A method for producing a composition comprising the following steps 1 to 4: Step 1: mixing the component A and the component E; Step 2: adding and mixing the component D to the mixture obtained in step 1; Step 3: further mixing the component C into the mixture obtained in step 2; Step 4: further mixing the component B into the mixture obtained in step 3; Here, the component A is The molecule has an XY diblock structure having an X block and a Y block or an XYX triblock structure, the number of repeating units derived from the silyl group-containing (meth)acrylic acid ester monomer contained in the X block is more than 2.0 on average, a repeating unit derived from a silyl group-containing (meth)acrylic acid ester monomer contained in the Y block is 0% by weight or more and less than 5% by weight based on the weight of all repeating units contained in the Y block, The molecular weight distribution (Mw / Mn) is 1.8 or less.

2. The above component A is CH ２ = C(R １ ) COOR ２ (In the formula, R １ is a hydrogen atom or a methyl group, R ２ The method according to claim 1 , wherein the repeating unit derived from

3. The method according to claim 1, wherein the number average molecular weight of the component A is 2,000 to 50,000.

4. 2. The method according to claim 1, wherein the component B is at least one selected from the group consisting of bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, aliphatic epoxy compounds, novolac type epoxy compounds, and glycidylamine type epoxy compounds.

5. The method according to claim 1 , wherein the component C is a ketimine.

6. A cured product obtained by curing the curable composition obtained by the method according to any one of claims 1 to 5.

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