thermosetting resin composition

Abstract

The present invention provides a curable resin composition having a high glass transition temperature, improved toughness resistance, excellent thermal oxidation resistance, and hydrolysis resistance, a substrate coated with the composition, and a process for forming the coated substrate. [Solution] A curable resin composition is provided, comprising a thermosetting resin, a toughening agent component containing a multi-stage polymer and a thermoplastic toughening agent, and a phenylindanediamine curing agent. This curable resin composition can be used as a coating for various applications, such as industrial, automotive, and electronic applications, particularly those involving high-temperature operating conditions.

Description

[Technical Field]

[0001] Cross-reference of related applications This application claims the interests of U.S. Provisional Patent Application No. 63 / 066,335, filed August 17, 2020. The entire contents of this application are expressly incorporated herein by reference.

[0002] This disclosure relates to curable resin compositions having, in general, a high glass transition temperature, improved toughness resistance, and excellent thermal oxidation and hydrolysis resistance. These curable resin compositions are particularly suitable for use as coatings in industrial, automotive, and electronic applications, especially those involving high-temperature operating conditions. [Background technology]

[0003] Thermosetting materials, such as cured epoxy resins, are well-known for their heat and chemical resistance. While they also exhibit good mechanical properties, they often lack toughness and tend to be very brittle. This is especially true as the crosslinking density of these materials increases, or when the monomer functionality is greater than 2. Attempts have been made to strengthen or toughen epoxy resins and other thermosetting materials, such as bismaleimide resins, benzoxazine resins, cyanate ester resins, epoxy vinyl ester resins, and unsaturated polyester resins, by incorporating various toughening materials.

[0004] Such toughening agents can be compared to one another based on their structural, morphological, or thermal properties. The skeletal structure of toughening agents can be aromatic, aliphatic, or a combination of both. Aromatic toughening agents, such as polyether ether ketones or polyimides, result in thermosetting materials that exhibit reasonable improvement in toughening, or so-called post-impact compression, and low moisture uptake when exposed to high-temperature, humid environments, due to the aromatic structure of the toughening agent. Conversely, aliphatic toughening agents, such as nylon (also known as polyamide), exhibit significant improvement in post-impact compression, but result in thermosetting materials with higher-than-desirable moisture uptake when exposed to high-temperature, humid environments, which can lead to a decrease in compressive strength and compression coefficient. Other toughening agents, such as core-shell polymers, can result in thermosetting materials with good damage resistance. However, these toughening agents tend to adversely affect the processability and glass transition temperature of thermosetting materials.

[0005] One type of toughening agent that has recently come into use in thermosetting resin compositions is multi-stage polymers, such as those described in Patent Documents 1, 2, 3, 4, 5, 6, and 7. Although it has been found that such toughening agents readily disperse in thermosetting matrices to produce homogeneous dispersions, the cured products may still lack appropriate toughness and chemical properties.

[0006] Therefore, there is a need to further improve the current state of this field by utilizing toughening agents and curing agents in thermosetting materials, which, upon curing, exhibit a high glass transition temperature and mechanical and chemical properties that make them particularly suitable for use as coatings for various substrates exposed to harsh operating conditions. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] WO2016102666 [Patent Document 2] WO2016102658 [Patent Document 3] WO2016102682 [Patent Document 4] WO2017211889 [Patent Document 5] WO2017220793 [Patent Document 6] WO2018002259 [Patent Document 7] WO2019012052 [Summary of the Invention]

[0008] The present disclosure generally provides a curable resin composition comprising (a) a thermosetting resin, (b) a toughening agent component comprising a multistage polymer and a thermoplastic toughening agent, and (c) a phenylindanediamine curing agent. The curable resin composition can be used in a variety of applications, including those where a composition exhibiting a glass transition temperature of at least 150°C, improved toughness, and high thermal oxidation resistance and hydrolysis resistance is required when rapidly cured. That is, the curable resin composition is particularly suitable for use as industrial piping (e.g., for the chemical and oil and gas industries), construction applications, and coatings for electronic devices or other commercial applications. [Modes for Carrying Out the Invention]

[0009] This disclosure generally provides curable resin compositions comprising (a) a thermosetting resin, (b) a toughening agent component comprising a multi-stage polymer and a thermoplastic toughening agent, and (c) a phenylindanediamine curing agent. It was unexpectedly discovered that the combination of the multi-stage polymer and the thermoplastic toughening agent, together with the phenylindanediamine curing agent, acts synergistically to result in a toughening effect greater than that expected for each component alone, and yields a cured coating exhibiting excellent thermal oxidation resistance and hydrolysis resistance. The curable resin compositions described herein demonstrate high heat resistance in both aqueous and dry environments required for advanced high-temperature applications. Coatings obtained by curing the curable resin compositions also exhibit a glass transition temperature Tg > 150°C, preferably Tg > 170°C, and most preferably Tg > 190°C.

[0010] The following terms shall have the meanings set forth below:

[0011] The terms "cure," "cured," or similar terms such as "curing" or "cure" refer to the curing of thermosetting resins by chemical crosslinking. The term "curable" means a composition that can be subjected to conditions that result in a cured or thermoset state or condition.

[0012] The term "multi-stage polymer" refers to a polymer formed sequentially by a multi-stage polymerization process. A multi-stage emulsion polymerization process is possible, in which case the first polymer is the first-stage polymer and the second polymer is the second-stage polymer (i.e., the second polymer is formed by emulsion polymerization in the presence of the first emulsion polymer).

[0013] The term "(meth)acrylic acid polymer" refers to a (meth)acrylic acid polymer containing a (meth)acrylic acid monomer, where the monomer constitutes 50% by weight or more of the polymer, and the polymer is essentially composed of such monomers.

[0014] The term “comprising” and its derivatives are not intended to exclude any additional elements, processes, or procedures, whether disclosed herein or otherwise. For the purpose of avoiding any doubt, all elements claimed herein through the use of the term “comprising” may include any additional adducts or compounds, unless otherwise stated. Conversely, the term “consisting essentially of” where it appears herein shall not, in any subsequent enumeration, imply the extenuating nature of the exercise. Except for those that are not essential, any other elements, processes, or procedures are excluded, and the term "consisting of" excludes any elements, processes, or procedures that are not specifically described or enumerated, where used. The term "or" refers to the enumerated elements individually or in any combination, unless otherwise specified.

[0015] The articles "a" and "an" are used herein to indicate that the grammatical object of the article is one or more than one (i.e., at least one). For example, "an epoxy resin" means one type of epoxy resin or more than one type of epoxy resin.

[0016] The phrases "in one embodiment" and "according to one embodiment" generally mean that the specific feature, structure, or characteristic following those phrases is included in at least one aspect of the disclosure, and may be included in more than one embodiment of the disclosure. Importantly, such terms do not necessarily refer to the same embodiment.

[0017] When “may,” “can,” “could,” or “might” are used in a specification to describe that an element or feature is included or has a certain characteristic, it is not required that the particular element or feature actually be included or have that characteristic.

[0018] When used herein, the term "approximately" allows for some degree of variability in a given value or range, for example, it may be within 10%, 5%, or 1% of the stated value or the stated range limit.

[0019] Values ​​expressed in range format must be interpreted flexibly, including not only the numerical limit of the range but also the individual numerical values ​​or subranges contained within that range, as if each numerical value and subrange were explicitly stated. For example, a range such as 1-6 must be considered to specifically disclose subranges such as 1-3, 2-4, 3-6, and the individual numbers contained within those ranges, such as 1, 2, 3, 4, 5, and 6. This applies regardless of the width of the range.

[0020] The terms “preferred” and “preferred” refer to embodiments that can provide a particular benefit under certain circumstances. However, other embodiments may also be preferred under the same or other circumstances. Furthermore, the enumeration of one or more preferred embodiments does not imply that other embodiments are unhelpful, nor is it intended to exclude other embodiments from the scope of this disclosure.

[0021] In accordance with the first embodiment, the present disclosure provides a curable resin composition comprising generally (a) a thermosetting resin, (b) a toughening agent component comprising a multi-stage polymer and a thermoplastic toughening agent, and (c) a phenylindanediamine curing agent.

[0022] In one embodiment, the thermosetting resin can be an epoxy resin, a bismaleimide resin, a benzoxazine resin, a cyanate ester resin, a phenolic resin, a vinyl ester resin, or a mixture thereof. In one particular embodiment, the thermosetting resin is an epoxy resin.

[0023] In general, any epoxy-containing compound is suitable for use as an epoxy resin in this disclosure, for example, the epoxy-containing compound disclosed in U.S. Patent No. 5,476,748. This is the case. U.S. Patent No. 5,476,748 is incorporated herein by reference. According to one embodiment, the epoxy resin is selected from monofunctional epoxy resins, difunctional epoxy resins (i.e., having two epoxide groups), trifunctional epoxy resins (i.e., having three epoxide groups), tetrafunctional epoxy resins (i.e., having four epoxide groups), and mixtures thereof.

[0024] Typical examples, though not limited, of monofunctional epoxy resins include: phenols, cresols, tert-butylphenol and other alkylphenols, butanol, 2-ethylhexanol, and C8-C14 alcohols, such as styrene oxides, cyclohexene oxides, and glycidyl ethers.

[0025] Typical examples, though not limited, of bifunctional epoxy resins include: bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, tetrabromobisphenol A diglycidyl ether, propylene glycol diglycidyl ether, butylene glycol diglycidyl ether, ethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether, bisphenol A polyethylene glycol diglycidyl ether, bisphenol A polypropylene glycol diglycidyl ether, 3,4-epoxycyclohexylmethyl carboxylate, hexahydrophthalate diglycidyl ester, methyltetrahydrophthalate diglycidyl ester, and mixtures thereof. Depending on the embodiment, the bifunctional epoxy resin may be modified with a monofunctional reactive diluent, such as p-tertiary butylphenol glycidyl ether, cresyl glycidyl ether, 2-ethylhexyl glycidyl ether, and C8-C 14 Examples include glycidyl ethers, but the program is not limited to these.

[0026] Typical examples, though not limited, of trifunctional epoxy resins include: para-aminophenol triglycidyl ethers, meta-aminophenol triglycidyl ethers, dicyclopentadiene-based epoxy resins, N,N,O-triglycidyl-4-amino-m- or -5-amino-o-cresol-type epoxy resins, and 1,1,1-(triglycidyloxyphenyl)methane-type epoxy resins.

[0027] Typical examples, though not limited, of tetrafunctional epoxy resins include: N,N,N',N'-tetraglycidylmethylenedianiline, N,N,N',N'-tetraglycidyl-m-xylenediamine, tetraglycidyldiaminodiphenylmethane, sorbitol polyglycidyl ether, pentaerythritol tetraglycidyl ether, tetraglycidylbisaminomethylcyclohexane, and tetraglycidyl glycol uryl.

[0028] Examples of commercially available epoxy resins that can be used include ARALDITE® PY306 epoxy resin (unmodified bisphenol-F liquid epoxy resin), ARALDITE® MY721 epoxy resin (tetrafunctional epoxy resin based on methylenedianiline), ARALDITE® MY0510 epoxy resin (trifunctional epoxy resin based on para-aminophenol), ARALDITE® GY6005 epoxy resin (bisphenol-A liquid epoxy resin modified with a monofunctional reactive diluent), ARALDITE® 6010 epoxy resin (bisphenol-A liquid epoxy resin), ARALDITE® MY06010 epoxy resin (trifunctional epoxy resin based on meta-aminophenol), and ARALDITE® GY285. Examples include, but are not limited to, epoxy resins (unmodified bisphenol-F liquid epoxy resins), ARALDITE® EPN1138, 1139, and 1180 epoxy resins (epoxyphenol novolac resins), ARALDITE® ECN1273 and 9611 epoxy resins (epoxy cresol novolac resins), ARALDITE® GY289 epoxy resin (epoxyphenol novolac resin), ARALDITE® PY307-1 epoxy resin (epoxyphenol novolac resin), and mixtures thereof.

[0029] In one embodiment, the amount of epoxy resin present in the curable resin composition can be about 10% to about 95% by weight, or about 20% to about 75% by weight, or about 30% to about 60% by weight, or about 40% to about 50% by weight, based on the total weight of the curable resin composition. In another embodiment, the amount of epoxy resin present in the curable resin composition can be about 50% to about 95% by weight, or about 65% to about 90% by weight, based on the total weight of the curable resin composition.

[0030] In yet another embodiment, the epoxy resin may consist of at least one trifunctional epoxy resin or tetrafunctional epoxy resin or a mixture thereof, and optionally at least one bifunctional epoxy resin. In such embodiments, the trifunctional epoxy resin may be present in the curable resin composition in an amount of about 25% to about 50% by weight, or about 35% to about 45% by weight, based on the total weight of the curable resin composition, and the tetrafunctional epoxy resin may be present in the curable resin composition in an amount of about 1% to 20% by weight, or about 5% to about 15% by weight, based on the total weight of the curable resin composition.

[0031] According to another embodiment, the thermosetting resin is a benzoxazine resin. The benzoxazine resin can be any curable monomer, oligomer, or polymer having at least one benzoxazine moiety. That is, in one embodiment, the benzoxazine can be represented by general formula (1) [ka] In the formula, b is an integer between 1 and 4; each R is independently hydrogen, substituted or unsubstituted C1-C 20 Alkyl, substituted or unsubstituted C2-C 20 Alkenyl group, substituted or unsubstituted C6-C 20 Aryl group, substituted or unsubstituted C2-C 20 Heteroaryl group, substituted or unsubstituted C4-C 20A carbon cyclic group, a substituted or unsubstituted C2-C 20 heterocyclic group, or a C3-C8 cycloalkyl group; each R1 is independently hydrogen, a C1-C 20 alkyl group, a C2-C 20 alkenyl group, or a C6-C 20 aryl group; and Z is a direct bond (when b = 2), a substituted or unsubstituted C1-C 20 alkyl group, a substituted or unsubstituted C6-C 20 aryl group, a substituted or unsubstituted C2-C 20 heteroaryl group, O, S, S=O, O=S=O, or C=O. As substituents, hydroxy, a C1-C 20 alkyl group, a C2-C 10 alkoxy group, mercapto, a C3-C8 cycloalkyl group, a C6-C 14 heterocyclic group, a C6-C 14 aryl group, a C6-C 14 heteroaryl -yl group, halogen, cyano, nitro, nitrone, amino, amide, acyl, oxyacyl, carboxyl, carbamate, sulfonyl, sulfonamide, and sulfuryl are included, but not limited thereto.

[0032] In a specific embodiment within formula (1), the benzoxazine can be represented by the following formula (1a)

Chemical formula

Chemical formula

[0033] In another embodiment, the benzoxazine may be included in the following general formula (2) [ka] In the formula, Y is C1-C 20 Alkyl alkyl group, C2-C 20 An alkenyl group, or a substituted or unsubstituted phenyl group; and each R2 is independently hydrogen, halogen, C1-C 20 Alkyl alkyl group, C2-C 20 Alkenyl group, or C6-C 20 It is an aryl group. Suitable substituents for phenyl are as described above.

[0034] In certain embodiments of formula (2), benzoxazine can be represented by the following formula (2a): [ka] In the formula, each R2 is independently C1-C 20 Alkyl or C2-C 20 Alkenyl groups, each of these groups optionally substituted or inserted with one or more O, N, S, C=O, COO, and NHC=O, and C6-C 20 It is an aryl group; and each R3 independently consists of hydrogen, C1-C 20 Alkyl or C2-C 20 Alkenyl groups, each of these groups is optionally substituted or inserted with one or more O, N, S, C=O, COOH, and NHC=O, or C6-C 20 It is an aryl group.

[0035] Alternatively, benzoxazine may be included in the following general formula (3) [ka] In the formula, p is 2; W is selected from biphenyl, diphenylmethane, diphenylisopropane, diphenyl sulfide, diphenyl sulfoxide, diphenyl sulfone, and diphenyl ketone; and R 1 It is defined as described above.

[0036] Benzooxazine is commercially available from several suppliers, including Huntsman Advanced Materials Americas LLC, Georgia Pacific Resins Inc., and Shikoku Chemicals Corporation.

[0037] Benzooxazines can also be obtained by reacting a phenol compound, such as bisphenol A, bisphenol F, or phenolphthalein, with an aldehyde, such as formaldehyde, and a primary amine, under conditions where water is removed. The molar ratio of the phenol compound to the aldehyde reactant can be about 1:3 to 1:10, or about 1:4 to 1:7. In yet another embodiment, the molar ratio of the phenol compound to the aldehyde reactant can be about 1:4.5 to 1:5. The molar ratio of the phenol compound to the primary amine reactant can be about 1:1 to 1:3, or about 1:1.4 to 1:2.5. In yet another embodiment, the molar ratio of the phenol compound to the primary amine reactant can be about 1:2.1 to 1:2.2.

[0038] Examples of primary amines include: aromatic mono or diamines, aliphatic amines, cycloaliphatic amines, and heterocyclic monoamines, such as aniline, o-, m-, and p-phenylenediamine, benzidine, 4,4'-diaminodiphenylmethane, cyclohexylamine, butylamine, methylamine, hexylamine, allylamine, furfurylamine ethylenediamine, and propylenediamine. The amines may be substituted with C1-C8 alkyl or allyl groups at their individual carbon portions. In one embodiment... Primary amines have the general formula R a A compound having NH2, where R a R is allyl, unsubstituted or substituted phenyl, unsubstituted or substituted C1-C8 alkyl, or unsubstituted or substituted C3-C8 cycloalkyl. aSuitable substituents for the group include, but are not limited to, amino, C1-C4 alkyl, and allyl groups. Depending on the embodiment, one to four substituents may be present in R. a It can exist as a base. In one particular embodiment, R a It is phenyl.

[0039] In one embodiment, benzoxazine may be present in the curable composition in an amount ranging from about 10% to about 90% by weight, based on the total weight of the curable composition. In another embodiment, benzoxazine may be present in the curable composition in an amount ranging from about 60% to about 90% by weight, based on the total weight of the curable composition.

[0040] The curable resin composition also includes a multi-stage polymer and a toughening agent component containing a thermoplastic toughening agent.

[0041] A multi-stage polymer (e.g., as described in WO2016 / 102411 and WO2016 / 102682, the contents of which are incorporated herein by reference) has at least two different stages of polymer composition, the first stage forming the core, and the second stage or all subsequent stages forming individual shells. The multi-stage polymer can be in the form of polymer particles, particularly spherical particles. Such polymer particles, also called core-shell particles, have a first stage that forms the core and a second stage or all subsequent stages that form individual shells. In one embodiment, the polymer particles can have a weight-average particle size of 20 nm to 800 nm, or 25 nm to 600 nm, or 30 nm to 550 nm, or 40 nm to 400 nm, or 75 nm to 350 nm, or 80 nm to 300 nm. The polymer particles can also be aggregated to form a polymer powder.

[0042] In other words, the polymer particles may have a multilayer structure comprising at least one layer (or step) (A) containing polymer (A1) having a glass transition temperature of less than about 10°C, and at least another layer (or step) (B) containing polymer (B1) having a glass transition temperature of more than about 30°C. In some embodiments, polymer (B1) is the outer layer of the polymer particles. In other embodiments, step (A) containing polymer (A1) is the first step, and step (B) containing polymer (B1) is grafted onto step (A) containing polymer (A1).

[0043] As described above, polymer particles can be obtained by a multi-step process, for example, a process involving two, three, or more steps. Polymer (A1) having a glass transition temperature of layer (A) below approximately 10°C is never produced during the final step of the multi-step process. This means that polymer (A1) is never present in the outer layer of the particle. Therefore, polymer (A1) having a glass transition temperature of layer (A) below approximately 10°C is present in either the core or one of the inner layers of the polymer particle.

[0044] In some embodiments, polymer (A1) having a glass transition temperature of less than approximately 10°C for layer (A) is produced during the first step of a multi-step process that forms the core of polymer particles having a multilayer structure and / or before polymer (B1).

[0045] In other embodiments, polymer (B1) having a glass transition temperature above approximately 30°C is produced in the final step of a multi-step process that forms the outer layer of polymer particles. There may be one or more additional intermediate layers obtained in one or more intermediate steps.

[0046] In one embodiment, at least a portion of the polymer (B1) of layer (B) is grafted onto the polymer made in the preceding layer. If there are only two steps, (A) and (B), each containing polymer (A1) and polymer (B1), then a portion of polymer (B1) is grafted onto the polymer ( It is grafted onto A1). Depending on the embodiment, at least 50% by weight of the polymer (B1) is grafted.

[0047] According to one embodiment, polymer (A1) is a (meth)acrylic acid polymer containing at least 50% by weight of monomers derived from alkyl acrylate. In a further embodiment, polymer (A1) contains one or more copolymerizable monomers that can copolymerize with alkyl acrylate, provided that polymer (A1) has a glass transition temperature of less than about 10°C. One or more copolymerizable monomers in polymer (A1) can be selected from (meth)acrylic acid monomers and / or vinyl monomers. The (meth)acrylic acid copolymerizable monomer is (meth)acrylic acid C1-C 12 The polymer (A1) may include monomers selected from alkyl groups. In further embodiments, the (meth)acrylic acid copolymer monomer in polymer (A1) includes C1-C4 alkyl (meth)acrylic acid monomers and / or C1-C8 alkyl acrylic acid monomers. Particularly preferred are the acrylic acid copolymer monomer or methacrylic acid copolymer monomer of polymer (A1) selected from methyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, tert-butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and mixtures thereof, provided that polymer (A1) has a glass transition temperature of less than about 10°C.

[0048] In another embodiment, polymer (A1) is crosslinked (i.e., a crosslinking agent is added to one or more other monomers). The crosslinking agent may have at least two polymerizable groups.

[0049] In one specific embodiment, polymer (A1) is an homologous polymer of butyl acrylate. In another specific embodiment, polymer (A1) is a copolymer of butyl acrylate and at least one crosslinking agent. The crosslinking agent may be present in an amount of less than 5% by weight of the copolymer.

[0050] In yet another embodiment, the polymer (A1) having a glass transition temperature of less than about 10°C is a silicone rubber polymer. The silicone rubber can be, for example, polydimethylsiloxane.

[0051] In yet another embodiment, the polymer (A1) having a glass transition temperature of less than about 10°C contains at least 50% by weight of polymer units derived from isoprene or butadiene, and step (A) is the innermost layer of the polymer particles. In other words, step (A), which contains polymer (A1), is the core of the polymer particles. For example, the polymer (A1) of the core can be made of an isoprene isoprene or butadiene isoprene, an isoprene-butadiene copolymer, a copolymer of isoprene with up to 98% by weight of a vinyl monomer, and a copolymer of butadiene with up to 98% by weight of a vinyl monomer. The vinyl monomer can be styrene, alkylstyrene, acrylonitrile, alkyl (meth)acrylate, or butadiene or isoprene. In one embodiment, the core is a butadiene isoprene.

[0052] Polymer (B1) can be made from the same polymer and copolymer containing monomers and / or vinyl monomers having double bonds. Preferably, polymer (B1) is a (meth)acrylic acid polymer. Preferably, polymer (B1) is (meth)acrylic acid C1-C 12 The polymer (B1) contains at least 70% by weight of a monomer selected from alkyls. More preferably, the polymer (B1) contains at least 80% by weight of a C1-C4 alkyl methacrylate monomer and / or a C1-C8 alkyl acrylate monomer. Particularly preferably, the acrylic acid monomer or methacrylate monomer of polymer (B1) is methyl acrylate, ethyl acrylate, or butyl acrylate, provided that polymer (B1) has a glass transition temperature of at least about 30°C. The polymer (B1) is selected from methyl methacrylate, ethyl methacrylate, butyl methacrylate, and mixtures thereof. Advantageously, the polymer (B1) contains at least 70% by weight of monomer units derived from methyl methacrylate.

[0053] In another embodiment, the multi-stage polymer as already described has an additional step, which is a (meth)acrylic acid polymer (P1). The primary polymer particles according to this embodiment will have a multilayer structure comprising at least one step (A) comprising a polymer (A1) having a glass transition temperature of less than about 10°C, at least one step (B) comprising a polymer (B1) having a glass transition temperature greater than about 30°C, and at least one step (P) comprising a (meth)acrylic acid polymer (P1) having a glass transition temperature of about 30°C to about 150°C. Preferably, the (meth)acrylic acid polymer (P1) is not grafted onto either polymer (A1) or (B1).

[0054] The (meth)acrylic acid polymer (P1) may have a mass-average molecular weight Mw of less than about 100,000 g / mol, or less than about 90,000 g / mol, or less than about 80,000 g / mol, or less than about 70,000 g / mol, preferably less than about 60,000 g / mol, more preferably less than about 50,000 g / mol, and even more preferably less than about 40,000 g / mol.

[0055] The (meth)acrylic acid polymer (P1) can have a mass-average molecular weight Mw of more than approximately 2000 g / mol, or more than approximately 3000 g / mol, or more than approximately 4000 g / mol, or more than approximately 5000 g / mol, preferably more than approximately 6000 g / mol, more preferably more than approximately 6500 g / mol, even more preferably more than approximately 7000 g / mol, and most preferably more than approximately 10,000 g / mol.

[0056] The mass-average molecular weight Mw of the (meth)acrylic acid polymer (P1) can be approximately 2,000 g / mol to approximately 100,000 g / mol, or approximately 3,000 g / mol to approximately 90,000 g / mol, or approximately 4,000 g / mol to approximately 80,000 g / mol, preferably approximately 5,000 g / mol to approximately 70,000 g / mol, more preferably approximately 6,000 g / mol to approximately 50,000 g / mol, and most preferably approximately 10,000 g / mol to approximately 40,000 g / mol.

[0057] Preferably, the (meth)acrylic acid polymer (P1) is a copolymer containing a (meth)acrylic acid monomer. More preferably, the (meth)acrylic acid polymer (P1) is a (meth)acrylic acid polymer. Even more preferably, the (meth)acrylic acid polymer (P1) is a (meth)acrylic acid C1-C 12 The polymer contains at least 50% by weight of monomers selected from alkyls. Advantageously, the (meth)acrylic acid polymer (P1) contains at least 50% by weight of monomers selected from C1-C4 alkyl methacrylates, C1-C8 alkyl acrylates, and mixtures thereof. More advantageously, the (meth)acrylic acid polymer (P1) contains at least 50% by weight of polymerized methyl methacrylate, more advantageously at least 60% by weight, and most advantageously at least 65% by weight of polymerized methyl methacrylate.

[0058] In one embodiment, the (meth)acrylic acid polymer (P1) contains 50% to 100% by weight of methyl methacrylate, 80% to 100% by weight of methyl methacrylate, or 80% to 99.8% by weight of methyl methacrylate and 0.2% to 20% by weight of a C1-C8 alkyl acrylate monomer. Advantageously, the C1-C8 alkyl acrylate monomer is selected from methyl acrylate, ethyl acrylate, or butyl acrylate.

[0059] In another embodiment, the (meth)acrylic acid polymer (P1) contains 0.01% to 50% by weight of the functional monomer. Preferably, the (meth)acrylic acid polymer (P1) contains the functional monomer The mass contains 0.01% to 30% by weight, more preferably 1% to 30% by weight, even more preferably 2% to 30% by weight, and advantageously 3% to 30% by weight.

[0060] In one embodiment, the functional monomer is selected from glycidyl (meth)acrylate, acrylic acid or methacrylic acid, amides derived from acrylic acid or methacrylic acid, such as dimethylacrylamide, 2-methoxyethyl acrylate or 2-methoxyethyl methacrylate, 2-aminoethyl acrylate or 2-aminoethyl methacrylate (which is optionally quaternized), acrylic acid or methacrylic acid monomers having a phosphonate or phosphate group, alkylimidazolidinone (meth)acrylate, and polyethylene glycol (meth)acrylate. Preferably, the polyethylene glycol group of polyethylene glycol (meth)acrylate has a molecular weight in the range of 400 g / mol to 10,000 g / mol.

[0061] In one embodiment, the toughening agent component also includes a thermoplastic toughening agent. In one embodiment, the thermoplastic toughening agent is a polyethersulfone. Examples, though not limited to, of polyethersulfone include particulate polyethersulfone sold by Sumitomo Chemicals under the trademark Sumnikaexcel®, and polyethersulfone sold by Solvay Chemicals under the trademarks Veradel® and Virantage®. High-density polyethersulfone particles may also be used. The shape of the polyethersulfone is not particularly important because it can dissolve during the formation of the curable resin composition. High-density polyethersulfone particles can be made according to the teachings of U.S. Patent No. 4,945,154, which is incorporated herein by reference. High-density polyethersulfone particles may also be used from those sold by Hexcel Corporation under the trademark HRI-1. In some embodiments, the average particle size of the polyethersulfone is less than 100 microns to promote and ensure that the polyethersulfone is completely dissolved in the thermosetting resin.

[0062] In another embodiment, the thermoplastic toughening agent can be any of the following thermoplastic polymers: polysulfone, polyetherimide, polyamide (PA), poly(phenylene) oxide (PPO), poly(ethylene oxide) (PEO), phenoxy, poly(methyl methacrylate) (PMMA), poly(vinylpyrrolidone) (PVP), poly(etheretherketone) (PEEK), poly(styrene) (PS), polycarbonate (PC), or a mixture thereof. According to one embodiment, polyethersulfone is the only thermoplastic toughening agent included in the curable resin composition (i.e., the curable resin composition does not contain any thermoplastic polymer toughening agents other than polyethersulfone).

[0063] In one embodiment, the amount of toughening agent component present in the curable resin composition is less than about 25% by weight, based on the total weight of the curable resin composition. In another embodiment, the amount of toughening agent component present in the curable resin composition is less than about 22.5% by weight, or less than about 20% by weight, or less than about 17.5% by weight, or less than about 15% by weight, based on the total weight of the curable resin composition. In another embodiment, the amount of toughening agent component present in the curable resin composition is at least about 1% by weight, or at least about 5% by weight, or at least about 7.5% by weight, based on the total weight of the curable resin composition. In yet another embodiment, the amount of toughening agent component present in the curable resin composition is about 1% to about 25% by weight, or about 5% to about 20% by weight, or about 7% to about 16% by weight, based on the total weight of the curable resin composition. In yet another embodiment, the amount of toughening agent component present in the curable resin composition is about 1% to about 15% by weight, based on the total weight of the curable resin composition.

[0064] In another embodiment, the amount of multistage polymer present in the curable resin composition is about 3% to about 20% by weight, or about 4% to about 15% by weight, or about 5% to about 10% by weight, based on the total weight of the curable resin composition. In yet another embodiment, the amount of thermoplastic toughening agent present in the curable resin mixture is about 0.1% to about 10% by weight, or about 0.5% to about 8% by weight, or about 1% to about 7% by weight, based on the total weight of the curable resin composition.

[0065] Curing of a curable resin composition can be achieved by adding phenylindanediamine. In one embodiment, phenylindanediamine is a compound having the following structure. [ka] In the formula, R 2 R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; 3 b is independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms; and b is independently an integer from 1 to 4, and the amino group of the indan ring is at position 5 or 6.

[0066] Phenylindanediamine can contain any combination of isomers or substituted isomers of phenylindanediamine compounds. For example, phenylindanediamine can contain 0 mol% to 100 mol% of 5-amino-3-(4'-aminophenyl)-1,1,3-trimethylindan in combination with 100 mol% to 0 mol% of 6-amino-3-(4'-aminophenyl)-1,1,3-trimethylindan. Furthermore, one or both of these isomers can be substituted with any of the substituted diamine isomers over the entire range of 0 to 100%. Examples of such substituted diamine isomers include 5-amino-6-methyl-3-(3'-amino-4'-methylphenyl)-1,1,3-trimethylindan, 5-amino-3-(4'-amino-Ar',Ar'-dichlorophenyl)-Ar,Ar-dichloro-1,1,3-trimethylindan, 6-amino-(4'-amino-Ar',Ar'-dichlorophenyl)-Ar,Ar-dichloro-1,1,3-trimethylindan, 4-amino-6-methyl-3(3'-amino-4'-methylphenyl)-1,1,3-trimethylindan, and Ar-amino-3-(Ar'-amino-2',4'-dimethylphenyl)-1,1,3,4,6-pentamethylindan. The prefixes Ar and Ar' in the above formulas indicate that the position of the given substituent is not limited to within the phenyl ring.

[0067] Among phenylindanediamines, R 2 However, independently, they are hydrogen or methyl, and R 3 However, those that are independently hydrogen, methyl, chloro, or bromo can be listed. In particular, suitable phenylindanediamines are R 2 R is hydrogen or methyl, and R3 is independently hydrogen, methyl, chloro, or bromo, and the amino group is at the 5th or 6th position and the 3' or 4' position. Due to relative availability, R is a particularly preferred phenylindanediamine. 2 is methyl, and each R 3Examples include compounds in which the atom is hydrogen, and the amino group is located at the 5th, 6th, or 4' position. These compounds are known as 5(6)-amino-3-(4'-aminophenyl)-1,1,3-trimethylindan (DAPI).

[0068] Phenylindanediamines and methods for preparing them are described in U.S. Patent Nos. 3,856,752 and 3,983,092, which are fully incorporated herein by reference with respect to their disclosure relating to the preparation of such materials.

[0069] In addition to phenylindanediamine, other curing agents may be included, including, but are not limited to, aromatic amines, cyclic amines, aliphatic amines, alkylamines, polyetheramines (including polyetheramines that may be derived from polypropylene oxide and / or polyethylene oxide), 9,9-bis(4-amino-3-chlorophenyl)fluorene (CAF), acid anhydrides, carboxylic acid amides, polyamides, polyphenols, cresol and phenol novolac resins, imidazoles, guanidines, substituted guanidines, substituted ureas, melamine resins, guanamine derivatives, tertiary amines, Lewis acid complexes, such as boron trifluoride and boron trichloride, and polymer captans. Any epoxy-modified amine products, Mannich-modified products, and Michael-modified addition products of the above curing agents are also usable. All of the curing agents mentioned above can be used individually or in any combination.

[0070] Examples of aromatic amines include 1,8-diaminonaphthalene, m-phenylenediamine, diethylenetoluenediamine, diaminodiphenylsulfone, diaminodiphenylmethane, diaminodiethyldimethyldiphenylmethane, 4,4'-methylenebis(2,6-diethylaniline), 4,4'-methylenebis(2-isopropyl-6-methylaniline), 4,4'-methylenebis(2,6-diisopropylaniline), and 4,4'-[1,4-phenylenebis(1-methyl-ethylaniline] Examples of aromatic amines include, but are not limited to, bis(4-amino-2-chloro-3,5-diethylphenyl)methane

[0071] Examples of cyclic amines include, but are not limited to, bis(4-amino-3-methyldicyclohexyl)methane, diaminodicyclohexylmethane, bis(aminomethyl)cyclohexane, N-aminoethylpyrazine, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro(5,5)undecane, m-xylenediamine, isophoronediamine, mentendiamine, 1,4-bis(2-amino-2-methylpropyl)piperazine, N,N'-dimethylpiperazine, pyridine, picoline, 1,8-diazabicyclo[5,4,0]-7-undecene, benzylmethylamine, 2-(dimethylaminomethyl)-phenol, 2-methylimidazole, 2-phenylimidazole, and 2-ethyl-4-methylimidazole.

[0072] Examples of aliphatic amines include diethylenetriamine, triethylenetetramine, tetraethylenepentaamine, 3-(dimethylamino)propylamine, 3-(diethylamino)-propylamine, 3-(methylamino)propylamine, tris(2-aminoethyl)amine; 3-(2-ethylhexyloxy)propylamine, 3-ethoxypropylamine, 3-methoxypropylamine, 3-(dibutylamino)propylamine, and tetramethylethylenediamine; ethylenediamine; 3,3'-iminobis(propylamine), N-methyl-3,3'-iminobis(propylamine); allylamine, diallyluamine Examples include, but are not limited to, mine, triallylamine, polyoxypropylenediamine, and polyoxypropylenetriamine.

[0073] Examples of alkylamines include, but are not limited to, methylamine, ethylamine, propylamine, isopropylamine, butylamine, sec-butylamine, t-butylamine, n-octylamine, 2-ethylhexylamine, dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, di-sec-butylamine, di-t-butylamine, di-n-octylamine, and di-2-ethylhexylamine.

[0074] Examples of acid anhydrides include cyclohexane-1,2-dicarboxylic anhydride, 1-cyclohexene-1,2-dicarboxylic anhydride, 2-cyclohexene-1,2-dicarboxylic anhydride, 3-cyclohexene-1,2-dicarboxylic anhydride, 4-cyclohexene-1,2-dicarboxylic anhydride, 1-methyl-2-cyclohexene-1,2-dicarboxylic anhydride, 1-methyl-4-cyclohexene-1,2-dicarboxylic anhydride, 3-methyl-4-cyclohexene-1,2-dicarboxylic anhydride, 4-methyl-4-cyclohexene-1,2-dicarboxylic anhydride, dodecenyl succinic anhydride, succinic anhydride, 4-methyl-1-cyclohexene-1,2-dicarboxylic anhydride, phthalic anhydride, hexahydrophthalic anhydride, and nadic methyl anhydride. Examples include, but are not limited to, anhydrides, dodecenyl succinic anhydride, tetrahydrophthalic anhydride, maleic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenonetetracarboxylic anhydride, bicyclo[2.2.1]hepta-5-ene-2,3-dicarboxylic anhydride, methylbicyclo[2.2.1]hepta-5-ene-2,3-dicarboxylic anhydride, bicyclo[2.2.1]hepta-5-ene-2,3-dicarboxylic anhydride, dichloromaleic anhydride, chloridenic anhydride, tetrachlorophthalic anhydride, and any derivatives or adducts thereof.

[0075] Examples of imidazoles include imidazole, 1-methylimidazole, 2-methylimidazole, 2-ethylimidazole, 2-isopropylimidazole, 2-n-propylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-isopropyl-2-methylimidazole, and 1-cyanoethyl-2-methylimidazole. Examples include, but are not limited to, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 1,2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-dodecyl-2-methylimidazole, and 1-cyanoethyl-2-phenyl-4,5-di(2-cyanoethoxy)methylimidazole.

[0076] Examples of substituted guanidines include methylguanidine, dimethylguanidine, trimethylguanidine, tetramethylguanidine, methylisobiguanidine, dimethylisobiguanidine, tetramethylisobiguanidine, hexamethylisobiguanidine, heptamethylisobiguanidine, and cyanoguanidine (dicyandiamide). Representative guanamine derivatives that can be listed include alkylated benzoguanamine resin, benzoguanamine resin, or methoxymethylethoxymethylbenzoguanamine. Examples of substituted ureas include p-chlorophenyl-N,N-dimethylurea (monulone), 3-phenyl-1,1-dimethylurea (phenulone), or 3,4-dichlorophenyl-N,N-dimethylurea (diurone).

[0077] Examples of tertiary amines include trimethylamine, tripropylamine, triisopropylamine, tributylamine, tri-sec-butylamine, tri-t-butylamine, tri-n-octylamine, N,N-dimethylaniline, N,N-dimethylbenzylamine, pyridine, N-methylpiperidine, N-methylmorpholine, N,N-dimethylaminopyridine, and morpholine derivatives, such as bis(2-(2,6-dimethyl-4-morpholino) Examples include, but are not limited to, ethyl)-(2-(4-morpholino)ethyl)amine, bis(2-(2,6-dimethyl-4-morpholino)ethyl)-(2-(2,6-diethyl-4-morpholino)ethyl)amine, tris(2-(4-morpholino)ethyl)amine, and tris(2-(4-morpholino)propyl)amine, diazabicyclooctane (DABCO), and heterocyclic compounds having an amidine linkage, such as diazabicyclono.

[0078] Amine-epoxy adducts are well known in the art, for example, U.S. Patent Nos. 3,756,984, 4,066,625, 4,268,656, 4,360,649, 4,542,202, 4,546,155, 5,134,239, 5,407,978, and 5 These are described in Patent Nos. 543,486, 5,548,058, 5,430,112, 5,464,910, 5,439,977, 5,717,011, 5,733,954, 5,789,498, 5,798,399, and 5,801,218. Each of these patents is incorporated herein by reference in its entirety. Such amine-epoxy adducts are reaction products between one or more amine compounds and one or more epoxy compounds. Preferably, the adduct is a solid that does not dissolve in epoxy resin at room temperature, but becomes soluble upon heating and acts as an accelerator to speed up the curing rate. Any type of amine can be used (heterocyclic amines and / or amines having at least one secondary nitrogen atom are preferred), but imidazole compounds are particularly preferred. Examples of imidazoles include 2-methylimidazole, 2,4-dimethylimidazole, 2-ethyl-4-methylimidazole, and 2-phenylimidazole. Other suitable amines include, but are not limited to, piperazine, piperidine, pyrazole, purine, and triazole. Any type of epoxy compound can be used as the other starting material for the adduct, and such epoxy compounds include monofunctional and polyfunctional epoxy compounds, for example, those already described with respect to epoxy resin components.

[0079] In one embodiment, the curable resin composition of the present disclosure may contain a phenylindanediamine curing agent in an amount of about 5% to about 50% by weight, or about 20% to about 50% by weight, or about 40% to about 50% by weight, based on the total weight of the curable resin composition.

[0080] In yet another embodiment, the curable resin composition may also contain one or more other additives useful for their respective intended applications. For example, useful optional additives include diluents, stabilizers, surfactants, flow regulators, mold release agents, matting agents, degassing agents, thermoplastic particles (e.g., carboxyl-terminated liquid butadiene acrylonitrile rubber (CTBN), acrylic-terminated liquid butadiene acrylonitrile rubber (ATBN), epoxy-terminated liquid butadiene acrylonitrile rubber (ETBN), liquid epoxy resin (LER) adducts for elastomers and pre-molded core-shell rubbers), curing initiators, curing inhibitors, wetting agents, processing aids, fluorescent compounds, UV stabilizers, antioxidants, impact modifiers, rust inhibitors, tackifiers, high-density particulate fillers (e.g., various natural clays, e.g., kaolin, bentonite, montmorillonite or modified montmorillonite, attapulgite, and Buckminster-Fuller earth; other natural or naturally derived materials, e.g., mica, calcium carbonate, and aluminum carbonate; various oxides, e.g., ferric oxide, titanium dioxide, calcium oxide, and silicon dioxide (e.g.) Examples include, but are not limited to, sand; various artificial materials, such as precipitated calcium carbonate; and various waste materials, such as crushed blast furnace slag; conductive particles (such as silver, gold, copper, nickel, aluminum, and conductive grade carbon and carbon nanotubes); and mixtures thereof.

[0081] If present, the amount of additives contained in the curable resin composition can be at least about 0.5% by weight, or at least 2% by weight, or at least 5% by weight, or at least 10% by weight, based on the total weight of the curable resin composition. In other embodiments, the amount of additives contained in the curable resin composition can be about 30% by weight or less, or 25% by weight or less, or 20% by weight or less, or 15% by weight or less, based on the total weight of the curable resin composition.

[0082] Curable resin compositions can be prepared, for example, by premixing the individual components and then mixing these premixes, or by mixing all the components together using conventional equipment such as a stirring vessel, stirring rod, ball mill, sample mixer, static mixer, high-shear mixer, or ribbon blender, or by hot melt.

[0083] In other words, according to another embodiment, the curable resin composition of the present disclosure can be prepared by mixing together about 10% to about 95% by weight of a thermosetting resin, about 1% to about 15% by weight of a toughening agent component, and about 5% to about 50% by weight of a curing agent, where the weight percentages are based on the total weight of the curable resin composition.

[0084] In another embodiment, a coated substrate can be formed by applying a curable resin composition to a substrate to coat at least a portion (or substantially all) of the substrate, and then curing it by heating at a temperature higher than about 80°C. The curable resin composition can be applied by any known means, such as spraying, immersion, or a fluidized bed. In another embodiment, after application, the curable resin composition can be cured by heating at a temperature in the range of about 80°C to about 180°C, preferably about 100°C to about 160°C. Heating can be achieved by any means known in the art, for example, by placing the coated substrate in an oven. IR irradiation can also be used to heat-cur the coated substrate. The powder-coated surface must be exposed to the curing temperature for a sufficient time for the composition to cure and become a substantially continuous, uniform coating. Typically, the composition is converted into a substantially continuous, uniform coating within a curing time of about 1 minute to about 10 minutes or longer. If desired, curing can be carried out in two or more stages, for example, by partially curing at a low temperature and then increasing the temperature to achieve complete curing. In further embodiments, when the curable resin composition is cured at a temperature in the range of about 80°C to about 160°C, 85% curing to a complete state can be achieved within 5 minutes, preferably within 2 minutes, more preferably within 1 minute, and most preferably within 45 seconds.

[0085] In another embodiment, the thermosetting resin composition, when mixed and cured, yields a film having a glass transition temperature of over 150°C, preferably over 170°C, most preferably over 180°C, and particularly preferably over 190°C.

[0086] The curable resin compositions of this disclosure can be used in a variety of applications, such as casting, lamination, impregnation, coating, bonding, sealing, painting, joining, insulation, or for embedding, pressing, injection molding, extrusion, sand casting, foaming, and corrosion-resistant materials.

[0087] According to some embodiments, the thermosetting resin composition can be used as a sealant, adhesive, or coating. It can be used in the preparation of agents and / or as a sealant, adhesive, or coating agent. A sealant, adhesive, or coating agent containing a curable resin composition can be applied to the surface (inside or outside or both) of one or more substrates and heated to form a cured film. The substrate may be metallic or nonmetallic. Examples of substrates include metal piping, such as those commonly used in the chemical and petroleum gas industries for transporting various chemicals, silicates, metal oxides, concrete, wood, plastics, cardboard, particleboard, ceramics, glass, graphite, cellulose materials, electronic chip materials, and semiconductor materials. Depending on the embodiment, the substrate may include the inner and / or outer surfaces of steel pipes, structural steel used in concrete or marine environments, storage tanks, valves, and conduits and protective pipes for petroleum gas production. If desired, the surface of the substrate may be subjected to mechanical treatment, such as blasting, before or after application of the curable resin composition, followed by acid cleaning or cleaning in the case of metal substrates, and then chemical treatment. Furthermore, the substrate to be coated can be preheated before applying the powder composition.

[0088] In embodiments in which a curable resin composition is used as a coating, the curable resin composition can be used in a single-layer coating system or as one coating layer in a multilayer film type. The curable resin composition according to this disclosure can be applied directly to the substrate surface or to a primer layer, which can be a liquid or powder primer. The curable resin composition according to this disclosure can also be applied as one coating layer in a multilayer coating system based on a liquid or powder coating, for example, a powder or liquid clear coat layer applied to a coloring and / or special effect base coat layer, or a single-layer colored powder or liquid topcoat applied to a substrate. The curable resin composition can be applied to the substrate in a single sweep or in several steps by known means, for example, by spraying, dipping, spreading, rolling, etc. After application, the coating applied to the substrate surface is then heated to a temperature sufficient to cure the composition and form a film-coated substrate. Depending on the embodiment, the film coating generally has a thickness of about 1 to 10 mils, preferably about 2 to 4 mils, after curing.

[0089] In another embodiment of the present disclosure, a curable resin composition can be used as an adhesive for gluing or bonding parts made of the same or different substrates to form an article. The curable resin composition is first placed in contact with at least one of two or more of the same or different substrates to be bonded. In one embodiment, the curable resin composition is sandwiched between a first substrate and a second substrate. The curable resin composition and the substrates are then heated to a temperature above 80°C. Heating forms an adhesive bond such that the substrates are bonded together to form an article.

[0090] Although various embodiments of this disclosure have been described in detail above, it should be acknowledged that this disclosure provides a large number of applicable concepts of the present invention that can be realized in a wide variety of specific situations. The specific embodiments discussed herein are merely illustrative of specific ways of creating and using the present invention and do not define the scope of the invention. [Examples]

[0091] An exemplary resin formulation was prepared using the components listed in "Example 1" of Table 1. These components were DAPI, epoxy resin (Araldite® MY0510, available from Huntsman International LLC or its affiliates), methyl butadiene styrene ("MBS") core-shell additive powder (Clearstrength® XT100, available from Arkema), and polyethersulfone. The formulation was prepared by blending in a toughening agent (Virantage® VW-10200RFP, available from Solvay Specialty Polymers USA, LLC).

[0092] Next, the formulation of Example 1 was cured at 160°C for 3 hours, and then post-cured at 200°C for 1 hour. The cured samples were then subjected to high-temperature aging at 150°C and 170°C in an air-circulating oven, and subsequently, the Tg change was tested by DMA, as well as the flexibility strain and strength, over a period of 35 to 42 days.

[0093] Comparative Examples 1 to 3 (Comparative Examples 1, 2, and 3) were prepared, cured, and evaluated in the same manner as in Example 1 above, but using different formulations as shown in Table 1. Specifically, the composition of Comparative Example 1 did not contain either the MBS core-shell additive or the polyethersulfone toughening agent; the composition of Comparative Example 2 contained the MBS core-shell additive but did not contain the polyethersulfone toughening agent; and Comparative Example 3 contained the polyethersulfone toughening agent but did not contain the MBS core-shell additive.

[0094] The test data for Example 1 and Comparative Examples 1-3 are shown in Tables 2-4 below.

[0095] [Table 1]

[0096] [Table 2]

[0097] [Table 3]

[0098] The results in Tables 2 and 3 clearly demonstrate the unexpected synergistic effect when the polyethersulfone toughening agent is used in combination with the core-shell additive. As demonstrated in Comparative Examples 2 and 3, those skilled in the art would expect that the combination of the polyethersulfone toughening agent and the core-shell additive would lower the Tg value of the system containing only the polyethersulfone toughening agent (Comparative Example 3). However, Example 1 unexpectedly shows that this combination results in a higher Tg than Comparative Examples 3 and 2. Similarly, the unexpectedly improved properties are demonstrated in Table 3, which shows that the combination of the polyethersulfone toughening agent and the core-shell additive itself, when the cured sample is aged at 170°C, exhibits a significantly increased flexibility strength compared to both Comparative Examples 2 and 3. Those skilled in the art would expect similar benefits in the various practical forms of the curable resin compositions disclosed herein.

Claims

1. A curable resin composition comprising (a) a thermosetting resin, (b) a toughening agent component containing a multi-stage polymer and a thermoplastic toughening agent, and (c) a phenylindanediamine curing agent.

2. The composition according to claim 1, wherein the thermosetting resin is an epoxy resin.

3. The composition according to claim 2, wherein the epoxy resin is selected from a monofunctional epoxy resin, a bifunctional epoxy resin, a trifunctional epoxy resin, a tetrafunctional epoxy resin, and mixtures thereof.

4. The composition according to claim 1, further comprising 4,4'-methylene-bis-(3-chloro-2,6-diethyl-aniline).

5. The composition according to claim 1, wherein the thermoplastic toughening agent is a polyethersulfone.

6. The phenylindanediamine curing agent is a compound having the following structure. 【Chemistry 1】 In the formula, the amino group of the indan ring is at position 5 or 6, R ３ b is independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms, and b is independently an integer from 1 to 4. The composition according to claim 1.

7. A curable resin composition, the following (a) A thermosetting resin in an amount of approximately 50% to 95% by weight, (b) A toughening agent component comprising a multi-stage polymer and a thermoplastic toughening agent in an amount of approximately 1% to 15% by weight, and (c) Approximately 5% to 50% by weight of phenylindanediamine curing agent, This includes, and the weight percentage is based on the total weight of the curable resin composition. The aforementioned composition.

8. The composition according to claim 7, wherein the toughening agent component comprises about 5% to about 10% by weight of the multistage polymer and about 0.1% to about 10% by weight of the thermoplastic toughening agent.

9. The phenylindanediamine curing agent is a compound having the following structure. 【Chemistry 2】 In the formula, the amino group of the indan ring is at position 5 or 6, R ３ b is independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms, and b is independently an integer from 1 to 4. The composition according to claim 7.

10. The composition according to claim 7, wherein the thermoplastic toughening agent is a polyethersulfone.

11. A substrate at least partially coated with the composition described in claim 1.

12. The substrate according to claim 11, wherein the substrate is a metal pipe.

13. The substrate according to claim 11, wherein the substrate is nonmetallic.

14. The base material according to claim 11, wherein the base material is a steel pipe, structural steel, storage tank, valve, and oil and gas production conduit and protective pipe.

15. The following steps: (a) A step of applying the curable resin composition according to claim 1 to the surface of a substrate, and (b) A step of heating the curable resin composition to a temperature above 80°C to cure the curable resin composition, A process for forming a coated substrate, including [a specific component].

16. The process according to claim 15, wherein the substrate is a metal pipe.

17. The process according to claim 15, wherein the surface is the outer surface of the substrate.

18. The process according to claim 15, wherein the surface is the inner surface of the substrate.

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