Curable composition and cured product

Abstract

To provide a curable composition capable of providing a cured product reduced in surface tackiness and bleed-out.SOLUTION: The curable composition comprises (A) a hydrolyzable silyl group-containing organic polymer, (B) a hydrolyzable silyl group-containing compound, and (C) a curing catalyst. The component (B) is one or more selected from the group consisting of compounds represented by the following formulae (1) to (4).SELECTED DRAWING: None

Description

[Technical Field]

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

[0002] Products using hydrolyzable silyl group-containing organic polymers are widely used worldwide in curable compositions such as sealants, pressure sensitive adhesives, and adhesives. For example, Patent Document 1 discloses a curable composition containing a vinyl polymer (A) having at least one crosslinkable silyl group and whose main chain is produced by living radical polymerization, and hydrophobic finely powdered silica (B).

[0003] In conventional techniques, it has been necessary to blend various raw materials to obtain desired physical properties, such as the use of a plasticizer to adjust the flexibility of the cured product or the ease of handling of the curable composition.

[0004] However, in general, cured products obtained by curing curable compositions that use large amounts of plasticizers may have poor surface stickiness (also known as surface tack) or the plasticizer may bleed out onto the surface of the cured product during use, resulting in practical problems such as reduced design, physical properties, and usability. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2005-320519 Summary of the Invention [Problem to be solved by the invention]

[0006] In view of the above background, there has been a demand for new plasticizers and curable compositions that provide cured products with reduced surface tack and bleed-out. [Means for solving the problem]

[0007] The present inventors have conducted extensive research to solve the above problems and have completed the present invention.

[0008] That is, the present invention includes the following aspects. <1> a hydrolyzable silyl group-containing organic polymer as component (A); Component (B) is one or more hydrolyzable silyl group-containing compounds selected from the group consisting of compounds represented by the following formulas (1) to (4), [ka] (In the formulas (1) to (4), R 1 ~R 6 each independently represents a divalent organic group, X represents a hydrolyzable silyl group, and FA represents a fatty acid. (C) a curing catalyst; For 100 parts by weight of the component (A), The content of the (B) component is 0.01 parts by weight to 1000.00 parts by weight, The content of the component (C) in the curable composition is 0.001 to 20,000 parts by weight. <2> The main component of the main chain of the component (A) is one or more selected from polyoxyalkylene, poly((meth)acrylic acid ester), polyolefin, polyurethane, polysulfide, epoxy resin, and polysiloxane. <1> The curable composition according to claim 1. <3> The molecular weight distribution of the component (A) is 1.00 to 5.00. <1> or <2> The curable composition according to claim 1. <4> The hydrolyzable silyl groups of the components (A) and (B) are represented by the following general formula (5): <1> ~ <3> The curable composition according to any one of the preceding claims. -Si(R 7 ) 3-a (Y) a (5) (In the formula, R 7each independently represents a hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group may contain a heteroatom. Each Y independently represents a hydroxyl group or a hydrolyzable group. a represents a natural number of 1 to 3. <5> R 1 ~R 6 is an ester bond, an ether bond, an amide bond, a urethane bond, a thioether bond, a carbonate bond, a urea bond, or a divalent hydrocarbon group having two or more carbon atoms which may have a hetero atom, or contains any of these; <1> ~ <4> The curable composition according to any one of the preceding claims. <6> The component (B) is represented by the following general formulas (7) to (10): <1> ~ <5> The curable composition according to any one of the preceding claims. [ka] (In the formulas (7) to (10), X and FA are the same as those in the formulas (1) to (4), and R 1a ~R 6a each independently represents a divalent organic group. <7> <1> ~ <6> A cured product obtained by curing the curable composition according to any one of the preceding items. <8> <1> ~ <6> 10. An adhesive comprising the curable composition according to any one of the preceding items. <9> <1> ~ <6> A pressure-sensitive adhesive comprising the curable composition according to any one of the preceding items. <10> <1> ~ <6> A sealant comprising the curable composition according to any one of the preceding items. <11> <1> ~ <6> A sealant comprising the curable composition according to any one of the preceding items. <12> A compound represented by any one of the following general formulas (7) to (10): [ka] (In the formulas (7) to (10), R 1a ~R 6aeach independently represents a divalent organic group, X represents a hydrolyzable silyl group, and FA represents a fatty acid. [Effects of the Invention]

[0009] According to one embodiment of the present invention, it is possible to provide a curable composition that can provide a cured product with reduced surface tack and bleed-out. DETAILED DESCRIPTION OF THE INVENTION

[0010] An embodiment of the present invention will be described below, but the present invention is not limited to this embodiment.

[0011] The present invention is not limited to the configurations described below, and various modifications are possible within the scope of the claims.

[0012] Furthermore, embodiments or examples obtained by combining the technical means disclosed in different embodiments or examples are also included within the technical scope of the present invention.

[0013] Furthermore, new technical features can be formed by combining the technical means disclosed in each embodiment.

[0014] All academic and patent literature cited in this specification is incorporated herein by reference.

[0015] Furthermore, unless otherwise specified in this specification, "A to B" representing a numerical range means "A or more (A or larger than A) and B or less (B or smaller than B)."

[0016] 1. Technical Concept of the Present Invention Conventionally, curable compositions containing hydrolyzable silyl group-containing organic polymers have been known in the fields of sealants, adhesives, pressure-sensitive adhesives, potting agents, etc. In order to improve the flexibility of the cured product, it is common practice to blend a plasticizer into such curable compositions.

[0017] However, in the case of a curable composition containing a plasticizer, there have been cases where the surface of the cured product becomes sticky (surface tack) after curing, and the plasticizer bleeds out from the surface of the cured product.

[0018] In view of these circumstances, the present inventors have conducted extensive research with the aim of providing a curable composition capable of providing a cured product with reduced surface tack and bleed-out. As a result, the present inventors have independently and surprisingly discovered a novel finding that, by using a curable composition containing a hydrolyzable silyl group-containing organic polymer and a hydrolyzable silyl group-containing compound represented by any one of formulas (1) to (4), a cured product with reduced surface tack and bleed-out can be obtained, and have completed the present invention.

[0019] In one embodiment, the cured product has flexibility and strength equivalent to or greater than those of conventional cured products containing plasticizers. Therefore, it can be used in situations where the bonded surface has a complex shape or requires conformability to deformation, while still maintaining strength. In one embodiment, the cured product has improved heat resistance compared to conventional cured products.

[0020] Furthermore, the hydrolyzable silyl group-containing compounds represented by formulas (1) to (4) are glycerin lipid derivatives and have low dependency on fossil resources, which is preferable from the viewpoint of sustainability required in a future carbon-recycling society.

[0021] [2. Curable composition] A curable composition according to one embodiment of the present invention comprises a hydrolyzable silyl group-containing organic polymer as component (A), a hydrolyzable silyl group-containing compound as component (B), and a curing catalyst as component (C), wherein the component (B) is at least one compound selected from the group consisting of compounds represented by the following formulas (1) to (4): [ka] (In the formulas (1) to (4), R 1 ~R 6each independently represents a divalent organic group, X represents a hydrolyzable silyl group, and FA represents a fatty acid. The content of the component (B) is 0.01 to 1000.00 parts by weight, and the content of the component (C) is 0.001 to 20.000 parts by weight, relative to 100 parts by weight of the component (A).

[0022] In this specification, the "curable composition according to one embodiment of the present invention" may be referred to as the "curable composition of the present invention."

[0023] The present curable composition has the above-described structure and therefore has the advantage of being able to provide a cured product with reduced surface tack and bleed-out.

[0024] Furthermore, the present curable composition contains a hydrolyzable silyl group-containing polymer as component (A), which allows it to be cured by atmospheric moisture, making it easy to handle and providing a cured product with high tackiness or adhesiveness.

[0025] Furthermore, this curable composition contains a hydrolyzable silyl group-containing compound as component (B). This compound is a glycerin lipid derivative and can be produced from biomass-derived raw materials, which are essential for a sustainable society. Therefore, it is highly sustainable, reduces GHG emissions from the plasticizer itself or the curable composition, reduces environmental impact, and is highly safe. It also improves the heat resistance of the cured product.

[0026] In this specification, the tackiness of a cured product is evaluated by the test method described in the Examples below. Cured products with evaluation results of 1 to 3 can be said to have reduced surface tackiness.

[0027] In this specification, the bleeding out of the cured product is evaluated by the test method described in the Examples below. A cured product in which no adhesion of the liquid component is observed can be said to have reduced bleeding out.

[0028] In this specification, the flexibility of a cured product is evaluated by its modulus at 50% elongation (also referred to as "M50") (see the Examples of the present application for specific measurement methods). If the M50 of a cured product obtained by curing a curable composition using an external stimulus (e.g., moisture) is smaller than the M50 of a cured product obtained by curing only component (A), it can be said that the flexibility of the cured product is improved.

[0029] In this specification, the heat resistance of a cured product is evaluated by the 5% weight loss temperature (see the examples of the present application for specific measurement methods). A cured product with a 5% weight loss temperature of 300°C or higher can be said to have high heat resistance.

[0030] <Component (A): Hydrolyzable Silyl Group-Containing Polymer> The curable composition contains a hydrolyzable silyl group-containing organic polymer as component (A).

[0031] The hydrolyzable silyl group-containing organic polymer may be a curable resin. It can also be said that the curable composition contains the hydrolyzable silyl group-containing organic polymer, which is component (A), as the curable resin.

[0032] In this specification, the term "hydrolyzable silyl group-containing organic polymer" refers to an organic polymer having an average of 0.5 or more hydrolyzable silyl groups per molecule. The hydrolyzable silyl group-containing organic polymer may be an aggregate of organic polymer molecules having different numbers of hydrolyzable silyl groups per molecule. In such an aggregate, the average number of hydrolyzable silyl groups per molecule is 0.5 or more.

[0033] The assemblies may include any combination of organic polymer molecules having no hydrolyzable silyl groups (non-functionalized polymer molecules), organic polymer molecules having one hydrolyzable silyl group (mono-functionalized polymer molecules), and organic polymer molecules having one or more hydrolyzable silyl groups (poly-functionalized polymer molecules). In one embodiment, the assemblies are composed exclusively of mono-functionalized polymer molecules. In one embodiment, the assemblies include non-functionalized polymer molecules and / or poly-functionalized polymer molecules in addition to mono-functionalized polymer molecules. In one embodiment, the assemblies include non-functionalized polymer molecules and poly-functionalized polymer molecules.

[0034] The position of the hydrolyzable silyl group in the organic polymer molecule having the hydrolyzable silyl group is not particularly limited. For example, a monofunctionalized polymer molecule may have a hydrolyzable silyl group at only one end of the main chain. For example, a multifunctionalized polymer molecule may have a hydrolyzable silyl group at both ends of the main chain.

[0035] In the following description, the "number of hydrolyzable silyl groups contained on average per molecule of the hydrolyzable silyl group-containing organic polymer" may also be referred to as the "number of introduced hydrolyzable silyl groups" or simply as the "functionalization rate."

[0036] The structure of the hydrolyzable silyl group is not particularly limited, and any hydrolyzable silyl group commonly used in this technical field may be used.

[0037] In one embodiment, the hydrolyzable silyl group of the component (A) is represented by the following general formula (5).

[0038] -Si(R 7 ) 3-a (Y) a (5) (In the formula, R 7 each independently represents a hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group may contain a heteroatom. Each Y independently represents a hydroxyl group or a hydrolyzable group. a represents a natural number of 1 to 3.

[0039] Multiple R in one hydrolyzable silyl group 7 When exists, the R 7 The structures of may be the same or different.

[0040] R 7 Examples of the alkyl group include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms.

[0041] Y represents a hydroxyl group or a hydrolyzable group. Examples of the hydrolyzable group include a hydroxyl group, a halogen group, an alkoxy group, an aryloxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, an oxime group, a mercapto group, an alkenyloxy group, a perfluoroalkyloxy group, a polyfluoroalkyloxy group, a perfluoroaryloxy group, and a polyfluoroaryloxy group.

[0042] Among these, alkoxy groups such as methoxy and ethoxy groups are more preferred, with methoxy and ethoxy groups being even more preferred, and methoxy groups being particularly preferred, because they are mildly hydrolyzable, easy to handle, and highly available.

[0043] Generally, the fewer the carbon atoms in an alkoxy group, the more reactive it tends to be. That is, the reactivity decreases in the order of methoxy, ethoxy, and propoxy. Taking advantage of this property, the specific structure of the hydrolyzable silyl group can be appropriately determined depending on the production method and intended use of component (A).

[0044] a is a natural number of 1 to 3. From the viewpoint of forming a network structure by condensation and easily obtaining a cured product, a is preferably 2 or 3. On the other hand, from the viewpoint of obtaining a cured product with high flexibility, a is preferably 1.

[0045] Specific examples of the hydrolyzable silyl group include a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, a methyldimethoxysilyl group, a methyldiethoxysilyl group, a methyldiisopropoxysilyl group, a (chloromethyl)dimethoxysilyl group, a (methoxymethyl)dimethoxysilyl group, a vinyldimethoxysilyl group, and a vinyldiethoxysilyl group.

[0046] From the viewpoints of the physical properties of the obtained cured product and the availability and ease of handling of the raw material compounds, the hydrolyzable silyl group is preferably a methyldialkoxysilyl group or a trialkoxysilyl group. From the viewpoints of the ease of handling of the curable composition and the flexibility of the cured product, the hydrolyzable silyl group is preferably a methyldialkoxysilyl group. From the viewpoint of a fast curing rate, the hydrolyzable silyl group is preferably a trialkoxysilyl group.

[0047] Specifically, the methyldialkoxysilyl group is preferably a methyldimethoxysilyl group or a methyldiethoxysilyl group, and the trialkoxysilyl group is preferably a trimethoxysilyl group or a triethoxysilyl group.

[0048] The lower limit of the number of hydrolyzable silyl groups contained on average per molecule of the polymer of component (A) is preferably 0.5 or more, more preferably 0.8 or more, and even more preferably 1.0 or more.

[0049] The upper limit of the number of hydrolyzable silyl groups contained on average per molecule of the polymer of component (A) is preferably 10 or less, more preferably 8 or less, and even more preferably 5 or less.

[0050] If the hydrolyzable silyl group is within the above range, the flexibility and strength of the cured product are sufficient, and surface tackiness can be reduced.

[0051] The distribution of the hydrolyzable silyl groups may be random or block-like.

[0052] The hydrolyzable silyl group may be located anywhere in the polymer chain. Preferably, the hydrolyzable silyl group is located at or near the end of the polymer chain. More preferably, the hydrolyzable silyl group is located at or near the end of the polymer molecule.

[0053] In one embodiment of the present invention, the term "near the end of the polymer chain" refers to a region from the end of the polymer chain to a specific position in the polymer chain. The weight of the region from the end of the polymer chain to the specific position is 20% by weight or less, more preferably 15% by weight or less, and even more preferably 10% by weight or less, based on the total weight of the polymer molecule being 100% by weight.

[0054] In one embodiment of the present invention, "localized near the end of the polymer chain" means that 70% or more, more preferably 80% or more, and even more preferably 90% or more of the hydrolyzable silyl groups contained in the polymer molecule are localized near the end of the polymer chain.

[0055] The hydrolyzable silyl group can be introduced into component (A) by a conventionally known method, such as an addition reaction (e.g., hydrosilylation) or a condensation reaction (e.g., a reaction to form a urethane bond, an ester bond, or an ether bond).

[0056] The lower limit of the number average molecular weight of component (A) is preferably 200 or more, more preferably 300 or more, and even more preferably 500 or more.

[0057] The upper limit of the number average molecular weight of component (A) is preferably 1,000,000 or less, more preferably 500,000 or less, and even more preferably 200,000 or less.

[0058] When the number average molecular weight is within the above range, the curable composition is easy to handle, the cured product has sufficient flexibility and strength, and the surface tack of the cured product is reduced.

[0059] The molecular weight distribution of component (A) is preferably 1.00 to 10.00, more preferably 1.00 to 5.00, and even more preferably 1.00 to 3.00. The molecular weight distribution is a value (Mw / Mn) expressed as the ratio of weight average molecular weight Mw to number average molecular weight Mn.

[0060] A molecular weight distribution within the above range is preferred because the curable composition is easy to handle and the cured product has sufficient flexibility, elongation and strength.

[0061] The main chain of component (A) is not particularly limited and can be selected depending on the physical properties and characteristics desired for the cured product. The main component of the main chain is preferably one or more polymer skeletons selected from the group consisting of polyoxyalkylene, poly((meth)acrylic acid ester), polyolefin, polyurethane, polysulfide, epoxy resin, and polysiloxane. Examples of polyolefins include polybutene, polyisoprene, hydrogenated polyisoprene, polyisobutylene, polybutadiene, and hydrogenated polybutadiene.

[0062] As used herein, when it is said that "the main component of the main chain is X," the weight ratio of X may be 50% by weight or more, 70% by weight or more, or 90% by weight or more, with the total weight of the main chain being 100% by weight. In one embodiment, the weight ratio of X may be 50% by weight or more, 70% by weight or more, or 90% by weight or more, with the total weight of component (A) being 100% by weight.

[0063] When it is desired that the viscosity of the curable composition is low and the adhesiveness or tackiness of the cured product is high, it is preferable to select, as the polymer skeleton, one or more types selected from the group consisting of polyoxyalkylene, poly((meth)acrylic acid ester), polybutene, polyisoprene, hydrogenated polyisoprene, polyisobutylene, polybutadiene, hydrogenated polybutadiene, polyurethane, epoxy resin, and polysiloxane.

[0064] When high gas barrier properties of the cured product are desired, it is preferable to select, as the polymer skeleton, one or more types selected from the group consisting of poly((meth)acrylic acid ester), polybutene, polyisoprene, hydrogenated polyisoprene, polyisobutylene, polybutadiene, hydrogenated polybutadiene, epoxy resin, and polysiloxane.

[0065] When high strength of the cured product is desired, it is preferable to select one or more types of polymer skeleton from polyoxyalkylene, polybutene, polyisoprene, hydrogenated polyisoprene, polyisobutylene, polybutadiene, hydrogenated polybutadiene, polyurethane, epoxy resin, and polysiloxane.

[0066] When the main component of the main chain of component (A) is polyoxyalkylene, a commercially available product may be used, or the component may be produced by the user.

[0067] Examples of commercially available products include Kaneka MS Polymer (registered trademark) S810, S257, S327, S203H, S303H (all manufactured by Kaneka Corporation), Silyl (registered trademark) SAX220, SAX350, SAT400, SAX510, SAX520, SAX580, SAX590, SAX750 (all manufactured by Kaneka Corporation), Exestar (registered trademark) ES-S2410, ES-S2420, ES-S3630 (all manufactured by AGC Corporation), and GENIOSIL (registered trademark) STP-E10, STP-E15, STP-E30, STP-E35 (all manufactured by Wacker).

[0068] When producing the polyoxyalkylene component (A), the production methods described in WO2023 / 162664

[0041] and subsequent publications by the same applicant can be used.

[0069] When the main component of the main chain of component (A) is poly((meth)acrylic acid ester), a commercially available product may be used, or it may be produced by oneself.

[0070] When a commercially available product is used, examples thereof include Kaneka TA Polymer (registered trademark) SA100S, SA110S, SA120S, SA310S, and SA410S (all manufactured by Kaneka Corporation), ARUFON (registered trademark) US-6100, US-6110, US-6120, US-6130, US-6140, US-6150, US-6170, US-6180, and US-6190 (all manufactured by Toagosei Co., Ltd.), Actflow (registered trademark) NE-1000 (manufactured by Soken Chemical & Engineering Co., Ltd.), and Joncryl (registered trademark) (manufactured by BASF).

[0071] When producing the poly((meth)acrylic acid ester) of component (A), the production methods described in WO2023 / 162664

[0060]

[0080] and subsequent publications by the same applicant can be used.

[0072] Alternatively, an organic polymer having a narrow molecular weight distribution may be produced by a living radical polymerization method. Specific examples of living radical polymerization methods can be found in the following non-patent documents:

[0073] Atom transfer radical polymerization (ATRP); J. Am. Chem. Soc., 1995, 117, 5614; Macromolecules, 1995, 28, 1721. ·Single electron transfer polymerization (SET-LRP); J. Am. Chem. Soc., 2006, 128, 14156; JPSChem, 2007, 45, 1607. Reversible Addition-Fragmentation Chain Transfer Polymerization (RAFT); Polymer Research Journal, 2011, 68, 223; JP 2014-111798 A

[0074] Other living radical polymerization methods include the nitroxide radical method (NMP method), polymerization using organotellurium compounds (TERP method), polymerization using organoantimony compounds (SBRP method), polymerization using organobismuth compounds (BIRP method), and iodine atom transfer polymerization (ITP method).

[0075] When the main component of the main chain of component (A) is polyisobutylene, a commercially available product may be used, or it may be produced by oneself.

[0076] When producing the polyisobutylene of component (A), for example, the production methods described in WO2013 / 047314, JP2013-216782A, and WO2017 / 099043A, all of which are filed by the same applicant, can be used. More specifically, the following Production Method 1 and Production Method 2 can be mentioned.

[0077] ◆Manufacturing method 1 Production method 1 includes the following steps. 1. A process for producing a polyisobutylene polymer by carrying out living cationic polymerization of isobutylene using a polymerization initiator and a Lewis acid catalyst in the presence of an electron donor component. An example of the polymerization initiator is dicumyl chloride. An example of the Lewis acid catalyst is TiCl4. An example of the electron donor component is a nitrogen-containing compound (e.g., 2-methylpyridine, 2,6-dimethylpyridine, triethylamine, etc.). 2. A step of reacting the terminals of the polyisobutylene polymer with allyltrialkylsilane to introduce allyl groups. 3. A step of introducing a hydrolyzable silyl group by reacting the allyl group with a hydrosilane compound through a hydrosilylation reaction.

[0078] According to Production Method 1, a polyisobutylene polymer having a hydrolyzable silyl group at its terminal can be produced.

[0079] In Production Method 1, it is particularly preferable to use, as the solvent, methyl chloride, butyl chloride, hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, toluene, etc., from the standpoints of availability, solubility of the raw materials and polymer, and economy.

[0080] In Production Method 1, the reaction is preferably carried out at a low temperature (for example, −70° C.).

[0081] In step 3 of production method 1, the functionalization rate can be controlled by adjusting the amount of the hydrosilane compound used.

[0082] The number of hydrolyzable silyl groups introduced per molecule can also be adjusted by changing the polymerization initiator in step 1 of production method 1. That is, the number of hydrolyzable silyl groups contained per molecule can be adjusted by changing the number of polymerization initiation sites contained in the polymerization initiator.

[0083] ◆Manufacturing method 2 Production method 2 includes the following steps. 1. A process for producing a monomer having both a functional group capable of undergoing cation polymerization with isobutylene (cationically polymerizable functional group) and a hydrolyzable silyl group. 2. A step of randomly copolymerizing isobutylene and the monomer obtained in step 1 by cationic polymerization.

[0084] According to Production Method 2, a polyisobutylene polymer having a hydrolyzable silyl group in the side chain of the polyisobutylene polymer can be produced.

[0085] When the main component of the main chain of component (A) is polyurethane, component (A) can be produced, for example, by Production Method 3 or Production Method 4 described below.

[0086] ◆Manufacturing method 3 A method for obtaining component (A) by reacting a polyhydric polyol, a polyfunctional isocyanate, and a compound having a hydrolyzable silyl group and a hydroxyl group.

[0087] ◆Manufacturing method 4 A method for obtaining component (A) by reacting a polyhydric polyol with a compound having a hydrolyzable silyl group and an isocyanate group.

[0088] In Production Methods 3 and 4, the polyhydric polyol may have various skeletons. For example, polyhydric polyols having an ethylene oxide skeleton, a propylene oxide skeleton, a polyester polyol skeleton, other polyether skeletons, an OH group-containing polybutadiene skeleton, an OH group-containing hydrogenated polybutadiene skeleton, an OH group-containing polyisobutylene skeleton, etc. can be used.

[0089] When the main component of the main chain of component (A) is an epoxy resin, component (A) can be obtained by reacting a polyhydric polyol with a compound having a hydrolyzable silyl group and an isocyanate group.

[0090] The main skeleton of the polyhydric polyol may be the above-mentioned polymer, or may be a low molecular weight compound such as ethylene glycol, propylene glycol, pentaerythritol, glycerin, tartaric acid, monosaccharide, etc. Component (A) can also be obtained by introducing a hydrolyzable silyl group into a polyhydric polyol that has been copolymerized in advance with a polyfunctional isocyanate.

[0091] For example, a hydrolyzable silyl group-containing epoxy resin can be obtained by adding a compound having a hydrolyzable silyl group and an isocyanate group to a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, or a phenol novolac resin.

[0092] Furthermore, the main component of the main chain of component (A) may be, for example, a polymer (copolymer) obtained by polymerizing one or more of the following monomers: aromatic vinyl monomers such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, and styrenesulfonic acid and salts thereof; fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene, and vinylidene fluoride; silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; maleic anhydride, maleic acid, and monoalkyl and dialkyl esters of maleic acid; fumaric acid, and monoalkyl and dialkyl esters of fumaric acid; maleimide monomers such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, and cyclohexylmaleimide; Nitrile group-containing vinyl monomers such as acrylonitrile and methacrylonitrile; amide group-containing vinyl monomers such as acrylamide and methacrylamide; vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, and vinyl cinnamate; alkenes such as ethylene and propylene; conjugated dienes such as butadiene and isoprene; vinyl chloride; vinylidene chloride; allyl chloride; allyl alcohol; and the like.

[0093] <Component (B): Hydrolyzable Silyl Group-Containing Compound> Component (B) is one or more hydrolyzable silyl group-containing compounds selected from the group consisting of compounds represented by the following formulas (1) to (4): Component (B) has a structure in which a fatty acid and a group having a hydrolyzable silyl group are bonded to glycerin. Component (B) is involved in a condensation reaction with component (A) through the action of the curing catalyst (component (C) described below), and joins the crosslinking system.

[0094] [ka] (In the formulas (1) to (4), R 1 ~R 6each independently represents a divalent organic group, X represents a hydrolyzable silyl group, and FA represents a fatty acid.

[0095] In formulas (1) to (4), R 1 ~R 6 is not particularly limited. 1 ~R 6 may each independently be an alkylene group, an alkenylene group, an alkynylene group or an arylene group, and these groups may contain heteroatoms.

[0096] In formulas (1) to (4), R 1 ~R 6 From the viewpoint of the reaction efficiency of introducing a hydrolyzable silyl group into component (B), each of the groups may independently be an ester bond, an ether bond, an amide bond, a urethane bond, a thioether bond, a carbonate bond, a urea bond, or a divalent hydrocarbon group having two or more carbon atoms which may have a heteroatom, or a group containing any of these.

[0097] Among these, from the viewpoint of ease of manufacturing component (B), R 1 ~R 6 are each independently preferably an ester bond, an ether bond, a urethane bond or a carbonate bond, more preferably an ester bond, a urethane bond or a carbonate bond, and even more preferably a urethane bond or a carbonate bond.

[0098] From the viewpoints of the reactivity, ease of production, and availability of component (B), it is particularly preferred that component (B) has a hydrolyzable silyl group-containing moiety and glycerin bonded via a urethane bond. That is, it is particularly preferred that component (B) have a structure represented by the following general formulas (7) to (10).

[0099] [ka] (In the formulas (7) to (10), X and FA are the same as those in the formulas (1) to (4), and R 1a ~R 6aeach independently represents a divalent organic group.

[0100] In formulas (7) to (10), R 1a ~R 6a is not particularly limited. 1a ~R 6a is R 1 ~R 6 Among these, from the viewpoint of ease of synthesis and availability of raw materials, R 1a ~R 6a are each independently preferably an alkylene group or an arylene group, more preferably an alkylene group.

[0101] In formulas (7) to (10), R 1a ~R 6a From the viewpoints of ease of synthesis and availability of raw materials, each of the groups preferably represents one or more selected from the group consisting of a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heplen group, an octylene group, a nonylene group, and a decylene group, more preferably represents one or more selected from the group consisting of a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, and a hexylene group, and even more preferably represents one or more selected from the group consisting of a methylene group, an ethylene group, and a propylene group.

[0102] The X group in component (B) is not particularly limited, and examples of the X group include the hydrolyzable silyl group in component (A) described above.

[0103] The FA of component (B) is not particularly limited, but is preferably one or more selected from the group consisting of stearic acid, (meth)acrylic acid, palmitic acid, acetic acid, butyric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, montanic acid, palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eicosenoic acid, erucic acid, conjugated linoleic acid, punicic acid, eleostearic acid, ricinoleic acid, hydroxystearic acid, epoxidized fatty acids, eicosapentaenoic acid, 12-hydroxystearic acid, glycolic acid, 16-hydroxyhexadecanoic acid, 15-hydroxypentadecanoic acid, 2-hydroxypalmitic acid, lactic acid, 3-hydroxybutanoic acid, docosahexaenoic acid, and trans fatty acids produced by partial hydrogenation of these acids. If the FA has such a structure, it is possible to impart flexibility to the cured product while reducing surface tackiness.

[0104] From the viewpoint of reducing surface tackiness, the FA of component (B) is preferably one or more selected from the group consisting of lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, montanic acid, punicic acid, eleostearic acid, eicosapentaenoic acid, 12-hydroxystearic acid, glycolic acid, 16-hydroxyhexadecanoic acid, 15-hydroxypentadecanoic acid, 2-hydroxypalmitic acid, lactic acid, 3-hydroxybutanoic acid, and docosahexaenoic acid. On the other hand, from the viewpoint of low cost and easy availability, the FA of component (B) is more preferably one or more selected from the group consisting of acetic acid, lauric acid, oleic acid, palmitic acid, and stearic acid.

[0105] When the FA group of component (B) has hydroxy groups, hydrolyzable silyl groups may be introduced into some or all of the hydroxy groups.

[0106] As the component (B), one or more compounds may be used alone, or two or more compounds with different chemical formulas may be used in combination.

[0107] The (B) component can be selected as desired depending on the physical properties of the cured product. For example, if a highly flexible cured product is desired, the melting point of the (B) component is preferably 300°C or lower, more preferably 200°C or lower, and even more preferably 100°C or lower. On the other hand, if a cured product with high strength, elongation, and hardness is desired, the melting point of the (B) component is preferably -100°C or higher, more preferably -80°C or higher, and even more preferably -50°C or higher. By adjusting the melting point of the (B) component as described above, the physical properties of the cured product can be adjusted as desired.

[0108] The lower limit of the content of component (B) in the curable composition is preferably 0.01 parts by weight or more, more preferably 0.1 parts by weight or more, per 100 parts by weight of component (A). The upper limit of the content of component (B) is preferably 1000.00 parts by weight or less, more preferably 500.00 parts by weight or less, per 100 parts by weight of component (A). By keeping the content of component (B) within the above range, it is possible to reduce surface tackiness while maintaining a balance between strength and flexibility of the cured product.

[0109] The method for producing component (B) is not particularly limited, but it can be produced, for example, by introducing a hydrolyzable silyl group into a monoglyceride or diglyceride to which the target fatty acid is bonded, by any of the following reactions (i) to (iv):

[0110] (i) A method of adding a compound having a hydrolyzable silyl group and an isocyanate group (this is preferably carried out in the presence of a tin catalyst or bismuth catalyst from the viewpoint of reaction rate). (ii) A method of condensing a compound having a hydrolyzable silyl group and an acid halide group (the reaction is preferably carried out in the presence of a basic substance such as an amine). (iii) A method of condensing a hydrolyzable silyl group with a compound having an aryl orthoformate skeleton or a chloroformate skeleton (the reaction is preferably carried out in the presence of a basic substance such as an amine). (iv) A method of condensing a compound having a hydrolyzable silyl group and a halogen group (the reaction is preferably carried out in the presence of a basic substance).

[0111] <(C) component; curing catalyst> Component (C) is a component that catalyzes the hydrolysis and condensation of the hydrolyzable silyl groups in components (A) and (B) and promotes curing.

[0112] The component (C) is not particularly limited, but examples thereof include organotin compounds, organobismuth compounds, metal carboxylates, amine compounds, carboxylic acids, and alkoxy metals.

[0113] Specific examples of the component (C) that can be suitably used include the compounds described in commonly assigned WO2023 / 162664, paragraphs

[0101] and following. Among these, organotin compounds, metal carboxylates, mixtures of carboxylic acids and amine compounds, and alkoxy metals are preferred.

[0114] Examples of organotin compounds include dibutyltin dilaurate, dibutyltin dioctanoate, dibutyltin diversatate, dibutyltin distearate, dibutyltin bis(butyl maleate), dibutyltin diacetate, dibutyltin oxide, dibutyltin di(acetylacetonate), dioctyltin bis(acetylacetonate), dioctyltin dilaurate, dioctyltin dioctanoate, dioctyltin diversatate, dioctyltin distearate, dioctyltin diacetate, and dioctyltin oxide.

[0115] Examples of metal carboxylates include tin octoate, tin laurate, tin neodecanoate, and tin versatate.

[0116] Examples of carboxylic acids include lauric acid, 2-ethylhexanoic acid, neodecanoic acid, and versatic acid. Examples of amine compounds include octylamine, laurylamine, stearylamine, and N,N-diethylamino-1,3-propanediamine. The carboxylic acid and amine compound may be mixed at any ratio depending on the desired curing speed.

[0117] Examples of alkoxy metals include titanium tetraethoxide, titanium tetraisopropoxide, and titanium tetrabutoxide.

[0118] The curing catalyst of component (C) may be used alone or in combination of two or more types.

[0119] The lower limit of the content of component (C) in the curable composition is preferably 0.001 parts by weight or more, more preferably 0.01 parts by weight or more, and even more preferably 0.1 parts by weight or more, per 100 parts by weight of component (A). The upper limit of the content of component (C) is preferably 20,000 parts by weight or less, more preferably 10,000 parts by weight or less, per 100 parts by weight of component (A). If the content of component (C) is within the above range, the curable composition can be cured within the desired time to obtain a cured product.

[0120] <Other ingredients> The present curable composition may contain components other than the above-mentioned components (A), (B), and (C) (hereinafter, these may be referred to as "other components"), as necessary.

[0121] Other components include adhesion promoters such as silane coupling agents and tackifiers, fillers, hollow microparticles, plasticizers, storage stabilizers, antioxidants, ultraviolet absorbers, flame retardants, antistatic agents, pigments, thixotropy-imparting agents (anti-sagging agents), compatibilizers, curing regulators, radical inhibitors, metal deactivators, antiozonants, phosphorus-based peroxide decomposers, lubricants, antifoaming agents, foaming agents, anti-termite agents, anti-fungal agents, and light stabilizers, as well as elastomers (e.g., styrene-based block copolymers) that adjust the rubber properties of the cured product, thiol compounds, tertiary amine compounds, adhesion promoters, and solvents.

[0122] Specific examples of other components include those described in paragraphs

[0134] to

[0151] of JP 2006-291073 A, paragraphs

[0232] to

[0235] of JP 2007-308692 A, paragraphs

[0089] to

[0093] of International Publication WO2005 / 116134 A, JP-B-4-69659, JP-B-7-108928, JP 63-254149 A, JP 64-22904 A, JP 2001-72854 A, and paragraphs

[0111] to

[0143] of International Publication WO2023 / 162664 A, and can also be suitably used in the present invention.

[0123] <Physical Properties of the Curable Composition> The lower limit of the viscosity of the curable composition at 50°C is preferably 0.0001 Pa·sec or more, more preferably 0.001 Pa·sec or more, and even more preferably 0.01 Pa·sec or more. The upper limit of the viscosity of the curable composition at 50°C is preferably 10,000 Pa·sec or less, more preferably 1,000 Pa·sec or less, and even more preferably 500 Pa·sec or less. A viscosity within the above range has the advantage of being adaptable to various application or filling methods and easy to handle.

[0124] When the curable composition is used in a method suitable for applying or filling a low-viscosity composition (for example, spraying, inkjet printing, screen printing, caulking gun, spray gun, etc.), the viscosity is, for example, preferably 0.0001 Pa·sec to 5000 Pa·sec, and more preferably 0.0001 Pa·sec to 3000 Pa·sec. If the viscosity is within the above range, the curable composition is easy to handle and can be easily discharged from the discharge port.

[0125] When the curable composition is used for applications such as form-in-place gaskets (FIPG), cured-in-place gaskets (CIPG), molded-in-place gaskets (MIPG), liquid injection molding (LIM), and other dispensing applications, the viscosity is preferably 0.001 Pa·sec to 10,000 Pa·sec, and more preferably 0.001 Pa·sec to 5,000 Pa·sec. A viscosity within the above range has the advantage of providing good thixotropy and facilitating molding into the desired shape. Furthermore, a viscosity of 10,000 Pa·sec or less is preferable from the standpoint of productivity, as it can be discharged at a good discharge rate.

[0126] <Method for producing the present curable composition> A curable composition can be obtained by mixing the above-mentioned components (A), (B), and (C), and, if necessary, other components.

[0127] The method for mixing the multiple components is not particularly limited, and examples include methods of mixing the multiple components using a hand mixer, static mixer, planetary mixer, disper, roll, kneader, single-screw extruder, twin-screw extruder, Banbury mixer, Brabender mixer, high-shear mixer, etc. Mixing may be performed in the dark, if necessary.

[0128] The present curable composition may be a one-component type, a two-component type, or a multi-component type having three or more components.

[0129] When the present curable composition is a one-component type, all of the components are blended in advance, and therefore, it is preferable to dehydrate and dry raw materials containing moisture before use, or to dehydrate them by heating, reducing pressure, or the like during the production of the curable composition.

[0130] Alternatively, dehydration can be achieved by adding other components with dehydrating properties. Specific examples of such components include silanes (methyltrimethoxysilane, phenyltrimethoxysilane, n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, γ-mercaptopropylethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-glycidopropyltrimethoxysilane, mercarbamatemethyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, or tetraalkoxysilane condensates, etc.), carbodiimides (orthoesters such as methyl orthoformate and methyl orthoacetate, dicyclohexylcarbodiimide, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide, etc.). The inclusion of these compounds improves the storage stability of the curable composition.

[0131] When the present curable composition is a one-component type, the water content in the curable composition is preferably 5% by weight or less, more preferably 1% by weight or less, even more preferably 3000 ppm or less, and particularly preferably 1000 ppm or less. When the water content is within the above range, the storage stability is good and the composition is suitable for long-term storage.

[0132] <Method for applying or filling the curable composition of the present invention> The method for applying or filling the curable composition onto an adherend is not particularly limited, and any known method for applying or filling a sealant, pressure-sensitive adhesive, or adhesive can be used. Such methods include dispensing using a cartridge or an automatic coater, spraying, inkjet printing, screen printing, gravure printing, dipping, spin coating, die coating, and filling using a caulking gun or spray gun.

[0133] If the curable composition has a high viscosity at room temperature and is difficult to handle, the curable composition may be heated to the desired viscosity. The temperature of the curable composition after heating is preferably 100°C or lower, more preferably 80°C or lower. Heating the curable composition at 100°C or lower has the advantage that component (C) is less likely to volatilize. This provides safety benefits and prevents changes in the compounding ratio of each component in the curable composition.

[0134] [3. Cured product] A cured product according to one embodiment of the present invention is obtained by curing the present curable composition described in the section [2. Curable Composition]. The cured product according to one embodiment of the present invention is also simply referred to as the present cured product.

[0135] The cured product has sufficient flexibility and strength, and can have reduced surface tack. The cured product also has good gas barrier properties, tackiness, adhesiveness, ease of handling, etc. Furthermore, the cured product has good heat resistance.

[0136] <Physical properties of the cured product> The present cured product can be used in a variety of applications, and can be suitably used, for example, in applications where rubber-like properties and / or relatively soft properties are required.

[0137] The tensile stress (MPa) of a cured product when it is elongated by X% is sometimes referred to as the "modulus at X% elongation." The "modulus at X% elongation" of a cured product is sometimes referred to as "MX." For example, "M50" refers to the "modulus at 50% elongation," which is the tensile stress (MPa) of a cured product when it is elongated by 50%.

[0138] The M50 of the cured product is preferably 0.01 MPa to 20.00 MPa, and more preferably 0.01 MPa to 10.00 MPa. If the M50 is within the above range, the cured product has the advantage of achieving a good balance of high flexibility, high strength, and reduced surface tack.

[0139] The "tensile strength at break" of a cured product is sometimes referred to as "Tb." Also, the "tensile elongation at break" of a cured product is sometimes referred to as "Eb."

[0140] The lower limit of Tb of the present cured product is preferably 0.01 MPa or more, more preferably 0.10 MPa or more. The upper limit of Tb of the present cured product is preferably 50.00 MPa or less, more preferably 40.00 MPa or less. If the lower limit of Tb is within the above range, the cured product has the advantage of having sufficient strength and being easy to handle. If the upper limit of Tb is within the above range, the cured product has the advantage of maintaining rubber-like properties. If Tb is within the above range, the product also has the advantage of being easily applicable to various applications such as sealing agents, moisture-proofing agents, potting agents, and gasket materials.

[0141] The lower limit of Eb of the present cured product is preferably 10% or more, more preferably 30% or more, and even more preferably 50% or more. The upper limit of Eb of the present cured product is preferably 1000% or less, more preferably 500% or less. Eb within the above range has the advantage of being able to obtain a cured product that can follow the movement of an adherend without peeling or breaking.

[0142] The gel fraction of the present cured product is preferably higher than that of cured products containing conventionally known plasticizers. For example, the gel fraction is preferably 50% or more, more preferably 60% or more, and even more preferably 70% or more. If the gel fraction is within the above range, bleeding out of the plasticizer is reduced, thereby resolving issues such as reduced designability.

[0143] The heat resistance of the present cured product is preferably higher than that of cured products containing conventionally known plasticizers. For example, the 5% weight loss temperature of the present cured product is preferably 270°C or higher, more preferably 280°C or higher, and even more preferably 290°C or higher. If the 5% weight loss temperature is within the above range, it can be said that the product has good durability as well as heat resistance. Therefore, the cured product can be used for a long period of time, and is preferable because it can also be used at high temperatures.

[0144] The methods for measuring the various physical properties of the cured product will be described in detail in the examples below.

[0145] <Curing method> The method for curing the curable composition can also be considered as a method for producing a cured product. In one embodiment of the present invention, the method for producing a cured product involves exposing the curable composition to an external stimulus (moisture) to promote condensation (crosslinking) of components (A) and (B).

[0146] The temperature during curing may be room temperature, or may be heated to about 100° C. Generally, curing tends to proceed more quickly at high temperatures than at low temperatures, so heating may be performed as necessary.

[0147] The curable composition may be placed in a mold and then cured, i.e., the cured product may be a molded article.

[0148] [4.Applications] The present curable composition can be suitably used in a variety of applications. Examples of such applications include sealing materials, pressure-sensitive adhesives, sealants, gasket materials, adhesives, coating materials, covering materials, resist materials, vibration-proofing materials, vibration-damping materials, shock-absorbing materials, buffer materials, electrical insulating materials, foams, paints, inks, casting agents, potting agents, molding materials, underfill materials, die-bonding materials, and fillers in electrical and electronic components (LEDs, batteries, sensors, semiconductors, circuit boards, displays, home appliances, optical communications and optical circuits, optical recording, magnetic recording, etc.), pharmaceuticals and medical products, automotive and marine parts, building components, and acoustic components. The present curable composition can also be used in various forms, such as sheets (films), tapes, and molded articles (packing, O-rings, belts, tubes, valves, hoses, etc.).

[0149] Among these, the present cured product can be suitably used in the fields of adhesives, pressure sensitive adhesives, sealants and sealing agents, where both high flexibility and reduced surface tackiness are often required. [Example]

[0150] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Measurements and evaluations in the examples and comparative examples were carried out by the following methods.

[0151] [Measurement and evaluation methods] < 1 H NMR analysis> The compounds obtained in each synthesis example 1 H NMR analysis was carried out under the following conditions: Equipment: Bruker Avance III 400MHz The solvent used was deuterated chloroform, and the measurement was carried out at room temperature.

[0152] <Surface tack> The stickiness of the surface of a 1.0 mm thick sheet-like cured product was evaluated by touching with a finger. The evaluation was on a scale of 1 to 5, with 1 being the least sticky surface and 5 being the most sticky surface (uncured). In other words, the smaller the number, the less sticky the surface and the reduced surface tackiness.

[0153] <Hardness (A type)> Six sheets of the cured product, each 1.0 mm thick, were stacked together to form a sample. The hardness (Type A) of the sample was measured using a Type A durometer in accordance with JIS K 6253:2012.

[0154] <Tensile properties> The tensile properties of a 1.0 mm thick sheet-like cured product were measured in accordance with JIS K 6251:2017. First, the sheet-like cured product was punched into a No. 7 dumbbell shape, and the resulting dumbbell-shaped cured product was used as a test piece. Next, a tensile test was performed using the resulting test piece at a temperature of 23°C and a tensile speed of 200 mm / min to measure the modulus at 50% elongation, tensile strength at break, and tensile elongation at break.

[0155] <Gel fraction> Approximately 1 g of the sheet-like cured product with a thickness of 1.0 mm was used as a sample, and the weight of the cured product was measured and designated as W1 (g). The sample was then immersed in toluene (toluene in an amount approximately 200 times the weight of the sample was used) and left to stand at room temperature for one week. The precipitate was then collected and dried at 80°C under reduced pressure for 24 hours. The weight of the dried precipitate was measured and designated as W2 (g). The gel fraction was calculated using the following formula: Gel fraction (%) = (W2 / W1) × 100.

[0156] <5% weight loss temperature> A 1.0 mm thick sheet-like cured product was used as a sample for thermogravimetric analysis using a STA7200 (Hitachi High-Tech Science Corporation) to measure the 5% weight loss temperature. The measurement was performed under a nitrogen gas flow, with the temperature rising from 30°C to 500°C at a rate of 10°C / min, to obtain a thermogravimetric curve. The temperature at which the sample weight had decreased by 5% was determined from the thermogravimetric curve and was taken as the 5% weight loss temperature.

[0157] <Whether or not there is bleed-out> A 1.0 mm thick sheet of the cured product was used as a sample and cured in an oven at 80°C for one week, then removed and cooled to room temperature. The surface of the cured product was then touched with a finger. If any liquid component was found to be adhering to the surface, it was determined that bleeding had occurred.

[0158] 〔material〕 The materials used in the following examples and comparative examples are as follows.

[0159] <Component (A)> Polypropylene glycol containing hydrolyzable silyl groups at both ends (Kaneka Corporation, "S203H") Telechelic polyacrylate containing hydrolyzable silyl groups at both ends (Kaneka Corporation, "SA100S") <(B) component> Hydrolyzable silyl group-containing glyceride (GS-1): The main component is a mixture of formula (1) and formula (2) (wherein R 1 and R 2 is a -(CO)(NH)CH2CH2CH2- group, X is -Si(OEt)3, and the main component of FA is oleic acid. Hydrolyzable silyl group-containing glyceride (GS-2): The main component is a mixture of formula (1) and formula (2) (wherein R 1 and R 2 is a -(CO)(NH)CH2CH2CH2- group, X is -Si(OMe)3, and the main component of FA is oleic acid. Hydrolyzable silyl group-containing glyceride (GS-3): The main component is a mixture of formula (1) and formula (2) (wherein R 1 and R 2 is a -(CO)(NH)CH2CH2CH2- group, X is -Si(Me)(OMe)2, and the main component of FA is oleic acid. Hydrolyzable silyl group-containing glyceride (GS-4): The main component is a mixture of formula (3) and formula (4) (wherein R 3 and R 4 is a -(CO)(NH)CH2CH2CH2- group, X is -Si(OMe)3, and the main component of FA is oleic acid. Hydrolyzable silyl group-containing glyceride (GS-5): The main component is a mixture of formula (1) and formula (2) (wherein, in formula (1) and formula (2), R 1 and R 2 is a -(CO)(NH)CH2CH2CH2- group, X is -Si(OMe)3, and the main component of FA is stearic acid. Hydrolyzable silyl group-containing glyceride (GS-6): The main component is a mixture of formula (3) and formula (4) (wherein R 3 and R 4 is a -(CO)(NH)CH2CH2CH2- group, X is -Si(OMe)3, and the main component of FA is stearic acid. <Plasticizers other than component (B)> Diisononyl phthalate (Mitsubishi Gas Chemical Company, Inc.) Glycerin fatty acid ester (Riken Vitamin Co., Ltd., "Biocizer") <(C) component> Dibutyltin catalyst (Nitto Kasei Co., Ltd., "Neostan U-220H")

[0160] [Synthesis Example (Synthesis of Component (B)] <Synthesis Example 1> 10.0 g of glycerol dioleate was stirred under high vacuum at 100°C for 1 hour. Next, the system was purged with nitrogen, and 4.0 g of (3-isocyanatopropyl)triethoxysilane and 0.50 μL of a urethane curing catalyst (Nitto Kasei, "Neostan U-830") were added. After stirring at 100°C for 5 hours, a pale yellow liquid hydrolyzable silyl group-containing glyceride (GS-1) was obtained.

[0161] The obtained hydrolyzable silyl group-containing glyceride (GS-1) 1 The H-NMR results were as follows: 1 H NMR (400MHz, CDCl3): δ=5.50-4.94(m, 5H), 4.40-4.05(m, 4H), 3.95-3.71(q, 6H), 3.26-3.06(m, 2H), 2.40-2.23(t, 4 H), 2.15-1.92(m, 8H), 1.71-1.55(m, 6H), 1.48-1.04(m, 49H), 0.90(t, 6H), 0.74-0.54(m, 2H).

[0162] <Synthesis Example 2> 10.0 g of glycerol dioleate was stirred under high vacuum at 100°C for 1 hour. Next, the system was purged with nitrogen, and 3.1 g of (3-isocyanatopropyl)trimethoxysilane and 0.50 μL of a urethane curing catalyst (Nitto Kasei, "Neostan U-830") were added. After stirring at 100°C for 4 hours, a pale yellow liquid hydrolyzable silyl group-containing glyceride (GS-2) was obtained.

[0163] The obtained hydrolyzable silyl group-containing glyceride (GS-2) 1 The H-NMR results were as follows: 1 H NMR (400MHz, CDCl3): δ=5.50-4.85(m, 5H), 4.42-4.06(m, 4H), 3.70-3.49(s, 9H), 3.26-3.06(m, 2H), 2.41-2.21(m, 4 H), 2.15-1.90(m, 8H), 1.71-1.51(m, 6H), 1.48-1.05(m, 40H), 0.90(t, 6H), 0.74-0.54(m, 2H).

[0164] <Synthesis Example 3> 20.0 g of glycerol dioleate was stirred under high vacuum at 100°C for 1 hour. Next, the system was purged with nitrogen, and 5.5 g of (3-isocyanatopropyl)methyldimethoxysilane and 1.0 μL of a urethane curing catalyst (Nitto Kasei, "Neostan U-830") were added. After stirring at 100°C for 4 hours, a pale yellow liquid hydrolyzable silyl group-containing glyceride (GS-3) was obtained.

[0165] The obtained hydrolyzable silyl group-containing glyceride (GS-3) 1 The H-NMR results were as follows: 1 H NMR (400MHz, CDCl3): δ=5.50-4.85(m, 5H), 4.40-4.05(m, 4H), 3.54(s, 6H), 3.26-3.05(m, 2H), 2.41-2.21(m, 4H), 2.15- 1.88(m, 8H), 1.71-1.51(m, 6H), 1.48-1.05(m, 40H), 0.90(t, 6H), 0.74-0.54(m, 2H), 0.13(s, 3H).

[0166] <Synthesis Example 4> 10.0 g of glycerol oleate was stirred under high vacuum at 110°C for 1 hour. Next, the system was purged with nitrogen, and 10.9 g of (3-isocyanatopropyl)trimethoxysilane and 0.50 μL of a urethane curing catalyst (Nitto Kasei, "Neostan U-830") were added. After stirring at 110°C for 3 hours, a pale yellow liquid hydrolyzable silyl group-containing glyceride (GS-4) was obtained.

[0167] The obtained hydrolyzable silyl group-containing glyceride (GS-4) 1 The H-NMR results were as follows: 1H NMR (400MHz, CDCl3): δ=5.46-4.74(m, 3H), 4.40-4.00(m, 4H), 3.57(s, 18H), 3.26-2.88(m, 4H), 2.41-2.21(m, 2H), 2.15-1.87(m, 4H), 1.75-1.48(m, 6H), 1.48-1.05(m, 20H), 0.88(t, 3H), 0.64(t, 4H).

[0168] <Synthesis Example 5> 20.0 g of glycerol distearate was stirred under high vacuum at 100°C for 1 hour. Next, the system was purged with nitrogen, and 6.2 g of (3-isocyanatopropyl)trimethoxysilane and 1.0 μL of a urethane curing catalyst (Nitto Kasei, "Neostan U-830") were added. After stirring at 100°C for 3 hours, a white waxy hydrolyzable silyl group-containing glyceride (GS-5) was obtained.

[0169] The obtained hydrolyzable silyl group-containing glyceride (GS-5) 1 The H-NMR results were as follows: 1 H NMR (400MHz, CDCl3): δ=5.38-4.83(m, 1H), 4.40-4.04(m, 4H), 3.57(s, 9H), 3.26-3.01(m, 2H), 2.42- 2.20(m, 4H), 1.75-1.50(m, 6H), 1.44-1.05(m, 56H), 0.88(t, 6H), 0.64(t, 2H).

[0170] <Synthesis Example 6> 20.0 g of glycerol stearate was stirred under high vacuum at 110°C for 1 hour. Next, the system was purged with nitrogen, and 21.8 g of (3-isocyanatopropyl)trimethoxysilane and 1.0 μL of a urethane curing catalyst (Nitto Kasei, "Neostan U-830") were added. After stirring at 110°C for 2 hours, a white waxy hydrolyzable silyl group-containing glyceride (GS-6) was obtained.

[0171] The obtained hydrolyzable silyl group-containing glyceride (GS-6) 1 The H-NMR results were as follows: 1 H NMR (400MHz, CDCl3): δ=5.28-4.76(m, 1H), 4.40-4.00(m, 4H), 3.57(s, 18H), 3.26-2.90(m, 4H), 2.43 -2.21(m, 2H), 1.75-1.48(m, 6H), 1.48-1.05(m, 28H), 0.88(t, 3H), 0.64(t, 4H).

[0172] Examples and Comparative Examples (Production of Curable Composition) <Comparative Examples 1 to 6, Examples 1 to 9> The components were weighed in the proportions shown in Table 1 and mixed uniformly to obtain a curable composition.

[0173] (Production of cured product) <Comparative Examples 1 to 6, Examples 1 to 9> The resulting curable composition was applied to a polyethylene terephthalate sheet coated with a release agent to a thickness of 1.0 mm, and then cured at room temperature for 3 days and then in an oven at 50°C for 4 days to obtain a sheet-like cured product.

[0174] The resulting cured product was in the form of a 1.0 mm thick sheet, and various physical properties were evaluated. The results are shown in the "Cured Product" column of Table 1.

[0175] [Table 1] JPEG2026014110000008.jpg193149

[0176] 〔result〕 Examples 1 to 6 and Comparative Examples 1 to 3 are systems that use a polyoxyalkylene polymer as component (A). In these systems, when a plasticizer other than component (B) was used, as in Comparative Examples 2 and 3, the surface tack was large and bleed-out occurred. Furthermore, when a plasticizer other than component (B) was used, the modulus at 50% elongation was lower than in Comparative Example 1, but the strength at break was also lower than in Comparative Example 1. In other words, the inclusion of a plasticizer improved the flexibility of the cured product, but reduced its strength.

[0177] On the other hand, when component (B) was used as in Examples 1 to 6, surface tack was significantly reduced and no bleed-out occurred. A high gel fraction of the cured product indicates a low level of extractable components, which also indicates that bleed-out was reduced in the cured products of the Examples. Furthermore, although the modulus at 50% elongation was similar to that of Comparative Examples 2 and 3, the strength at break was higher than that of Comparative Examples 2 and 3. In other words, by including component (B), flexibility equivalent to that of the prior art was achieved, while strength was improved compared to the prior art.

[0178] As can be seen from these results, by incorporating component (B), it is possible to achieve high flexibility, high strength, and reduced surface tack, which were difficult to achieve simultaneously with conventional plasticizers.

[0179] Furthermore, it was found that the heat resistance of the cured product was also improved. Although the reason for this is not entirely clear, it is presumed that the silylated glyceride has bulky fatty acid groups, which makes it resistant to deterioration due to oxygen and / or heat.

[0180] Examples 7 to 9 and Comparative Examples 4 to 6 are systems in which a poly((meth)acrylic acid ester) polymer was used as component (A). It can be seen that similar results to those described above were obtained in these systems as well. This demonstrates that the present invention is applicable regardless of the type of component (A).

[0181] The silylated glyceride, which is component (B), can be produced using a glyceride compound, which is a bio-based raw material, as the main raw material. Considering that conventionally known plasticizers, such as phthalate plasticizers, are produced from fossil resources, this feature is also desirable from the perspective of product sustainability in a sustainable society.

Claims

1. a hydrolyzable silyl group-containing organic polymer as component (A); Component (B) is one or more hydrolyzable silyl group-containing compounds selected from the group consisting of compounds represented by the following formulas (1) to (4), 【Chemistry 1】 (In the formulas (1) to (4), R １ ~R ６ each independently represents a divalent organic group, X represents a hydrolyzable silyl group, and FA represents a fatty acid. (C) a curing catalyst; For 100 parts by weight of the component (A), The content of the component (B) is 0.01 parts by weight to 1000.00 parts by weight, The content of the component (C) is 0.001 to 20,000 parts by weight.

2. 2. The curable composition according to claim 1, wherein a main component of the main chain of the component (A) is one or more selected from the group consisting of polyoxyalkylene, poly((meth)acrylic acid ester), polyolefin, polyurethane, polysulfide, epoxy resin, and polysiloxane.

3. 2. The curable composition according to claim 1, wherein the molecular weight distribution of the component (A) is 1.00 to 5.

00.

4. The curable composition according to claim 1 , wherein the hydrolyzable silyl groups of the components (A) and (B) are represented by the following general formula (5): —Si(R ７ ( ３－ａ (Y) ａ (5) (In the formula, R ７ each independently represents a hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group may contain a heteroatom; each Y independently represents a hydroxyl group or a hydrolyzable group; and a represents a natural number of 1 to 3.

5. The R １ ~R ６ is an ester bond, an ether bond, an amide bond, a urethane bond, a thioether bond, a carbonate bond, a urea bond, or a divalent hydrocarbon group having two or more carbon atoms which may have a heteroatom, or contains any of these.

6. The curable composition according to claim 1, wherein the component (B) is represented by the following general formulas (7) to (10): 【Chemistry 2】 (In the formulas (7) to (10), X and FA are the same as those in the formulas (1) to (4), and R １ａ ~R ６ａ each independently represents a divalent organic group.

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

8. An adhesive comprising the curable composition according to any one of claims 1 to 6.

9. A pressure-sensitive adhesive comprising the curable composition according to any one of claims 1 to 6.

10. A sealant comprising the curable composition according to any one of claims 1 to 6.

11. A sealant comprising the curable composition according to any one of claims 1 to 6.

12. A compound represented by any one of the following general formulas (7) to (10): 【Transformation 3】 (In the formulas (7) to (10), R １ａ ~R ６ａ each independently represents a divalent organic group, X represents a hydrolyzable silyl group, and FA represents a fatty acid.

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