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WO2019182155A1 - Composition durcissable, produit durci, procédé de production d'un produit durci, et procédé de réparation d'un endommagement d'un produit durci - Google Patents

Composition durcissable, produit durci, procédé de production d'un produit durci, et procédé de réparation d'un endommagement d'un produit durci Download PDF

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Publication number
WO2019182155A1
WO2019182155A1 PCT/JP2019/012277 JP2019012277W WO2019182155A1 WO 2019182155 A1 WO2019182155 A1 WO 2019182155A1 JP 2019012277 W JP2019012277 W JP 2019012277W WO 2019182155 A1 WO2019182155 A1 WO 2019182155A1
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group
compound
cured product
component
formula
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Japanese (ja)
Inventor
未紗子 岡部
淳 遠田
葉山　康司
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Mitsubishi Chemical Corp
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Mitsubishi Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule

Definitions

  • the present invention relates to a curable composition, a cured product, a method for producing a cured product, and a method for repairing scratches on the cured product.
  • the present application is filed on March 23, 2018, Japanese Patent Application No. 2018-057022 filed in Japan, March 23, 2018, Japanese Patent Application No. 2018-057023 filed in Japan, and March 23, 2018. Claims priority based on Japanese Patent Application No. 2018-057025 filed in Japan, the contents of which are incorporated herein by reference.
  • Non-Patent Document 2 proposes a photoresist by two-stage curing in which a DA network and an acrylate network are combined.
  • the conjugated diene and dienophile react with each other to form a DA network, and the DA network forms a solid photoresist in which the acrylate is supported.
  • an acrylate network is formed.
  • the DA network is decomposed by the rDA reaction, dissociated into the original conjugated diene and dienophile, and then removed by development together with the unexposed acrylate.
  • the compound (1) is a compound (4) represented by the following formula (4)
  • the compound (2) is a compound (5) represented by the following formula (5)
  • the cured product of [1] wherein the compound (3) is the compound (6) represented by the following formula (6).
  • the curable composition was applied to the surface of the 100 ⁇ m-thick polyethylene terephthalate film that had been subjected to the release treatment with an applicator so that the thickness after curing was 35 ⁇ m, and the coating film was heated at 70 ° C. for 30 minutes. Then, the coating film is irradiated with ultraviolet rays using a high-pressure mercury lamp under the condition of an integrated light quantity of 500 mJ / cm 2 and cured at 23 ° C. for 1 day to form a cured film.
  • ⁇ 2 >> The curable composition according to ⁇ 1 >>, wherein the component (C) has a mass average molecular weight of 3000 or more.
  • ⁇ 13 The curable composition according to any one of the above ⁇ 1 >> to ⁇ 10 >> is subjected to a retro Diels Alder reaction at a temperature equal to or higher than a temperature at which the above component (A) and the above component (B) are subjected to a Diels Alder reaction. ) And the component (B) at a temperature lower than the dissociation temperature to obtain a semi-cured product, and the semi-cured product is irradiated with active energy rays to obtain a cured product.
  • (Meth) acrylate is a general term for acrylate and methacrylate.
  • (Meth) acryloyl group is a general term for an acryloyl group and a methacryloyl group.
  • (Meth) acrylamide is a general term for acrylamide and methacrylamide.
  • DA reaction means Diels Alder reaction.
  • RDA reaction means Retro Diels Alder reaction.
  • Mass average molecular weight of component (C) is determined by gel permeation chromatography measurement (GPC measurement).
  • the “tensile modulus of the cured film at 23 ° C.” is obtained as follows. A cured film peeled off from a polypropylene plate and cut to a width of 10 mm was obtained by performing a tensile test using a tensile tester under the conditions of a temperature of 23 ° C., a humidity of 55% RH, a tensile speed of 50 mm / min, and a distance between chucks of 50 mm.
  • the straight line connecting the stress at 0% elongation and the stress at 0.5% elongation of the stress-strain curve is extended, and the stress converted at 100% elongation is taken as the tensile modulus.
  • the “storage elastic modulus of the cured film at 23 ° C. or 150 ° C.” is measured as follows. About the cured film which peeled from the polypropylene plate and cut
  • the reason why the cured product of the present invention exhibits the effects of the present invention is as follows.
  • the cured product of the present invention forms a thermoreversible DA network as described above. Further, the cured product of the present invention forms a urethane (meth) acrylate network in which urethane (meth) acrylate is cured and reacted.
  • the hybrid polymer network in which the DA network having covalent crosslinks and the urethane (meth) acrylate network are combined has a higher elastic modulus than the cured product of the urethane (meth) acrylate network alone, and is a hard cured product. There is a tendency.
  • the sum of the number of moles of the compound (1) contained in the cured product and the smaller number of moles contained in 1 g of the cured product in the compounds (2) and (3) is 0.05 mmol or more.
  • the wound can be filled by oozing out into the scratched part. Therefore, the wound repairability of the cured product of the present invention is improved.
  • the ratio of the DA network in the cured product is sufficient, at a temperature lower than the temperature at which the rDA reaction occurs, strong cross-linking due to carbon-carbon bonds is formed, and chemical resistance is improved.
  • the tensile elastic modulus at 23 ° C. of the cured product is sufficiently high, the hard coat property is excellent, the cured product is difficult to be damaged, and the elastic recovery force tends to repair the scratch.
  • Compound (1) is represented by the following formula (1).
  • R 1 to R 4 , R 7 and R 8 are not particularly limited.
  • R 1 to R 4 , R 7 and R 8 may be, for example, a hydrogen atom, an alkyl group which may have a substituent, an aryl which may have a substituent, or a substituent. Good heteroaryl, alkoxy group and the like can be mentioned.
  • R 1 to R 4 , R 7 and R 8 are mutually independent substituents, and may be the same or different from each other.
  • X 1 is not particularly limited as long as it is a divalent group.
  • Specific examples of X 1 include, for example, an oxygen atom, a nitrogen atom, a sulfur atom, an alkylene group which may have a substituent; a phenylene group which may have a substituent; —Si (R 31 ) R
  • Organic groups such as 32- groups are mentioned.
  • R 31 and R 32 are each independently an alkyl group having 1 to 20 carbon atoms.
  • oxygen atoms are preferable as R 31 and R 32 from the viewpoint of small steric hindrance and ease of raw material procurement.
  • the carbon number of the alkylene group which may have a substituent is preferably 1 or more, and more preferably 2 or more.
  • the alkylene group which may have a substituent has preferably 20 or less, more preferably 10 or less. Therefore, the alkylene group which may have a substituent preferably has 1 to 20 carbon atoms, and more preferably 2 to 10 carbon atoms.
  • the solubility of the compound (1) in an organic solvent tends to be improved, which can be advantageous in processes such as coating and film formation.
  • X 2 is not particularly limited as long as it is a divalent group.
  • Specific examples of X 2 include an oxygen atom, a nitrogen atom, an alkylene group which may have a substituent; an imide group; an —NR 12 — group; a combination of these groups, and the like.
  • R 12 is preferably an alkyl group having 1 to 20 carbon atoms.
  • Alkylene group which may have a substituent has the same meaning as the alkylene group which may have a substituent at X 1 of the above.
  • the details and preferred embodiments of the alkylene group for X 2 are the same as the alkylene group which may have a substituent for X 1 .
  • X 2 is preferably an imide group from the viewpoint of stability of compound (1), heat resistance, and ease of procurement of raw materials.
  • the electron withdrawing group include, for example, an imide group, an amide group, a carboxyl group, a carbonyl group, a fluoro group, a chloro group, a bromo group, an iodo group, a trifluoro group, a cyano group, a nitro group, a sulfoxide group, and a sulfone group.
  • an imide group is preferable from the viewpoints of stability of compound (1), heat resistance, ease of procurement of raw materials, and the like.
  • the following compound (4) is preferable.
  • R 1 to R 4 , R 7 and R 8 are substituents
  • R 11 is an oxygen atom or —NR 12 —
  • R 12 is a substituent
  • X 3 is an oxygen atom
  • Y and Z are an oxygen atom or a sulfur atom
  • At least one of R 1 to R 4 and X 3 is a group having an electron donating group
  • At least one of R 7 , R 8 and R 11 is a group having an electron withdrawing group.
  • the following compound (7) or compound (10) is more preferable, and the following compound (13) is more preferable.
  • Compound (2) is represented by the following formula (2).
  • Compound (3) is represented by the following formula (3).
  • R 1 to R 4 are substituents, X 1 is a divalent group, and at least one of R 1 to R 4 and X 1 is a group having an electron donating group.
  • R 7 and R 8 are substituents, X 2 is a divalent group, and at least one of R 7 , R 8 and X 2 is a group having an electron withdrawing group.
  • R 1 ⁇ R 4 in Formula (2) or Formula (3) R 7, R 8, X 1, X 2 is, R 1 ⁇ R 4 in the formula (1), R 7, R 8, X 1, X 2 is synonymous with each other.
  • the compound (2) the following compound (5) is preferable.
  • the compound (3) the following compound (6) is preferable.
  • R 1 to R 4 are substituents
  • X 3 is an oxygen atom, a nitrogen atom or an alkylene group which may have a substituent
  • R 1 to R 4 and X 3 At least one is a group having an electron donating group.
  • R 7 and R 8 are substituents
  • R 11 is an oxygen atom or —NR 12 —
  • R 12 is a substituent
  • Y and Z are oxygen atoms or sulfur atoms
  • At least one of R 7 , R 8 and R 11 is a group having an electron withdrawing group.
  • R 1 to R 4 , R 7 , R 8 , X 3 , R 11 , Y and Z in formula (5) or formula (6) are the same as R 1 to R 4 , R 7 , R 8 , X 3 , R 11 , Y and Z have the same meanings.
  • the following compound (8) is preferable, the following compound (11) is more preferable, and the following compound (14) is more preferable.
  • the compound (6) the following compound (9) is preferable, the following compound (12) is more preferable, and the following compound (15) is more preferable.
  • R 1 to R 4 and R 14 are substituents, and at least one of R 1 to R 4 and R 14 is a group having an electron donating group; R 7 and R 8 are substituents; R 12 is a substituent, and at least one of R 7 , R 8 and R 12 is a group having an electron withdrawing group.
  • R 1 to R 4 , R 7 , R 8 , R 12 , R 14 in formula (8), (9), (11), (12), (14) or (15) are represented by formula (1), formula It is synonymous with R 1 to R 4 , R 7 , R 8 , R 12 , R 14 in (4) or Formula (13).
  • the rDA reaction and DA reaction of the DA network containing each of the compound (4), the compound (7) and the compound (10) are expressed as follows.
  • the wound repair property of the cured product is particularly remarkably improved.
  • the reason is not clear, it is possible to improve compatibility with urethane (meth) acrylate and improve affinity with compound (3) when rDA reaction occurs.
  • the following compound (2-1) can be mentioned.
  • R 101 to R 103 are n-valent organic groups
  • R 104 to R 106 are single bonds or alkylene groups having 1 to 10 carbon atoms
  • R 107 to R 115 are A hydrogen atom or an alkylene group having 1 to 20 carbon atoms.
  • X 10 is preferably an oxygen atom or a sulfur atom.
  • R 101 to R 103 have the same meaning as Q 1 described later.
  • the chemical resistance of the cured product is particularly improved.
  • the reason for this is not clear, but the fact that the core part is biuret-type, the furan part spreads in the three-dimensional direction, the degree of crosslinking tends to be higher, and a dense DA network is formed.
  • the following compound (2-2) may be mentioned.
  • the compound (2) is the following component (A).
  • a compound (3) is the following component (B).
  • component (A) and the component (B) will be described.
  • Component (A) Compound having a conjugated diene structure.
  • Component (B) Compound having a dienophile structure (excluding urethane (meth) acrylate).
  • conjugated diene structure examples include a cyclic conjugated diene structure and a chain conjugated diene structure.
  • a cyclic conjugated diene structure is preferable because the diene structure is chemically stable and easily causes an rDA reaction.
  • a cyclic conjugated diene structure having a hetero atom is more preferable, and a furan skeleton is particularly preferable.
  • Specific examples of the conjugated diene structure include the following structures.
  • Some hydrogen atoms of the conjugated diene structure may be substituted with one or both of other atoms and other atomic groups constituting the compound.
  • Examples of other atoms include halogen atoms.
  • Examples of the other atomic group include a monovalent organic group or a divalent or higher organic group that links two or more conjugated diene structures.
  • the content of the conjugated diene structure in component (A) is preferably more than 2 mmol / g, more preferably 2.2 mmol / g or more. Moreover, 10 mmol / g or less is preferable and 7.5 mmol / g or less is more preferable.
  • the combination of the upper and lower limits is not particularly limited, but is preferably more than 2 mmol / g and not more than 10 mmol / g, more preferably not more than 2.2 to 7.5 mmol / g. If the content of the conjugated diene structure is not less than the lower limit of the above range, a DA network can be sufficiently formed.
  • Component (A) preferably does not have an acid group from the viewpoint of obtaining a cured product having excellent chemical resistance.
  • the acid group include a carboxy group, a phenolic hydroxyl group, a phosphonic acid group, and a sulfonic acid group.
  • Component (A) preferably contains a compound having two or more conjugated diene structures from the viewpoint of easily forming a DA network.
  • the number of conjugated diene structures is preferably an integer of 2 to 4 from the viewpoint of easy availability of raw materials.
  • the component (A) preferably has a urethane bond or a urea bond from the viewpoint that the compatibility with the component (C) is good and a transparent cured product is obtained.
  • the component (A) preferably has no sulfur atom in the molecule from the viewpoints of odor and storage stability. Specifically, it is preferable not to use a compound having a sulfur-containing group such as a thiol group (furfuryl mercaptan or the like) as a raw material for the component (A).
  • Component (A) is a compound represented by the following formula (I) from the point of easily forming a DA network, the point of obtaining a cured product excellent in chemical resistance, the point of obtaining a transparent cured product and the point of odor. It is preferable that (I) is included.
  • Q 1 is an n-valent organic group
  • R 201 is a single bond or an alkylene group having 1 to 10 carbon atoms
  • n is an integer of 2 or more
  • R 202 to R 204 are any groups.
  • Q 1 preferably has no acid group and no sulfur atom.
  • X 30 is preferably an oxygen atom or a sulfur atom.
  • R 201 is preferably an alkylene group having 1 to 6 carbon atoms, more preferably a methylene group, from the viewpoint of easy availability of raw materials.
  • n is preferably an integer of 2 to 4 from the viewpoint of easy availability of raw materials.
  • Specific examples of Q 1 include the following groups.
  • R 210 is a divalent hydrocarbon group
  • R 211 is a trivalent hydrocarbon group
  • a plurality of R 210 are the same or different. May be.
  • the divalent hydrocarbon group include an alkylene group, a cycloalkylene group, and an arylene group.
  • the alkylene group, cycloalkylene group, arylene group and the like are not particularly limited, and may have a substituent. Although carbon number of an alkylene group is not specifically limited, 1 or more are preferable and 2 or more are more preferable.
  • the alkylene group preferably has 20 or less carbon atoms, more preferably 10 or less.
  • the alkylene group may be linear or branched.
  • carbon number of a cycloalkylene group is not specifically limited, 3 or more are preferable and 4 or more are more preferable.
  • the carbon number of the cycloalkylene group is preferably 20 or less, and more preferably 10 or less.
  • the arylene group is not particularly limited, and examples thereof include a group derived from a single ring or a plurality of rings.
  • the number of rings contained in the groups derived from a plurality of rings is not particularly limited, but is usually 2 to 4 and preferably 3 or less.
  • carbon number of an arylene group is not specifically limited, It is 6 or more, 20 or less are preferable and 15 or less are more preferable.
  • Examples of the substituent that the alkylene group, cycloalkylene group, and arylene group may have include an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a hydroxyl group, a cyano group, a carboxy group, and a halogen atom.
  • the trivalent hydrocarbon group may contain an aromatic or alicyclic structure, and may have an alkyl group, a hydroxyl group or the like as a branch.
  • the trivalent hydrocarbon group may have an ether bond, an ester bond, a carbonate bond, a urethane bond, a urea bond, an amide bond, a ketone group, and the like.
  • carbon number of a trivalent hydrocarbon group is not specifically limited, It is 1 or more, 50000 or less are preferable and 40000 or less are more preferable.
  • the compound represented by the formula (I) can be obtained, for example, by reacting a polyisocyanate with a furan compound having a hydroxyl group or an amino group (furfuryl alcohol, furfurylamine, etc.).
  • the compound represented by the formula (I) is preferably a reaction product of polyisocyanate and furfuryl alcohol from the viewpoint of easy availability of raw materials.
  • Component (B) A compound having a dienophile structure (excluding component (C)) is a component that forms a thermoreversible DA network by DA reaction with component (A).
  • a component (B) may be used individually by 1 type, and may use 2 or more types together.
  • a maleimide skeleton is particularly preferable because the dienophile structure is chemically stable and easily causes an rDA reaction.
  • Specific examples of the dienophile structure include the following structures.
  • Some hydrogen atoms having a dienophile structure may be substituted with one or both of other atoms and other atomic groups constituting the compound.
  • other atoms include halogen atoms.
  • the other atomic group include a monovalent organic group or a divalent or higher valent organic group that connects two or more dienophile structures.
  • Component (B) preferably has no acid group from the viewpoint of obtaining a cured product having excellent chemical resistance.
  • the acid group include a carboxy group, a phenolic hydroxyl group, a phosphonic acid group, and a sulfonic acid group.
  • Component (B) preferably contains a compound having two or more dienophile structures from the viewpoint of easily forming a DA network.
  • the number of dienophile structures is preferably 2.
  • Component (B) is a compound (II) represented by the following formula (II) from the viewpoint of easily forming a DA network, a cured product having further excellent chemical resistance, and the availability of raw materials. ) Is preferably included.
  • phenylene bismaleimide 4,4′-bismaleimide diphenylmethane, polyphenylmethane maleimide, 3,3′-dimethyl-5,5 ′ are preferable in view of availability.
  • -Diethyl-4,4'-diphenylmethane bismaleimide is preferred.
  • Urethane (meth) acrylate is a component that forms an irreversible urethane (meth) acrylate network by a curing reaction with active energy rays. In the cured product of the present invention, the urethane (meth) acrylate forms a urethane (meth) acrylate network. Urethane (meth) acrylate may be used individually by 1 type, and may use 2 or more types together.
  • Urethane (meth) acrylate preferably has no acid group from the viewpoint of excellent chemical resistance.
  • the acid group include a carboxy group, a phenolic hydroxyl group, a phosphonic acid group, and a sulfonic acid group.
  • the mass average molecular weight (Mw) of urethane (meth) acrylate is not particularly limited.
  • the mass average molecular weight (Mw) of the urethane (meth) acrylate is preferably 1500 or more, more preferably 3000 or more, and still more preferably 4000 or more. Moreover, 300000 or less is preferable, 200000 or less is more preferable, 100000 or less is further more preferable, 50000 or less is more preferable, 40000 or less is especially preferable. If the mass average molecular weight (Mw) is not less than the lower limit of the above range, the three-dimensional processability of the cured product tends to be good.
  • the mass average molecular weight (Mw) of the urethane (meth) acrylate is preferably 1500 to 300000, more preferably 3000 to 200000, further preferably 4000 to 100000, particularly preferably 4000 to 50000, and most preferably 4000 to 40000.
  • the mass average molecular weight (Mw) can be determined by gel permeation chromatography measurement (GPC measurement).
  • the urethane (meth) acrylate preferably has a storage elastic modulus at 23 ° C. of the cured film III formed by the following method of 5 ⁇ 10 4 Pa or more, and more preferably 1 ⁇ 10 5 Pa or more.
  • the storage elastic modulus at 23 ° C. of the cured film III is preferably 5 ⁇ 10 12 Pa or less, more preferably 5 ⁇ 10 10 Pa or less, and further preferably 1 ⁇ 10 9 Pa or less. If the storage elastic modulus at 23 ° C. of the cured film III is not less than the lower limit of the above range, in addition to the wound repair by dissociation of the DA network by the rDA reaction into the compound (2) and the compound (3), Repair can also be expected.
  • the storage elastic modulus at 23 ° C. of the cured film III is not more than the upper limit of the above range, the wound repair by the dissociation into the compound (2) and the compound (3) by the rDA reaction of the DA network and the wound repair by the elastic recovery force There is no hindrance and the cured product of the curable composition of the present invention tends to have excellent wound repairability.
  • the storage elastic modulus of the cured film III at 23 ° C. is preferably 5 ⁇ 10 4 to 5 ⁇ 10 12 Pa, more preferably 5 ⁇ 10 4 to 5 ⁇ 10 10 Pa, and 5 ⁇ 10 4 to 1 ⁇ 10. 10 Pa is more preferable.
  • the storage elastic modulus at 23 ° C. of the cured film III is appropriately adjusted depending on the hydrogen bond density of the urethane bond and the covalent bond density of the (meth) acryloyl group.
  • the storage elastic modulus of the cured film III can be adjusted by adding another polyol to the urethane (meth) acrylate raw material in addition to the chain aliphatic diol having 2 to 12 carbon atoms.
  • Thickness after curing is 35 ⁇ m on the surface of the peel-treated side of a 100 ⁇ m-thick polyethylene terephthalate film obtained by removing a mixture of urethane (meth) acrylate dissolved in a solvent (methyl ethyl ketone, butyl acetate, cyclohexanone, etc.)
  • a solvent methyl ethyl ketone, butyl acetate, cyclohexanone, etc.
  • the film is applied with an applicator, heated at 70 ° C. for 30 minutes, irradiated with ultraviolet rays under a condition of an integrated light quantity of 500 mJ / cm 2 using a high pressure mercury lamp, and cured at 23 ° C. for 1 day.
  • polyisocyanate examples include chain aliphatic polyisocyanate, aromatic polyisocyanate, and alicyclic polyisocyanate. It is preferable that polyisocyanate contains alicyclic polyisocyanate from the point which raises the hardness of hardened
  • chain aliphatic polyisocyanates examples include aliphatic diisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, dimer acid diisocyanate, etc.), aliphatic triisocyanates (tris (isocyanatohexyl) isocyanurate, etc.), and the like. .
  • aromatic polyisocyanate examples include aromatic diisocyanates (tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, m-phenylene diisocyanate, naphthalene diisocyanate, etc.).
  • alicyclic polyisocyanates examples include alicyclic diisocyanates (bis (isocyanatemethyl) cyclohexane, cyclohexane diisocyanate, bis (isocyanatocyclohexyl) methane, isophorone diisocyanate, etc.), alicyclic triisocyanates (tris (isocyanate isophorone) isocyanurate, etc.) Isophorone diisocyanate is preferable.
  • chain aliphatic diol having 2 to 12 carbon atoms include ethylene glycol, propylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 1,2-butane.
  • chain aliphatic diol having 2 to 12 carbon atoms include ethylene glycol, propylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 1,2-butane.
  • Examples thereof include diol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,2-pentanediol, 1,5-pentanediol and the like.
  • the chain aliphatic diol having 2 to 12 carbon atoms is preferably ethylene glycol or 1,4-butanediol from the viewpoint of stain resistance of the cured product, wear resistance, and handling properties of the curable composition. Is particularly preferred. Here, it can be said that these specific examples are chain aliphatic diols having 2 to 5 carbon atoms.
  • the proportion of the chain aliphatic diol having 2 to 12 carbon atoms is preferably 40% by mass or more of the total diol component from the viewpoint of stain resistance of the cured product, wear resistance, and handleability of the curable composition. More preferably, it is more preferably 80% by weight or more, and particularly preferably 90% by weight or more.
  • the upper limit of the proportion of the chain aliphatic diol having 2 to 12 carbon atoms is usually 100% by mass.
  • the chain aliphatic diol having 2 to 12 carbon atoms is a concept including a chain aliphatic diol having 2 to 5 carbon atoms.
  • Examples of the polyfunctional (meth) acrylate having a hydroxyl group include bisphenol A diglycidyl ether diacrylate, 1,4-cyclohexanedimethanol diglycidyl ether diacrylate, ethylene glycol diglycidyl ether diacrylate, 1,4-butanediol diglycidyl ether.
  • Examples include diacrylate, 1,6-hexanediol diglycidyl ether diacrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol penta (meth) acrylate.
  • (meth) acrylate having a hydroxyl group from the viewpoint of the mechanical strength of the cured film, (meth) acrylate such as pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc. )
  • a hydroxyalkyl poly (meth) acrylate having an alkylene group having 2 to 4 carbon atoms between an acryloyl group and a hydroxyl group is preferred.
  • the molecular weight of the polyfunctional (meth) acrylate having a hydroxyl group is preferably 100 or more, and more preferably 200 or more.
  • the molecular weight of the polyfunctional (meth) acrylate having a hydroxyl group is preferably 800 or less, and more preferably 500 or less, from the viewpoint of the mechanical strength of the cured film. From the above, the molecular weight of the polyfunctional (meth) acrylate having a hydroxyl group is preferably from 100 to 800, more preferably from 200 to 500.
  • the polyfunctional (meth) acrylate having a hydroxyl group is an addition reactant or a polymer
  • the molecular weight is a number average molecular weight by GPC measurement.
  • a raw material for the component (C1) other than polyisocyanate, a chain aliphatic diol having 2 to 12 carbon atoms, and a polyfunctional (meth) acrylate having a hydroxyl group, as long as the effects of the present invention are not impaired.
  • These raw materials may be used.
  • Other raw materials include C6-C16 chain aliphatic diol, polyester polyol, polyether polyol, polycarbonate polyol, polyacryl polyol, alicyclic diol, polyalkylene glycol, high molecular weight polyol (excluding polyalkylene glycol) .), Hydroxyalkyl mono (meth) acrylates, chain extenders and the like.
  • the urethane bond amount of the component (C1) is preferably 0.1 ⁇ 10 ⁇ 3 to 10.0 ⁇ 10 ⁇ 3 eq / g, and is preferably 0.2 ⁇ 10 ⁇ 3 eq / g to 9.0 ⁇ 10 ⁇ 3 eq / G is more preferable, 0.5 ⁇ 10 ⁇ 3 to 9.0 ⁇ 10 ⁇ 3 eq / g is more preferable, and 1.0 ⁇ 10 ⁇ 3 to 8.0 ⁇ 10 ⁇ 3 eq / g is particularly preferable.
  • the urethane bond amount is at least the lower limit of the above range, the stain resistance of the cured product and the handleability of the curable composition are improved.
  • the amount of urethane bonds in component (C1) is the number of urethane bonds (the total number of isocyanate groups (the total value of the number of moles of polyisocyanate multiplied by the number of isocyanate group functional groups)) and isocyanate groups such as hydroxyl groups and amino groups.
  • the smaller of the total number of equivalents of all functional groups to be reacted is the total amount of the constituent components of component (C1) (the total amount of each raw material component excluding the amount of components added in excess (not the amount charged). ) Divided by.
  • the amount of the (meth) acryloyl group of the component (C1) is preferably 0.2 ⁇ 10 ⁇ 3 to 3.0 ⁇ 10 ⁇ 3 eq / g, and 0.4 ⁇ 10 ⁇ 3 to 2.7 ⁇ 10 ⁇ 3 eq / G is more preferable, and 0.5 ⁇ 10 ⁇ 3 to 2.5 ⁇ 10 ⁇ 3 eq / g is more preferable. If the amount of (meth) acryloyl group is not less than the lower limit of the above range, the stain resistance and wear resistance of the cured product will be improved. If the amount of the (meth) acryloyl group is not more than the upper limit of the above range, the stretchability of the cured product is improved.
  • the amount of the (meth) acryloyl group of the component (C1) is the number of (meth) acryloyl groups (the number of (meth) acryloyl group functional groups is added to the number of moles of the polyfunctional (meth) acrylate having a hydroxyl group excluding the excessively added component amount.
  • the sum of the multiplied values) is divided by the total amount of the constituent components of the component (C1) (the total amount of each raw material component excluding the excessively added component amount (not the charged amount)).
  • Component (C1) can be produced by subjecting polyisocyanate to a polyfunctional (meth) acrylate having a chain aliphatic diol having 2 to 12 carbon atoms and a hydroxyl group. Specifically, it can be produced by the method described in JP 2016-186039 A.
  • the amount of all isocyanate groups in component (C1) and the amount of all functional groups that react with isocyanate groups such as hydroxyl groups and amino groups are usually equimolar. Therefore, the polyisocyanate used as the raw material, the chain aliphatic diol having 2 to 12 carbon atoms, the polyfunctional (meth) acrylate having a hydroxyl group, and the other raw materials are used in an amount equal to the amount of all isocyanate groups in the component (C1).
  • the amount of the total functional group reacting with it is an equivalent amount or an amount which is 50 to 200 equivalent% in terms of the equivalent percentage of the total functional group reacting with it relative to the isocyanate group.
  • the amount of the polyfunctional (meth) acrylate having a hydroxyl group is preferably 3 to 70 mol%, more preferably 5 to 50 mol%, of the total amount of the compound having a functional group that reacts with an isocyanate group. 30 mol% or less is more preferable.
  • the molecular weight of the component (C1) can be controlled by the amount of the polyfunctional (meth) acrylate having a hydroxyl group.
  • a catalyst may be used.
  • the catalyst include tin-based catalysts (such as dibutyltin laurate, dibutyltin dioctate, dioctyltin dilaurate, and dioctyltin dioctate), bismuth-based catalysts (such as bismuth tris (2-ethylhexanate)), and the like.
  • the reaction temperature is preferably 20 to 120 ° C, more preferably 40 to 100 ° C, and further preferably 60 to 100 ° C.
  • the reaction temperature is preferably not higher than the boiling point of the organic solvent.
  • the reaction temperature is preferably 70 ° C. or less from the viewpoint of preventing the (meth) acryloyl group from reacting excessively.
  • the reaction time is usually 5 to 20 hours.
  • the number of moles of compound (1) contained in 1 g of the cured product of the present invention is 0.05 mmol or more.
  • the number of moles of compound (1) is n 11 mol / g
  • the number of moles of compound (2) is n 21 mmol / g
  • the number of moles of compound (3) is n 31.
  • the number of moles (n 11 mole) is equal to or greater than the above lower limit with respect to the total of 100 mole% of the number of moles (n 11 mole), the number of moles (n 21 mole), and the number of moles (n 31 mole), curing is achieved. Even if the reaction is sufficiently advanced, the cured product has sufficient hardness, and the effect of the cured product of the present invention is easily obtained.
  • the upper limit of the total number of moles (n 11 moles), the number of moles (n 11 moles), the number of moles (n 21 moles), and the number of moles (n 31 moles) is not particularly limited.
  • it may be 99 mol% or less, 90 mol% or less, or 80 mol% or less with respect to the total 100 mol% of the number of moles (n 11 mole), the number of moles (n 21 mole), and the number of moles (n 31 mole). .
  • cured material of this invention are not specifically limited.
  • the ratio (n 21 / n 31 ) of the number of moles (n 21 mole) of compound (2) to the number of moles (n 31 mole) of compound (3) in 1 g of the cured product is preferably 1 to 10. 5 to 10 is more preferable, 1.5 to 5 is more preferable, 1.5 to 3 is further preferable, and 1.5 to 2 is particularly preferable. If the ratio (n 21 / n 31 ) is within the above range, the elongation at break of the cured product tends to be improved.
  • the molecular weight of the DA network is lowered, the cured product is soft, and when it is made into a film, it tends to be a flexible film.
  • the ratio (n 21 / n 31 ) is, for example, 1 to 1.5, the elastic modulus of the cured product tends to be improved.
  • the molecular weight of the DA network is high, and there is a tendency that damage repairability, chemical resistance, and a decrease in elastic modulus during heating tend to occur, especially for applications that require chemical resistance. Become.
  • the ratio (n 21 / n 31 ) is, for example, 1.5 to 2
  • there is a tendency to easily exhibit flaw repairability, chemical resistance, and a decrease in elastic modulus during heating Tend to be useful for certain applications.
  • N 1 0.05mm Appl how to the sum N 1 0.05mm Appl more it is not particularly limited.
  • the sum of the number of moles of compound (1) and the smaller number of moles of compound (2) and compound (3) is The method etc. which mix a compound (2), a compound (3), and urethane (meth) acrylate so that it may become 0.05 mmol or more at the time of solid content 1g conversion are mentioned.
  • the proportions of urethane (meth) acrylate, compound (1), compound (2), and compound (3) in the cured product of the present invention may be appropriately adjusted depending on the application.
  • Ratio of the total mass of compound (1), compound (2) and compound (3) with respect to the total mass (100 mass%) of urethane (meth) acrylate, compound (1), compound (2) and compound (3) W is preferably 95% by mass or less, more preferably 90% by mass or less, further preferably 80% by mass or less, and particularly preferably 75% by mass or less. If the said ratio W is below the said upper limit, it is excellent in the dryness to the touch of the surface of hardened
  • the ratio W is preferably 4% by mass or more, and more preferably 10% by mass or more. If the ratio W is greater than or equal to the lower limit, dissociation of the compound (1) into the compound (2) and the compound (3) occurs due to the rDA reaction of the compound (1) in the molding temperature range, and the elastic modulus decreases, thereby reducing the urethane (meta ) Three-dimensional processability is better than the cured acrylate alone. From the above, the proportion W is preferably 4 to 95% by mass, more preferably 4 to 90% by mass, further preferably 4 to 80% by mass, particularly preferably 4 to 75% by mass, and most preferably 10 to 75% by mass. preferable. If the ratio W is within the above range, a cured product that is hard and excellent in three-dimensional formability, chemical resistance, and shape retention at high temperatures tends to be obtained.
  • the ratio of urethane (meth) acrylate from the viewpoint of wound repairability Is preferably 99% by mass or less, more preferably 80% by mass or less, still more preferably 75% by mass or less, and particularly preferably 70% by mass or less with respect to 100% by mass of the cured product.
  • 30 mass% or more is preferable and, as for the ratio of urethane (meth) acrylate, 50 mass% or more is more preferable.
  • the proportion of urethane (meth) acrylate is preferably 30 to 99% by mass, more preferably 30 to 80% by mass, still more preferably 30 to 75% by mass, and more preferably 30 to 70% by mass with respect to 100% by mass of the cured product. % Is particularly preferable, and 50 to 70% by mass is most preferable.
  • the ratio of urethane (meth) acrylate is 100% by mass of cured product from the viewpoint of wound repairability. 75 mass% or less is preferable, 70 mass% or less is more preferable, 65 mass% or less is more preferable, 60 mass% or less is especially preferable. Moreover, 10 mass% or more is preferable with respect to 100 mass% of hardened
  • the proportion of urethane (meth) acrylate is preferably 10 to 75% by mass, more preferably 10 to 70% by mass, further preferably 10 to 65% by mass, with respect to 100% by mass of the cured product. % Is particularly preferable, and 30 to 60% by mass is most preferable.
  • cured material of this invention may further have other components other than a compound (1), a compound (2), a compound (3), and urethane (meth) acrylate. What is necessary is just to adjust suitably the kind and ratio of another component according to a use etc. Specific examples of the other components include the same components as those described for the curable composition of the present invention described later.
  • the cured product of the present invention is excellent in shape retention at high temperatures.
  • the cured product of the present invention preferably has shape retention at 80 ° C or higher, more preferably has shape retention at 90 ° C or higher, and shape retention at 100 ° C or higher. Further preferred.
  • the fact that the cured product has a high-temperature shape-retaining property means that it does not drip (no fluidity) after holding the cured product (standing upright so that the film surface is vertical if it is a film) in a high-temperature environment. )
  • the glass transition point (Tg) of the cured product of the present invention is preferably 20 ° C. or higher.
  • the glass transition point (Tg) is, for example, preferably 20 to 200 ° C., more preferably 25 to 160 ° C.
  • the glass transition point (Tg) of the cured product can be measured by a method such as dynamic viscosity measurement (DMA measurement).
  • the haze value of the cured product of the present invention is preferably 10% or less, and more preferably 5% or less.
  • the lower limit of the haze value of the cured product is not particularly limited, and when the cured product is applied to a use requiring transparency, the haze value is preferably as small as possible.
  • the lower limit value of the haze value of the cured product is, for example, 0.001% or more.
  • the haze value of the cured product can be measured according to JIS K 7105 using a haze meter (for example, Haze Computer HZ-2 manufactured by Suga Test Instruments Co., Ltd.).
  • cured material of this invention is not specifically limited.
  • the tensile elastic modulus at 23 ° C. of the cured product is preferably 20 MPa or more, and more preferably 30 MPa or more.
  • cured material is not specifically limited, 3000 MPa or less is preferable and 2000 MPa or less is more preferable.
  • the tensile elastic modulus at 23 ° C. of the cured product is preferably 20 to 3000 MPa, more preferably 30 to 2000 MPa. When the tensile elastic modulus at 23 ° C.
  • the cured product is further excellent in scratch repairability and the hardness is further improved. If the tensile elastic modulus at 23 ° C. of the cured product is equal to or higher than the lower limit value, stickiness of the cured film surface and an increase in friction coefficient tend to be suppressed. Further, if the tensile modulus of the cured product at 23 ° C. is not more than the above upper limit value, it is difficult to prevent migration during the rDA reaction of each compound (2) and compound (3), and further excellent wound repair properties are obtained. Tend to be obtained. The tensile elastic modulus at 23 ° C. of the cured product can be measured by a method using a Tensilon tensile tester.
  • the storage elastic modulus at 150 ° C. of the cured product of the present invention is preferably 5 ⁇ 10 4 Pa or more, and more preferably 1 ⁇ 10 5 Pa or more. Further, the storage elastic modulus of the cured product at 150 ° C. is preferably 5 ⁇ 10 12 Pa or less, and more preferably 1 ⁇ 10 10 Pa or less. If the storage elastic modulus at 150 ° C. of the cured product is equal to or higher than the lower limit, in addition to the flaw repairability by dissociation of the DA network into the compound (2) and the compound (3) by the rDA reaction, flaw repair by elastic recovery force is also possible. It tends to be expected. If the storage elastic modulus at 150 ° C.
  • the storage elastic modulus at 150 ° C. of the cured product of the present invention can be adjusted by the ratio between the urethane (meth) acrylate network density and the DA network density.
  • a method of decreasing the proportion of urethane (meth) acrylate, storage of a single cured product of urethane (meth) acrylate In the case where the elastic modulus is lower than the cured product of the DA network alone, a method of increasing the proportion of urethane (meth) acrylate can be considered.
  • the method for repairing scratches on the cured product of the present invention is a method for repairing scratches generated on the cured product of the present invention.
  • a DA network formed by a DA reaction between the compound (2) and the compound (3) is converted into a compound ( In this method, the mixture is heated to a temperature at which it is dissociated into 2) and the compound (3) and then cooled.
  • R 1 to R 4 are substituents, X 1 is a divalent group, and at least one of R 1 to R 4 and X 1 is a group having an electron donating group.
  • R 7 and R 8 are substituents, X 2 is a divalent group, and at least one of R 7 , R 8 and X 2 is a group having an electron withdrawing group.
  • the details and preferred embodiments of the compound (2), the compound (3) and the urethane (meth) acrylate are the same as those described for the cured product of the present invention. It can also be said that the compound (2) is the above-mentioned component (A). Similarly, it can be said that the compound (3) is the above-mentioned component (B). The details and preferred embodiments of the component (A) and the component (B) are the same as those described for the cured product of the present invention.
  • the curable composition of the present invention among the solid content of the composition, the smaller number of moles of the number of moles of the conjugated diene structure possessed by the compound (2) and the number of moles of the dienophile structure possessed by the compound (3)
  • the sum of the number of moles of compound (1) is 0.05 mmol / g or more. Therefore, there is a sufficient DA network in the cured product obtained from the curable composition, and when the cured product is scratched, it can ooze out into the scratched portion and fill the scratch.
  • chemical resistance is improved at a temperature lower than the temperature at which the rDA reaction occurs, because strong cross-linking is formed by carbon-carbon bonds.
  • the curable composition of the present invention may further contain component (E): a polymerization initiator.
  • the curable composition of the present invention may further contain component (F): a liquid medium.
  • the curable composition of the present invention further contains components other than the components (A) to (F) (hereinafter also referred to as “other components”) as necessary within the range not impairing the effects of the present invention. You may go out.
  • the polymerization initiator is a component that improves the initiation efficiency of the polymerization reaction of the (meth) acryloyl group of component (C) that proceeds by irradiation with active energy rays.
  • the active energy ray used for the polymerization reaction of the (meth) acryloyl group is an electron beam
  • the curable composition of the present invention may not contain the component (E).
  • Examples of the component (E) include a photo radical polymerization initiator that generates radicals by light.
  • photo radical polymerization initiators benzophenone, 2,4,6-trimethylbenzophenone, 4,4-bis (diethylamino) benzophenone, 4-phenylbenzophenone, methyl orthobenzoylbenzoate, thioxanthone, diethylthioxanthone, isopropylthioxanthone, chlorothioxanthone, 2-ethylanthraquinone, t-butylanthraquinone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, benzoin methyl ether, benzoin ethyl ether, Benzoin isopropyl ether, benzoin isobutyl ether, methylbenzoyl formate,
  • benzophenone 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, , 4,6-Trimethylbenzoyldiphenylphosphine oxide, 2-hydroxy-1- [4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl] -2-methyl-propan-1-one 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2-hydroxy-1- [4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl 2-methyl-propan-1-one is more preferred.
  • the curable composition may contain a photocationic polymerization initiator as a polymerization initiator. It is preferable that the curable composition of this invention does not contain a photoinitiator. By not containing a photopolymerization initiator, there is a tendency that the modification of the curable composition due to the initiator decomposition product and the decrease in the mechanical strength of the cured product can be suppressed.
  • composition (F) Component (F):
  • the liquid medium is a component for dissolving the components (A) to (E), adjusting the viscosity when curing the curable composition, and obtaining a uniform cured product.
  • an organic solvent having a solubility parameter at 25 ° C. (hereinafter also referred to as “SP value”) of 8.0 to 11.5 is preferable. If SP value in 25 degreeC is more than the lower limit of the said range, the solubility of a component (C) is good. If SP value in 25 degreeC is below the upper limit of the said range, transparency of a curable composition is good.
  • Numerical values in parentheses are SP values at 25 ° C. The SP value is calculated by the method proposed by Fedors et al. Specifically, ROBERT F.R. FEDORS, “POLYMER ENGINEERING AND SCIENCE, FEBRUARY”, Vol. 14, No. 2, 1974, p. 147 to 154.
  • Examples of other components include an active energy ray-reactive monomer, an active energy ray-curable oligomer (excluding component (C)), a photosensitizer, an epoxy compound, and other additives.
  • Examples of active energy ray reactive monomers include vinyl compounds, (meth) acrylamide compounds, (meth) acrylates, and the like.
  • Examples of the active energy ray-curable oligomer include epoxy (meth) acrylate, acrylic (meth) acrylate, polyester (meth) acrylate, polycarbonate (meth) acrylate, polybutadiene (meth) acrylate, and polyether (meth) acrylate.
  • ethanolamine diethanolamine, triethanolamine, N-methyldiethanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, amyl 4-dimethylaminobenzoate, 4-dimethylaminoacetophenone Etc.
  • additives include fillers (glass fiber, glass beads, silica, alumina, calcium carbonate, mica, zinc oxide, titanium oxide, mica, talc, kaolin, metal oxide, metal fiber, iron, lead, metal powder, Carbon fiber, carbon black, graphite, carbon nanotube, fullerene, etc.), antioxidant, heat stabilizer, UV absorber, hindered amine light stabilizer (HALS), anti-fingerprint agent, surface hydrophilizing agent, antistatic agent, slipperiness Giving agent, plasticizer, mold release agent, antifoaming agent, leveling agent, anti-settling agent, surfactant, thixotropy imparting agent, lubricant, flame retardant, flame retardant aid, polymerization inhibitor, filler, silane coupling agent , Pigments, dyes, hue adjusting agents, curing agents, catalysts, curing accelerators and the like.
  • fillers glass fiber, glass beads, silica, alumina, calcium carbonate, mica, zinc oxide, titanium oxide, mica, talc, kaolin,
  • the sum N 2 is preferably not less than 0.3mm Cincinnatil / g, more preferably at least 0.5mm Cincinnatil / g.
  • the upper limit value of the sum N 2 is not particularly limited.
  • the sum N 2 may be appropriately adjusted according to the application of the curable composition.
  • the sum N 2 is preferably 10 mmol / g or less, more preferably 5 mmol / g or less, and further preferably 3 mmol / g or less.
  • the number of moles of compound (1) in 1 g of curable composition (n 12 mole) and the number of moles of compound (2) in 1 g of curable composition (n 22 mole) The total number of moles (n 12 mole) of the compound (1) in 1 g of the curable composition is 80 mol% with respect to 100 mole% in total with the number of moles (n 32 mole) of the compound (3) in 1 g of the curable composition.
  • the following is preferable, 60 mol% or less is more preferable, and 50 mol% or less is more preferable.
  • the lower limit of the total number of moles (n 12 moles), the number of moles (n 12 moles), the number of moles (n 22 moles), and the number of moles (n 32 moles) is not particularly limited.
  • may be a number of moles (n 12 m beginnerl) the moles (n 22 m réellel) the moles (n 32 m réellel) 1mol% or more relative to the total 100 mol% of the may be 10 mol% or more, may be 20 mol% or more .
  • the molar ratio of the conjugated diene structure of component (A) to the dienophile structure of component (B) in the curable composition of the present invention is preferably more than 1.0 and 10 or less, 1.1 More preferably, it is 2.5 or less. If the conjugated diene structure / dienophile structure is at least the lower limit of the above range, the unreacted dienophile structure (maleimide skeleton, etc.) in the component (B) decreases after the DA reaction between the component (A) and the component (B). .
  • the amount of component (D) in the curable composition of the present invention is preferably 10 parts by mass or less with respect to 100 parts by mass in total of component (C), active energy ray-reactive monomer and active energy ray-curable oligomer. 5 parts by mass or less is more preferable. If the amount of component (D) is less than or equal to the lower limit of the above range, the mechanical strength of the cured product is unlikely to decrease due to the decomposition product of component (D).
  • the solid content concentration of the curable composition of the present invention is preferably 5 to 90% by mass, more preferably 10 to 80% by mass, further preferably 15 to 70% by mass, and particularly preferably 15 to 60% by mass.
  • Solid content is all the components except a component (E), and includes not only a solid state thing but a semi-solid thing, and a viscous liquid substance.
  • the compounding amount of other components in the curable composition of the present invention is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, with respect to 100 parts by mass in total of the components (A) to (C). If the blending amount of other components is not more than the upper limit of the above range, the effects of the present invention are unlikely to be impaired.
  • the tensile elastic modulus at 23 ° C. of the cured film I formed by the following method is preferably 1 MPa or more, more preferably 5 MPa or more, further preferably 10 MPa or more, further preferably 20 MPa or more, and 30 MPa. The above is particularly preferable, and 35 MPa or more is most preferable.
  • the tensile elastic modulus at 23 ° C. of the cured film I is preferably 2000 MPa or less, more preferably 1500 MPa or less, further preferably 1000 MPa or less, and still more preferably 500 MPa or less. If the tensile modulus at 23 ° C.
  • the cured film I has a tensile modulus of elasticity at 23 ° C. that is less than or equal to the upper limit of the above range, the wound repair by the dissociation of the DA network into the component (A) and the component (B) by the rDA reaction and the wound repair by the elastic recovery force There is no hindrance and the cured product of the curable composition of the present invention tends to have excellent wound repairability.
  • the tensile elastic modulus at 23 ° C. of the cured film I can be adjusted by the mixing ratio of the component (C) and the DA network component (component (A) and component (B)).
  • the tensile modulus of the component (C) single film (the cured film III described above) is higher than that of the DA network single film, the proportion of the component (C) is decreased.
  • the tensile modulus of the component (C) single film is DA. If it is lower than the network single membrane, the proportion of the component (C) may be increased.
  • Method for forming cured film I The curable composition was applied to a 1 mm thick polypropylene plate that had been peeled off with an applicator so that the thickness after curing was 50 ⁇ m.
  • the coating film is irradiated with ultraviolet rays under conditions of 500 mJ / cm 2 and cured at 23 ° C. for 1 day to form a cured film I.
  • the curable composition is coated on a glass or polypropylene plate having a thickness of 1 mm with a bar coater to form a coating film, and then dried at 70 ° C. for 30 minutes.
  • the storage elastic modulus at 150 ° C. of the cured film II formed by the following method is preferably 5 ⁇ 10 4 Pa or more, and more preferably 1 ⁇ 10 5 Pa or more.
  • the storage elastic modulus of the cured film II at 150 ° C. is preferably 5 ⁇ 10 12 Pa or less, and more preferably 1 ⁇ 10 10 Pa or less. If the storage modulus at 150 ° C. of the cured film II is equal to or higher than the lower limit of the above range, scratches due to elastic recovery force in addition to wound repair by dissociation of component (A) and component (B) by the rDA reaction of the DA network There is a tendency to expect repairs. If the storage elastic modulus at 150 ° C.
  • the wound repair by the dissociation into the component (A) and the component (B) by the rDA reaction of the DA network and the wound repair by the elastic recovery force There is no hindrance, and the wound repairability of the cured product of the curable composition of the present invention is excellent.
  • Method for forming cured film II The curable composition was applied to the surface of the 100 ⁇ m-thick polyethylene terephthalate film that had been subjected to the release treatment with an applicator so that the thickness after curing was 50 ⁇ m, and the coating film was heated at 70 ° C. for 30 minutes. Then, the coating film is irradiated with ultraviolet rays using a high-pressure mercury lamp under the condition of an integrated light quantity of 500 mJ / cm 2 and cured at 23 ° C. for 1 day to form a cured film II.
  • the breaking elongation at 23 ° C. of the cured film I can be adjusted by the mixing ratio of the component (C) and the sum of the component (A) and the component (B).
  • cured material of a component (C) is suitably adjusted with the hydrogen bond density of a urethane bond, and the covalent bond density of a (meth) acryloyl group.
  • the hydrogen bond density of the urethane bond is high, the elongation at break of the cured product of the component (C) is lowered, but the dryness to touch is improved.
  • the elongation at break of the cured product of component (C) is low, but the dryness to the touch is improved. If necessary, the elongation at break of the cured product of component (C) can be adjusted by adding other polyol to the chain aliphatic diol having 2 to 12 carbon atoms to the raw material of component (C). it can.
  • the hard coat film can be formed, for example, as follows.
  • the curable composition of the present invention is applied to the surface of a substrate and heated to form a semi-cured film having a DA network.
  • the semi-cured film is irradiated with active energy rays to form a hard coat film having a hybrid polymer network in which a DA network and a urethane (meth) acrylate network are combined.
  • the heating temperature at the time of forming the semi-cured film is not less than the temperature at which the component (A) and the component (B) are DA-reacted and less than the temperature at which the component (A) and the component (B) are dissociated by the rDA reaction.
  • the heating temperature for forming the semi-cured film is preferably 40 to 95 ° C., and 70 to 90 ° C is more preferred.
  • the thickness of the hard coat film is appropriately set according to the application.
  • the thickness of the hard coat film is preferably 1 to 100 ⁇ m, more preferably 2 to 50 ⁇ m, and even more preferably 2 to 20 ⁇ m. If the thickness of the hard coat film is equal to or greater than the lower limit of the above range, the design and function will be good. If the thickness of the hard coat film is not more than the upper limit of the above range, the internal curability and the three-dimensional processability are good.
  • the heating temperature when the DA network is decomposed in the hard coat film is equal to or higher than the temperature at which the DA network dissociates into the component (A) and the component (B) by the rDA reaction.
  • the heating temperature for decomposing the DA network is preferably 100 to 160 ° C., and 110 to 150 ° C. Is more preferable.
  • the component (C) may have a storage elastic modulus at 23 ° C. of a cured film III ′ formed by the following method of 5 ⁇ 10 2 Pa or more, and 5 ⁇ 10 3.
  • the pressure may be Pa or higher, 5 ⁇ 10 4 Pa or higher, or 1 ⁇ 10 5 Pa or higher. If the storage elastic modulus at 23 ° C. of the cured film III ′ is equal to or higher than the lower limit of the above range, in addition to the wound repair by dissociation of the DA network into the component (A) and the component (B) by the rDA reaction, Wound repair can also be expected. If the storage elastic modulus at 23 ° C.
  • the wound repair by the dissociation into the component (A) and the component (B) by the rDA reaction of the DA network and the wound repair by the elastic recovery force The cured product of the curable composition of the first aspect of the present invention tends to have excellent wound repairability.
  • Method for forming cured film III ′ A mixture of component (C) dissolved in a solvent (methyl ethyl ketone, butyl acetate, cyclohexanone, etc.) has a thickness of 50 ⁇ m after curing on the surface of the peel-treated side of a 100 ⁇ m-thick polyethylene terephthalate film.
  • the coated film is heated at 70 ° C. for 30 minutes, irradiated with ultraviolet light under a condition of an integrated light quantity of 500 mJ / cm 2 using a high-pressure mercury lamp, and cured at 23 ° C. for 1 day to obtain a cured film III.
  • a solvent methyl ethyl ketone, butyl acetate, cyclohexanone, etc.
  • the storage elastic modulus at 150 ° C. of the cured film II ′ is not more than the upper limit of the above range, the wound repair by the dissociation of the DA network into the component (A) and the component (B) by the rDA reaction and the wound repair by the elastic recovery force
  • the cured product of the curable composition of the first aspect of the present invention is excellent in wound repairability.
  • n is an integer of about 0 to 20
  • m is an integer of about 0 to 20.
  • HEA 2-hydroxyethyl acrylate
  • V-300 mixture of 40-45% by mass of pentaerythritol triacrylate and 35-40% by mass of pentaerythritol tetraacrylate (catalog value) (trade name Biscoat 300, manufactured by Osaka Organic Chemical Co., Ltd.)
  • OH Value OH group equivalent (molecular weight per hydroxyl group) 468 is calculated from 120 (analysis table item), and all components are defined as consisting of pentaerythritol triacrylate (PET3A) and pentaerythritol tetraacrylate (PET4A).
  • GMA glycidyl methacrylate (trade name “Blemmer (registered trademark) GH” manufactured by NOF Corporation)
  • MMA Methyl methacrylate (trade name “Acryester (registered trademark) M” manufactured by Mitsubishi Rayon)
  • -EA ethyl acrylate-AA: acrylic acid-MEK-ST: methyl ethyl ketone-dispersed colloid (silica sol average primary particle size: 15 nm (catalog value), silica solid content: 30% by mass) (trade name "MEK-” manufactured by Nissan Chemical Industries, Ltd.) ST ”)
  • N 1 Sum of the number of moles of the compound (1) contained in 1 g of the cured product and the number of moles of the compound having the smaller number of moles contained in 1 g of the cured product among the compounds (2) and (3)
  • Mmol Mmol
  • N 2 Of the solid content of the composition, the smaller number of moles of the number of moles of the conjugated diene structure possessed by the compound (2) and the number of moles of the dienophile structure possessed by the compound (3); Sum with moles (mmol)
  • R is C 6 H 12 .
  • a component (A-5) represented by the following formula (A-5) (a trifunctional furan compound described in Non-Patent Document 1) was obtained.
  • the furfuryl group content was 3.6 mmol / g.
  • component (B-3) represented by the following formula (B-3) (3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethane bismaleimide, manufactured by Daiwa Kasei Kogyo Co., Ltd., BMI-5100 ) was prepared.
  • a component (B-1) (4,4′-bismaleimide diphenylmethane) represented by the following formula (B-1) was prepared.
  • reaction mixture was cooled to 60 ° C., dioctyltin dilaurate: 0.08 g, methylhydroquinone: 0.20 g, MEK: 46 g were added, and R-167: 45 g was added dropwise to initiate the reaction.
  • the reaction was carried out for 10 hours while heating to 70 ° C. in an oil bath.
  • MEK 193 g was added, and component 4 -1 (urethane (meth) acrylate) was obtained.
  • reaction mixture was cooled to 60 ° C., and then dioctyltin dilaurate: 0.08 g, methylhydroquinone: 0.20 g, MEK: 12 g were added, and HEA: 12 g was added dropwise to initiate the reaction.
  • the reaction was carried out for 10 hours while heating to 70 ° C. in an oil bath. After confirming the end point of the reaction by disappearance of the peak derived from the isocyanate (NCO) group in the infrared absorption spectrum, MEK: 200 g was added, and component 4 -2 was obtained.
  • NCO isocyanate
  • the reaction mixture was cooled to 60 ° C., and then 0.32 g of bismuth tris (2-ethylhexanoate), 0.20 g of methylhydroquinone, and 128 g of MEK were added, and 128 g of V-300 (PET3A: 82 g / PET4A: 46g)
  • the reaction was started dropwise.
  • the reaction was carried out for 10 hours while heating to 70 ° C. in an oil bath.
  • MEK 200 g was added, and component 4 -4 was obtained.
  • the weight average molecular weight was 5600 and the number average molecular weight was 2900.
  • Component 4-6 This was designated as Component 4-6.
  • the weight average molecular weight was 29,000, the number average molecular weight was 3,500, the urethane bond amount was 3.31 ⁇ 10 ⁇ 3 eq / g, and the acryloyl group amount was 6.61 ⁇ 10 ⁇ 4 eq / g. .
  • AA 49.7 g and tri (p-tris) phosphine: 1.83 g were added and reacted at 110 ° C. for 6 hours, whereby an acryloyl group and a methoxysilyl group, a glycidyl group and a carboxyl group, A (meth) acrylic acid ester-based polymer having a hydroxyl group generated by the above reaction and having a mass average molecular weight (Mw) of 12,000 and an unsaturated double bond concentration of 4.6 mmol / g and a hydroxyl group concentration of 4.6 mmol / g is obtained.
  • Component (AA-1) solid content: 30% by mass).
  • a cured film was produced from each curable composition by the following method.
  • the film-forming method A was used for the curable composition containing a polymerization initiator.
  • the film-forming method B was used for the curable composition which does not contain a polymerization initiator.
  • the curable composition is applied onto a blue plate glass or polypropylene plate using a bar coater or an applicator, the coating film is heated at 70 ° C. for 30 minutes, and an electrodeless ultraviolet irradiation device (D bulb) (manufactured by Heraeus) is used.
  • D bulb electrodeless ultraviolet irradiation device
  • the haze value of the cured film obtained by the film forming method was measured.
  • the haze value was measured according to JIS K7105 using a haze meter (“HAZE METER HM-65W” manufactured by Murakami Color Research Laboratory Co., Ltd.). Here, it means that transparency is so high that a haze value is small.
  • X Repair rate is less than 35%.
  • ⁇ Repair rate is 35% or more and less than 50%.
  • A The repair rate is 50% or more.
  • the haze value was measured according to JIS K7105 using a haze meter (“HAZE METER HM-65W” manufactured by Murakami Color Research Laboratory Co., Ltd.).
  • E represents a power.
  • “1.10E + 08” represents “1.10 ⁇ 10 8 ”.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

La présente invention concerne : un produit durci dur qui présente une excellente aptitude au traitement en trois dimensions, tout en présentant une excellente résistance chimique et/ou une excellente aptitude à la réparation d'un endommagement ; un procédé de production de ce produit durci ; une composition durcissable qui permet d'obtenir ce produit durci ; et un procédé de réparation d'un endommagement d'un produit durci. L'invention concerne un produit durci qui contient un composé (1) représenté par la formule (1), un composé (2) représenté par la formule (2), un composé (3) représenté par la formule (3) et un (méth)acrylate d'uréthane, et qui est conçu de telle sorte que la somme du nombre de moles du composé (1) contenu dans 1 g du produit durci et du nombre de moles du composé (2) ou du composé (3) contenu dans 1 g du produit durci, ledit nombre de moles étant inférieur à l'autre, soit supérieure ou égale à 0,05 mmol. (Dans les formules (1) à (3), chacun de R1 à R4, R7 et R8 représente un substituant ; chacun de X1 et X2 représente un groupe divalent ; au moins un parmi R1 à R4 et X1 représente un groupe comportant un groupe donneur d'électrons ; et au moins un parmi R7, R8 et X2 représente un groupe comportant un groupe extracteur d'électrons.)
PCT/JP2019/012277 2018-03-23 2019-03-22 Composition durcissable, produit durci, procédé de production d'un produit durci, et procédé de réparation d'un endommagement d'un produit durci Ceased WO2019182155A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022069948A1 (fr) * 2020-09-30 2022-04-07 Kaneka Corporation Résines de benzoxazine à haute température, procédés et utilisations associées

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11349877A (ja) * 1998-04-23 1999-12-21 Tektronix Inc 相変化インク・キャリア組成物
JP2004307859A (ja) * 2003-04-05 2004-11-04 Rohm & Haas Electronic Materials Llc 電子デバイス製造
JP2006193629A (ja) * 2005-01-14 2006-07-27 Yokohama Rubber Co Ltd:The 硬化性組成物およびその硬化物
JP2009067971A (ja) * 2007-09-18 2009-04-02 Kawasaki Kasei Chem Ltd ラジカル重合性組成物、その重合方法及びその重合物
JP2016027116A (ja) * 2014-06-23 2016-02-18 東洋インキＳｃホールディングス株式会社 接着剤組成物、積層シート、太陽電池用裏面保護シート

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11349877A (ja) * 1998-04-23 1999-12-21 Tektronix Inc 相変化インク・キャリア組成物
JP2004307859A (ja) * 2003-04-05 2004-11-04 Rohm & Haas Electronic Materials Llc 電子デバイス製造
JP2006193629A (ja) * 2005-01-14 2006-07-27 Yokohama Rubber Co Ltd:The 硬化性組成物およびその硬化物
JP2009067971A (ja) * 2007-09-18 2009-04-02 Kawasaki Kasei Chem Ltd ラジカル重合性組成物、その重合方法及びその重合物
JP2016027116A (ja) * 2014-06-23 2016-02-18 東洋インキＳｃホールディングス株式会社 接着剤組成物、積層シート、太陽電池用裏面保護シート

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022069948A1 (fr) * 2020-09-30 2022-04-07 Kaneka Corporation Résines de benzoxazine à haute température, procédés et utilisations associées

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