WO2022019256A1 - 硬化性化合物、硬化性組成物、及び、硬化性組成物の製造方法 - Google Patents

硬化性化合物、硬化性組成物、及び、硬化性組成物の製造方法 Download PDF

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WO2022019256A1
WO2022019256A1 PCT/JP2021/026927 JP2021026927W WO2022019256A1 WO 2022019256 A1 WO2022019256 A1 WO 2022019256A1 JP 2021026927 W JP2021026927 W JP 2021026927W WO 2022019256 A1 WO2022019256 A1 WO 2022019256A1
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meth
general formula
curable composition
saturated
acrylate
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English (en)
French (fr)
Japanese (ja)
Inventor
弘文 藤井
大介 平山
隆二 川村
悟志 奥田
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Nitto Shinko Corp
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Nitto Shinko Corp
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Priority to US18/016,482 priority Critical patent/US12570789B2/en
Priority to JP2022537995A priority patent/JP7712273B2/ja
Priority to EP21846926.0A priority patent/EP4186933A4/en
Priority to KR1020237004405A priority patent/KR20230035113A/ko
Priority to CN202180048444.0A priority patent/CN115776998B/zh
Publication of WO2022019256A1 publication Critical patent/WO2022019256A1/ja
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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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/04—Polymers provided for in subclasses C08C or C08F
    • C08F290/048—Polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6204—Polymers of olefins
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/6715—Unsaturated monofunctional alcohols or amines
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/69—Polymers of conjugated dienes
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/14—Polyurethanes having carbon-to-carbon unsaturated bonds

Definitions

  • the present invention relates to a curable compound, a curable composition containing the curable compound, and a method for producing the curable composition.
  • a curable composition that cures by light irradiation or moisture (moisture) is known.
  • This type of curable composition is, for example, a curable composition that is cured by light irradiation and has a number average molecular weight of 1,000 to 20,000 synthesized from a hydrogenated polybutadiene diol or a hydrogenated polyisoprene diol.
  • a curable composition containing a urethane acrylate (curable compound), a monofunctional (meth) acrylate monomer, and an initiator having an absorption band at a wavelength of 380 nm or more is known (for example, Patent Document 1). ).
  • the content of the initiator is 10 to 15 parts by mass with respect to 100 parts by mass in total of the curable compound and the monomer.
  • the curable composition described in Patent Document 1 is used in an electronic circuit coating application, for example, is applied onto an electronic circuit and then irradiated with light, and is cured by a reaction between the curable compound and the monomer.
  • the curable composition described in Patent Document 1 can be cured even with light from an LED light source, and can have good moisture resistance, electrical insulation, and the like.
  • the curable composition described in Patent Document 1 has been cured because the curable compound contained in the curable composition described in Patent Document 1 does not have an unsaturated bond due to hydrogenation.
  • the cured product may not necessarily have the tackiness (slightly adhesive) on the surface suppressed.
  • foreign matter for example, which may reduce the electrical insulation of the cured product
  • adheres to the surface of the cured product, or marks of contact between an object such as a packing material and the cured product remain on the surface of the cured product. Problems can arise.
  • the surface tackiness of the cured product is suppressed, there is a problem that the cured product does not have appropriate extensibility. Therefore, there is a demand for a curable composition in which the surface tackiness of the cured product after curing is suppressed and the cured product has appropriate extensibility.
  • the present invention provides a curable compound and a curable composition capable of obtaining a cured product having suppressed surface tackiness and appropriate extensibility. Is the subject.
  • Another object of the present invention is to provide a method for producing a curable composition for producing a curable composition containing the above-mentioned curable compound.
  • the curable compound according to the present invention is characterized by being represented by the following general formula (I).
  • X represents a branched-chain polyolefin structure containing a carbon-carbon double bond in the side chain
  • the two Ys are independently the following general formula (II) or the following general.
  • R a1 , R a2 , and R a3 each independently represent an organic group.
  • R b1 , R b2 , R b3 , and R c each independently represent an organic group.
  • R d1 , R d2 , and R d3 each independently represent an organic group.
  • R e1 , R e2 , and R e3 each independently represent an organic group.
  • Q represents a saturated hydrocarbon group having 2 or more carbon atoms and 4 or less carbon atoms
  • M represents H or CH 3 .
  • the curable composition according to the present invention comprises a branched polyolefin diol containing a carbon-carbon double bond in the side chain, an isocyanurate form of an aliphatic diisocyanate having a total carbon number of 6 or more and 10 or less, an adduct form, and a biuret. comprising at least one selected from the body, hydroxy saturated C 1 ⁇ C 4 alkyl (meth) acrylate, a urethane reaction product.
  • the method for producing a curable composition according to the present invention is a branched polyolefin diol containing a carbon-carbon double bond in the side chain, an isocyanurate form of an aliphatic diisocyanate having a total carbon number of 6 or more and 10 or less, and an adduct form. , and at least one selected from biurets, by urethanization reaction hydroxy saturated C 1 ⁇ C 4 alkyl (meth) acrylate, in the presence of a curable composition comprising the reaction product of the urethane-forming reaction It is characterized by manufacturing.
  • FIG. 1 is a schematic diagram schematically showing an example of a urethanization reaction product.
  • the curable compound of this embodiment is represented by the following general formula (I).
  • X represents a branched-chain polyolefin structure containing a carbon-carbon double bond in the side chain, and the two Ys are independent of each other and are represented by the following general formula (II) or the following.
  • R a1 , R a2 , and R a3 each represent an organic group independently of each other.
  • the portion described as (Z or NHCOO-) in the general formula (a) is not included in T in the general formula (II) or (III) (described for reference).
  • R b1 , R b2 , R b3 , and R c each independently represent an organic group.
  • R d1 , R d2 , and R d3 each independently represent an organic group.
  • R e1 , R e2 , and R e3 each independently represent an organic group.
  • Q represents a saturated hydrocarbon group having 2 or more carbon atoms and 4 or less carbon atoms
  • M represents H or CH 3 .
  • the solid double wavy line represents the one closer to X in the general formula (I)
  • the broken double wavy line represents the general formula (I). Represents the one farther from the X of.
  • the curable compound of the present embodiment contains at least one of the acryloyl group or the isocyanate group (-NCO) of the (meth) acrylate in the molecule.
  • the curable compound of the present embodiment is at least one of a (meth) acryloyl group or an isocyanate group (-NCO) involved in the curing reaction.
  • One is in the molecule. Therefore, it can be cured by irradiation with light such as ultraviolet rays and by moisture (humidity or the like) in the air.
  • a polymerization reaction occurs between the above compounds due to the (meth) acryloyl group.
  • Polymerization (curing reaction) can proceed by polymerizing compounds. Further, for example, through water (H 2 O) contained in the moisture in the air reacts with -NCO between the above compounds, compounds are bonded to each other. Polymerization (curing reaction) can also proceed by this bond. Therefore, the curable compound of the present embodiment can be sufficiently cured by light or moisture. The surface tackiness of the cured product is suppressed, and the cured product can have appropriate extensibility.
  • the curable compound of the present embodiment contains both a (meth) acryloyl group and an isocyanate group (-NCO) in the molecule
  • the curable compound of the present embodiment is subjected to either light or moisture. Can be sufficiently cured.
  • X is a branched-chain polyolefin structure containing a carbon-carbon double bond in the side chain.
  • the main chain is a saturated hydrocarbon (alkylene group) and the side chain is a polyolefin structure containing a carbon-carbon double bond.
  • Such a polyolefin structure preferably contains a carbon-carbon double bond at the tip of the side chain.
  • branched-chain polyolefins examples include polybutadiene (1,2-polybutadiene, 1,2-polybutadiene containing a 1,4 addition polymerization butadiene structure) and polyisoprene (1,2-polyisoprene, 3,4-). Polyisoprene) and the like.
  • a part of the side chain in X may be composed of saturated hydrocarbons. In other words, some of the side chains of the plurality of side chains may be composed of saturated hydrocarbons (alkyl groups). It is preferable that 5% or more (for example, 10% or more) of the total number of side chains (number of moles) in X contains a carbon-carbon double bond.
  • the molecular weight of the polyolefin structure in the general formula (I) is preferably 1000 or more and 6000 or less.
  • the molecular weight of the polyolefin structure can be determined by a standard polystyrene-equivalent value measured by GPC (gel permeation chromatography) before synthesizing the curable compound of the general formula (I).
  • the two Ys represent either the general formula (II) or the general formula (III) independently of each other.
  • the two Ys may have the same molecular structure or different molecular structures from each other.
  • each T has a structure of a part of an isocyanurate form, an adduct form, or a biuret form of an aliphatic diisocyanate having a total carbon number of 6 or more and 10 or less independently of each other. Represents.
  • each T corresponds to the structure obtained by removing -NCO from the isocyanurate form, adduct form, or biuret form as described above.
  • the structure represented by the general formula (a) is the above-mentioned isocyanurate structure
  • the structure represented by the general formula (b) is the above-mentioned adduct body structure
  • the general formula (c) or (d) is used.
  • the structure represented by is a biuret body structure.
  • a plurality of Ts may be the same as each other or may be different from each other.
  • the notation "Z or NHCOO-" described in parentheses is not included in T in the general formula (II) or (III).
  • the aliphatic diisocyanate having a total carbon number of 6 or more and 10 or less is a linear alkylene group having 4 or more and 8 or less carbon atoms at both ends. Each has an isocyanate group. Since T contained in Y is composed of, for example, an isocyanurate structure, an adduct structure, or a biuret structure of an aliphatic diisocyanate, it has a benzene ring structure and a saturated cycloalkyl structure (the ring is only a carbon atom). Does not include any of the configured saturated structures).
  • T is composed of an isocyanurate structure, an adduct body structure, or a biuret body structure of an aliphatic diisocyanate
  • Y does not have a benzene ring structure. Since Y does not have a benzene ring structure, the weather resistance of the cured product after curing is improved.
  • aliphatic diisocyanate having a total carbon number of 6 or more and 10 or less examples include hexamethylene diisocyanate (HMDI).
  • the above isocyanurate is a trimer of the above aliphatic diisocyanate.
  • the structure excluding the terminal-NCO of such a trimer corresponds to the structure represented by the general formula (a).
  • the above-mentioned adduct is a reaction product of the above-mentioned aliphatic diisocyanate and triol having 3 or more and 6 or less carbon atoms.
  • the structure excluding the terminal-NCO of such a reactant corresponds to the structure represented by the general formula (b).
  • Triol having 3 or more carbon atoms and 6 or less carbon atoms contains only carbon (C), oxygen (O) and hydrogen (H) as elements.
  • examples of the triol having 3 or more carbon atoms and 6 or less carbon atoms include trimethylolpropane (CH 3- CH 2- C (CH 2- OH) 3 ) and glycerin.
  • the above-mentioned biuret body is a reaction product of the above-mentioned aliphatic diisocyanate with water or a tertiary alcohol.
  • the structure of the terminal-NCO inner part of such a reactant corresponds to the structure represented by the general formula (c) or the general formula (d), respectively.
  • the two Ls in the general formula (III) are residues of the diol (glycol) which may contain an ether bond independently of each other.
  • Each L is preferably a glycol residue having 2 or more and 6 or less carbon atoms.
  • L is, for example, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol (1,2-butanediol, 1,3-butanediol, 1,4-butanediol, etc.), pentylene glycol (1,2-pen). It may be each residue such as tanzier, 1,5-pentanediol), neopentyl glycol and the like.
  • L is a residue after each hydroxy group (-OH) of the diol compound has undergone a urethanization reaction with -NCO, for example, if L is a residue of dipropylene glycol, L is -C 3 H 6 It is represented by -OC 3 H 6-. L is preferably a residue of dipropylene glycol or neopentyl glycol in that the above-mentioned curable compound has good solubility and the cured product can have good heat resistance.
  • the two Ls in the general formula (III) are independent of each other and may be the same or different from each other. In other words, the plurality of L contained in the curable compound represented by the general formula (I) may be the same as each other or may be different from each other.
  • each of the plurality of Zs independently represents the molecular structure or -NCO represented by the above general formula ( ⁇ ).
  • At least one of the plurality of Zs in the curable compound represented by the general formula (I) may have the molecular structure represented by the above general formula ( ⁇ ), and at least one may be ⁇ NCO.
  • the curable compound represented by the general formula (I) may have at least one molecular structure represented by the general formula ( ⁇ ) and -NCO in the molecule.
  • all the plurality of Zs in the curable compound represented by the general formula (I) may have the molecular structure represented by the above general formula ( ⁇ ), or all the plurality of Zs are -NCO. There may be.
  • the plurality of Zs represented by the general formulas (II) and (III) are independent of each other in the curable compound represented by the general formula (I), and may be the same or different from each other. good. Since each of the two Ys represented by the general formula (I) contains a plurality of Zs (two Zs or four Zs), the general formula (I) includes four or more and eight or less Zs. .. In the general formula (I) including the general formulas (II) and (III), the plurality of Zs are individually and independently defined.
  • R a1 to R a3 , R b1 to R b3 , R c , R d1 to R d3 , and R e1 to R e3 are organic groups containing at least a carbon atom.
  • R a1 to R a3 , R b1 to R b3 , R c , R d1 to R d3 , and R e1 to R e3 may contain a urea bond, a burette bond, or an allophanate bond.
  • R a1 to R a3 , R b1 to R b3 , R d1 to R d3 , and R e1 to R e3 are preferably saturated hydrocarbons having 4 or more and 8 or less carbon atoms, and are linear saturated hydrocarbons having 6 carbon atoms. Although hydrogen is more preferable, it may contain heteroatoms (N, O, S, P, etc.) and may have a branched chain structure.
  • Rc is preferably a saturated hydrocarbon having 4 or more carbon atoms and 8 or less carbon atoms, and more preferably a branched chain saturated hydrocarbon having 6 carbon atoms, but it is a heteroatom (N, O, S, P, etc.). It may contain, and may have a linear structure.
  • the saturated hydrocarbon group having 2 or more and 4 or less carbon atoms in Q is preferably linear.
  • Q is preferably a linear saturated hydrocarbon group having 2 or more and 4 or less carbon atoms.
  • the number of carbon atoms of the saturated hydrocarbon group in Q is preferably 2.
  • the molecular structure represented by the general formula ( ⁇ ) the one represented by the following formula ( ⁇ -1) is preferable. Since it has a molecular structure represented by the following formula ( ⁇ -1), it has an ethylene group with few steric hindrances, and has an advantage that the polymerization rate by irradiation with ultraviolet rays or the like is improved.
  • the carbon number of Q in the general formula ( ⁇ ) is 1 (that is, a methylene group), it is easily decomposed at the time of curing.
  • curable compound (curing compound) represented by the general formula (I) examples include compounds represented by the following general formulas (IA) to (IG).
  • R a1 , R a2 , and R a3 are each independently a linear saturated hydrocarbon having 4 or more and 8 or less carbon atoms, p is 15 or more and 300 or less, and M is H or CH. It is 3. ]
  • R a1 , R a2 , and R a3 are each independently a linear saturated hydrocarbon having 4 or more and 8 or less carbon atoms, p is 15 or more and 300 or less, and M is H or CH. It is 3. ]
  • R a1 , R a2 , and R a3 are each independently a linear saturated hydrocarbon having 4 or more and 8 or less carbon atoms, p is 15 or more and 300 or less, and M is H or CH. It is 3. ]
  • R a1 , R a2 , and R a3 are each independently a linear saturated hydrocarbon having 4 or more and 8 or less carbon atoms, p is 15 or more and 300 or less, and M is H or CH. It is 3. ]
  • R a1 , R a2 , and R a3 are each independently a linear saturated hydrocarbon having 4 or more and 8 or less carbon atoms, and p is 15 or more and 300 or less.
  • R b1 , R b2 , and R b3 are each independently a linear saturated hydrocarbon having 4 or more and 8 or less carbon atoms, p is 15 or more and 300 or less, and M is H or CH. It is 3. ]
  • the curable compound of the present embodiment is represented by, for example, the following general formula (IG).
  • R a1 , R a2 , and R a3 are each independently a linear saturated hydrocarbon having 4 or more and 8 or less carbon atoms, and X is as described above, and a plurality of Zs (8 Zs). ) Is as described above. ]
  • the curable composition of the present embodiment contains the above-mentioned curable compound, the surface tackiness of the cured cured product is suppressed for the same reason as described above, and the cured product has appropriate extensibility. Can have.
  • the curable composition of the present embodiment contains a branched polyolefin diol containing a carbon-carbon double bond in the side chain (hereinafter, also simply referred to as ⁇ A component>) and an aliphatic having a total carbon number of 6 or more and 10 or less. isocyanurate of a diisocyanate, adduct, and at least one selected from biuret (hereinafter, simply ⁇ B component> and also referred to) and hydroxy saturated C 1 ⁇ C 4 alkyl (meth) acrylate (hereinafter, simply ⁇ C (Also referred to as component>) and the urethanization reaction product.
  • ⁇ A component> branched polyolefin diol containing a carbon-carbon double bond in the side chain
  • the curable composition of the present embodiment contains the above-mentioned urethanization reaction product, it contains at least the curable compound represented by the above general formula (I).
  • the curable composition of the present embodiment also contains other products produced by the urethanization reaction.
  • the curable composition of the present embodiment also contains a trace amount of urethanization reaction catalyst formulated for the urethanization reaction. The urethanization reaction product will be described in detail later.
  • the curable composition of the present embodiment contains at least the curable compound represented by the above general formula (I), and can be cured by at least light irradiation. In addition, it may be cured by moisture. Further, the curable composition of the present embodiment also contains other products produced by the above-mentioned urethanization reaction, and such other products can also undergo a curing reaction by light irradiation or moisture.
  • the component A is a branched-chain polyolefin diol containing a carbon-carbon double bond in the side chain.
  • Polyolefin diols have hydroxy groups at both ends of the molecule.
  • the olefin moiety does not contain polar groups such as ether groups and ester groups, and is composed only of hydrocarbons.
  • the A component is composed of a main chain and a side chain.
  • the main chain may contain saturated hydrocarbons or unsaturated hydrocarbons.
  • the side chain of the olefin moiety contains a carbon-carbon double bond.
  • polybutadiene diol (1,2-polybutadiene diol, 1,2-polybutadiene diol including 1,4 addition polymerization butadiene structure), polyisoprene diol (1,2-polyisoprene diol, 3,4-polyisoprene) Diole) and the like.
  • polybutadienediol (1,2-polybutadienediol) is preferable in that it can impart sufficient mechanical flexibility to the cured product (coating) after curing.
  • the molecular weight of component A is preferably 1000 or more and 6000 or less.
  • the component B is a polyisocyanate, which is at least one selected from isocyanurates, adducts, and biurets of aliphatic diisocyanates having a total carbon number of 6 or more and 10 or less.
  • the B component has three or four isocyanate groups in the molecule.
  • the component B preferably has neither a benzene ring structure (aromatic ring structure) nor a saturated cycloalkyl structure (saturated structure in which the ring is composed of only carbon atoms) in the molecule.
  • the isocyanurate form as the B component is, for example, the above-mentioned hexamethylene diisocyanate (HMDI) trimer and has three isocyanate groups in the molecule.
  • HMDI hexamethylene diisocyanate
  • the adduct as the B component is, for example, a reaction product of trimethylolpropane and an aliphatic diisocyanate having a total carbon number of 6 or more and 10 or less (such as HMDI described above). Such an adduct has three isocyanate groups in the molecule.
  • the B component does not contain a benzene ring, it has good weather resistance after curing, and it has good solubility in the diluent when a diluent is allowed to coexist in the urethanization reaction.
  • an adduct form obtained by reacting hexamethylene diisocyanate (HMDI) with trimethylolpropane or an isocyanurate form (trimer) of hexamethylene diisocyanate (HMDI) is preferable.
  • the C component is a C 1 to C 4 saturated alkyl ester of (meth) acrylic acid, has one hydroxy group bonded to any carbon of a saturated hydrocarbon moiety having 1 or more and 4 or less carbon atoms, and has (meth). ) It has one acryloyl group.
  • the notation "C 1 to C 4 saturated alkyl” represents the number of carbon atoms (1 or more and 4 or less) of the hydrocarbon moiety ester-bonded to (meth) acrylic acid.
  • the C component is preferably hydroxy-saturated C 2 to C 3 alkyl (meth) acrylate (the number of carbon atoms in the saturated hydrocarbon moiety is 2 or more and 3 or less).
  • the notation "(meth) acrylic” in this specification means that both "acrylic" and "methacryl” are included.
  • Examples of the C component include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth).
  • Examples include acrylate.
  • the component C is preferably 2-hydroxyethyl (meth) acrylate, more preferably 2-hydroxyethyl acrylate, in that the polymerizable property by light irradiation is better.
  • the molar ratio (B / A) of the B component to the A component in the urethanization reaction is preferably 2.0 or more, and more preferably 4.0 or more. Further, the molar ratio (B / A) is preferably 8.0 or less. When the molar ratio (B / A) is 2.0 or more, there is an advantage that the curability of the above-mentioned curable compound and the curable composition becomes better, and the molar ratio (B / A) is improved. ) Is 8.0 or less, which has an advantage that the storage stability of the above-mentioned curable compound and curable composition becomes better.
  • the molar ratio (C / B) of the C component to the B component in the urethanization reaction is preferably 0.2 or more, and more preferably 0.4 or more.
  • the molar ratio (C / B) is preferably 1.2 or less, more preferably 1.0 or less.
  • a molar ratio (C / B) is 0.2 or more, there is an advantage that the photocurability of the above-mentioned curable compound and curable composition can be further enhanced, and such a molar ratio (C / B) is obtained.
  • Is 1.2 or less which has an advantage that the moisture curability of the above-mentioned curable compound and curable composition is further enhanced.
  • the molar ratio (C / A) of the C component to the A component in the urethanization reaction is preferably 2.0 or more. Further, the molar ratio (C / A) is preferably 8.0 or less, and more preferably 4.0 or less. When such a molar ratio (C / A) is 2.0 or more, there is an advantage that the photocurability of the above-mentioned curable compound and curable composition can be further enhanced, and such a molar ratio (C / A) is obtained. ) Is 8.0 or less, which has an advantage that the storage stability of the above-mentioned curable compound and curable composition becomes better.
  • the curing reactivity of the curable compound represented by the above-mentioned general formula (I) can be adjusted by changing the compounding molar ratio of each component to be urethanized. Specifically, by relatively increasing the blending amount of the C component, the curing reactivity (polymerization reactivity) of the curable compound by light irradiation or the like can be enhanced. For example, a curable compound that cures (polymerizes) only by light irradiation or the like by blending the A component and the C component in an amount that all the isocyanate groups of the B component react to urethanization, and further blending the C component excessively. Obtainable.
  • the curing reactivity of the curable compound due to moisture or the like can be enhanced.
  • the B component in an amount in which the isocyanate group is excessive with respect to the total amount of the hydroxy groups contained in the A component and the C component, a curable compound that can be cured by humidity or the like can be obtained.
  • the curable composition of the present embodiment is not particularly limited as long as it contains the urethanization reaction product of the above-mentioned A component, B component, and C component.
  • the curable composition of the present embodiment may contain a urethanization reaction product of the above-mentioned A component, B component, and C component, and further, the following D component.
  • the urethanization reaction product may be obtained by reacting the above-mentioned A component, B component, and C component with the following D component.
  • the curable composition of the present embodiment may contain a urethanization reaction product obtained by reacting the above-mentioned A component, B component, C component, and further A'component similar to the A component.
  • the A'component a branched-chain polyolefin diol whose side chain is composed only of saturated hydrocarbons is adopted, and a urethanization reaction product obtained by further reacting the A'component is contained. But it may be.
  • the D component is a diol (glycol) having 10 or less carbon atoms, and may contain an ether bond.
  • the D component is preferably a glycol having 2 or more and 6 or less carbon atoms.
  • the D component is, for example, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol (1,2-butanediol, 1,3-butanediol, 1,4-butanediol, etc.), pentylene glycol (1,2-). It is preferably at least one selected from the group consisting of pentannel, 1,5-pentanediol, etc.) and neopentyl glycol.
  • the D component is a di-component in that the produced urethanization reaction product is more easily dissolved in an alkyl (meth) acrylate monomer (described later), and the cured product can have better moisture resistance and heat resistance. It is preferably at least one of propylene glycol and neopentyl glycol.
  • the molar ratio (D / B) of the D component to the B component in the urethanization reaction is preferably 0.3 or more, and more preferably 0.5 or more.
  • the molar ratio (D / B) is preferably 0.8 or less, more preferably 0.7 or less.
  • the molar ratio (D / B) is 0.3 or more, there is an advantage that the extensibility of the cured product becomes better, and the molar ratio (D / B) is 0.8 or less. This has the advantage that the moisture resistance of the cured product and the storage stability of the above-mentioned curable compound and curable composition are improved.
  • Examples of the urethanization reaction product in which the D component is also reacted include a curable compound represented by the general formula (IG) and a reaction product schematically represented as shown in FIG. FIG. 1 schematically shows an example of a reaction product (curable compound) when Y in the general formula (I) is represented by the general formula (III).
  • Examples of the urethanization reaction product include compounds represented by the above general formula (I) such as the above general formulas (IA) to (IG).
  • examples of the urethanization reaction product include a compound having only an isocyanate group as a reactive group, a compound having only a (meth) acryloyl group as a reactive group, and the like.
  • the above-mentioned urethanization reaction product includes, for example, a compound which is a urethanization reaction product of A component and B component and the C component is not introduced into the molecule, and the B component and the C component. Examples thereof include compounds which are urethanization reaction products with and have the A component not introduced into the molecule.
  • the curable composition of the present embodiment may further contain a compound that does not undergo a urethanization reaction.
  • a compound may be a photopolymerizable monomer (detailed later) that produces a polymerization reaction product upon irradiation with light.
  • Examples of such a photopolymerizable monomer include a saturated cycloalkyl (meth) acrylate monomer having a saturated cyclic hydrocarbon structure and a (meth) acryloyl group in the molecule, or a saturated chain hydrocarbon structure and (meth). Examples thereof include a saturated chain alkyl (meth) acrylate monomer having an acryloyl group in the molecule.
  • Such a compound may be blended as a diluent before the urethanization reaction in order to reduce the viscosity in the urethanization reaction system, and may be blended after the urethanization reaction so as to give the cured product after curing the desired physical characteristics (later). In detail).
  • the curable composition of the present embodiment may contain unreacted A component, B component, and C component that have not undergone urethanization reaction.
  • the curable composition of the present embodiment may contain a urethanization reaction catalyst formulated to promote the urethanization reaction.
  • the curable composition of the present embodiment contains various reaction products and unreacted products. Therefore, it can be said that it is not practical to specify the molecular structure of all the contained compounds. In other words, it can be said that it is almost impractical to directly specify the structure or property of all the compounds contained in the curable composition of the present embodiment.
  • the molecular structure of the compound before the urethanization reaction has been specified and the product due to the urethanization reaction can be sufficiently predicted, it is sufficiently possible to predict the molecular structure of the reaction product.
  • the curable composition of the present embodiment may contain a photopolymerizable monomer, an isocyanate monomer, a photopolymerization initiator and the like further added after the urethanization reaction.
  • the curable composition of the present embodiment contains a compound having a benzene ring (aromatic hydrocarbon composed of 6 cyclic carbon atoms) in the molecule, a urethanization reaction product (curable compound), and a photopolymerizable monomer. , It is preferable not to contain it as an isocyanate monomer.
  • Examples of the photopolymerizable monomer include a monofunctional photopolymerizable monomer.
  • Examples of the monofunctional photopolymerizable monomer include an alkyl (meth) acrylate monomer having a hydrocarbon group (alkyl group) having 18 or less carbon atoms.
  • the monofunctional photopolymerizable monomer is, for example, a saturated cycloalkyl (meth) acrylate monomer having a saturated cyclic hydrocarbon structure and one (meth) acryloyl group in the molecule, or a saturated chain. Examples thereof include a saturated chain alkyl (meth) acrylate monomer having a state hydrocarbon structure and one (meth) acryloyl group in the molecule.
  • At least one of the above-mentioned saturated cycloalkyl (meth) acrylate monomer or the above-mentioned saturated chain-like alkyl (meth) acrylate monomer is photopolymerized without a urethanization reaction. It may be contained as a sex monomer.
  • These (meth) acrylate monomers are compounds that give rise to polymerization reaction products upon irradiation with light.
  • the saturated cycloalkyl (meth) acrylate monomer is preferably a saturated alicyclic monomer having 8 or more and 15 or less carbon atoms in the molecule.
  • the saturated cycloalkyl (meth) acrylate monomer shall contain neither a benzene ring nor a polar group such as an ether bond (-CH 2- O-CH 2- ), -OH group, and -COOH group in the molecule. Is preferable.
  • the saturated cycloalkyl structure may be a saturated hydrocarbon structure which does not contain a heteroatom and is composed of 4 or more and 8 or less carbon atoms.
  • the saturated cycloalkyl (meth) acrylate monomer may be monocyclic, bicyclic or polycyclic. Bicyclic or polycyclic saturated cycloalkyl structures may share two or more carbon atoms.
  • the bicyclic or polycyclic saturated cycloalkyl (meth) acrylate monomer at least one ring structure may be a saturated alkyl structure, and for example, all ring structures may be a saturated alkyl structure.
  • a methyl group or an ethyl group may be further bonded to the carbon having a saturated cyclic hydrocarbon structure.
  • the saturated cycloalkyl (meth) acrylate monomer includes isobornyl (meth) acrylate (containing a norbornane structure), dicyclopentadieneoxyethyl (meth) acrylate (containing a norbornane structure), and dicyclopentanyl (meth). ) Acrylate (containing norbornane structure), dicyclopentenyloxyethyl (meth) acrylate (containing norbornane structure), adamantyl (meth) acrylate, etc. Among them, saturated cycloalkyl (meth) acrylate monomer containing norbornane structure. Is preferable. When the above-mentioned curable composition contains a saturated cycloalkyl (meth) acrylate monomer, the moisture resistance of the cured product after curing can be improved.
  • the saturated chain alkyl (meth) acrylate monomer is preferably a (meth) acrylate monomer having a saturated chain hydrocarbon having 8 or more and 15 or less carbon atoms in the molecule.
  • Saturated chain alkyl (meth) acrylate monomer, a benzene ring, and an ether bond (-CH 2 -O-CH 2 - ), - none of the polar groups such as OH groups and -COOH groups do not contain in the molecule Is preferable.
  • the saturated chain hydrocarbon structure does not contain atoms other than C and H, and even if it is a saturated chain hydrocarbon structure composed of 7 or more and 11 or less carbon atoms. good.
  • the flexibility of the cured product obtained by the curable composition can be further improved.
  • the saturated chain hydrocarbon structure may be linear or branched.
  • the saturated chain hydrocarbon structure may be a saturated linear hydrocarbon structure or a saturated branched chain hydrocarbon structure.
  • the saturated chain alkyl (meth) acrylate monomer may be a saturated linear alkyl (meth) acrylate monomer or a saturated branched chain alkyl (meth) acrylate monomer.
  • a saturated branched alkyl (meth) acrylate monomer is preferable in that the above-mentioned urethanization reaction product can be more sufficiently dissolved in the curable composition. As a result, a more uniform cured product film can be obtained without being affected by the substrate on which the cured product is supported, the thickness of the cured product, or the curing reaction conditions.
  • the hydrocarbon structure of the saturated linear alkyl (meth) acrylate monomer may be any saturated linear alkyl structure.
  • the saturated linear alkyl (meth) acrylate monomer include n-heptyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, and n-decyl (meth) acrylate. Examples thereof include tridecyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth) acrylate.
  • the hydrocarbon structure of the saturated branched chain alkyl (meth) acrylate monomer may be a saturated branched chain alkyl structure, and may be an iso structure, a sec structure, a neo structure, or a tert structure.
  • examples of the saturated branched chain alkyl (meth) acrylate monomer include isoheptyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, isodecyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. Can be mentioned.
  • the saturated branched chain-like alkyl (meth) acrylate monomer has better solubility with the urethanization reaction product, and is easy to obtain a more uniform cured film. At least one of a meta) acrylate and an isodecyl (meth) acrylate is preferred.
  • the monofunctional photopolymerizable monomer described above may be used alone or in combination of two or more.
  • the curable composition of the present embodiment preferably contains both the above-mentioned saturated cycloalkyl (meth) acrylate monomer and the above-mentioned saturated chain-like alkyl (meth) acrylate monomer as a photopolymerizable monomer, and has a norbornan structure. It is more preferable to include a saturated cycloalkyl (meth) acrylate monomer containing the saturated cycloalkyl (meth) acrylate monomer and a saturated branched alkyl (meth) acrylate monomer.
  • the mass ratio ( ⁇ / ⁇ ) of the saturated cycloalkyl (meth) acrylate monomer ( ⁇ ) to the saturated chain alkyl (meth) acrylate monomer ( ⁇ ) is 1 or more and 8 or less. It is preferably 5 or less, and even more preferably 3 or less.
  • the saturated chain alkyl (meth) acrylate monomer is a saturated branched chain alkyl (meth) acrylate monomer, it is preferably in the above mass ratio ( ⁇ / ⁇ ) range.
  • the mass ratio ( ⁇ / ⁇ ) When the mass ratio ( ⁇ / ⁇ ) is 1 or more, the extensibility of the cured product becomes better, and when the mass ratio ( ⁇ / ⁇ ) is 8 or less, the electrical performance (electricity) of the cured product is improved. It has the advantage of better insulation). Therefore, when the mass ratio ( ⁇ / ⁇ ) is within the above range, there is an advantage that a cured product having both electrical insulation performance and elongation performance can be obtained in a better balance.
  • the photopolymerizable monomer a benzene ring and an ether bond (-CH 2- O-CH 2- ), -OH group and -COOH group are used in that the weather resistance of the cured product after curing is improved.
  • Monomers that do not contain any of the polar groups such as are preferred.
  • the curable composition of the present embodiment may contain a polyfunctional photopolymerizable monomer.
  • the polyfunctional (meth) acrylate monomer include neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, and 1,6-hexanediol di (meth) acrylate.
  • Examples of the isocyanate monomer include an aromatic diisocyanate monomer, an alicyclic diisocyanate monomer, and an aliphatic diisocyanate monomer. These monomers may have 2 or more and 4 or less isocyanate groups in the molecule.
  • Examples of the aromatic diisocyanate monomer include each monomer such as tolylene diisocyanate, diphenylmethane diisocyanate, diphenylpropane diisocyanate, triphenylmethane diisocyanate, phenylenedi isocyanate, xylylene diisocyanate, naphthalenedi isocyanate and trizine diisocyanate.
  • Examples of the alicyclic diisocyanate monomer include hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, cyclohexylylene diisocyanate, 3-isocyanatemethyl-3,5,5-trimethylcyclohexylisocyanate (isophorone diisocyanate), and the like.
  • Examples of the aliphatic diisocyanate monomer include monomers such as 3-isocyanate ethyl-3,5,5-trimethylcyclohexyl isocyanate and 3-isocyanateethyl-3,5,5-triethylcyclohexylisocyanate.
  • the aliphatic diisocyanate monomer examples include hexamethylene diisocyanate monomer and the like. Can be mentioned.
  • the isocyanate monomer may be an adduct-form, a biuret-form, an isocyanurate-form, or a polypeptide-form of at least one of the above-mentioned monomers. These monomers may be used alone or in combination of two or more.
  • As the isocyanate monomer a monomer that does not contain a benzene ring and does not contain an unsaturated bond is preferable in that the weather resistance of the cured product after curing becomes better.
  • the photopolymerization initiator is not particularly limited as long as it is a compound that generates radicals by irradiated light (ultraviolet rays or the like).
  • Examples of the photopolymerization initiator include an acetophenone-based photoinitiator, a benzoin-based photoinitiator, a benzophenone-based photoinitiator, a thioxanthone-based photoinitiator, and an acylphosphine oxide-based photoinitiator.
  • the photopolymerization initiator a commercially available product can be used.
  • the curable composition of the present embodiment may contain a photosensitizer, a polymerization inhibitor, an antioxidant, a dye (fluorescent dye), a pigment and the like, if necessary.
  • the curable composition of the present embodiment preferably contains 10% by mass or more of the compound represented by the general formula (I). As a result, the cured product after curing can be more suppressed in surface tackiness and can have appropriate extensibility.
  • the curable compound of the present embodiment may contain 90% by mass or less of the compound represented by the general formula (I).
  • the curable composition of the present embodiment may contain 10% by mass or more of the above-mentioned photopolymerizable monomer that does not undergo a urethanization reaction, such as an alkyl (meth) acrylate monomer, or 85% by mass or less.
  • the curable composition of the present embodiment may contain 2% by mass or more of an isocyanate monomer other than the above-mentioned curable compound, or may contain 20% by mass or less.
  • a branched polyolefin diol (the above component A) containing a carbon-carbon double bond in the side chain and an aliphatic diisocyanate isosia having a total carbon number of 6 or more and 10 or less are used.
  • a curable composition containing the reaction product of the urethanization reaction is produced.
  • the method for producing a curable composition of the present embodiment is a urethane containing the above-mentioned curable compound by at least the urethanization reaction in the presence of the above-mentioned A component, B component, C component and a urethanization reaction catalyst. It comprises a reaction step of synthesizing a chemical reaction product.
  • the method for producing a curable composition of the present embodiment further includes an addition step of adding a photopolymerizable monomer, an isocyanate monomer, and a photopolymerization initiator after the reaction step.
  • the A component, B component, C component, urethanization reaction catalyst, and D component that can be further used in the above production method are as described above.
  • each of the above components is mixed, and in order to prevent a reaction with humidity, usually, the reaction step is carried out after replacing the air in the reaction vessel with nitrogen.
  • reaction step general reaction conditions suitable for the urethanization reaction can be adopted.
  • the urethanization reaction is carried out by maintaining the temperature at 50 to 70 ° C. for 0.5 to 3 hours.
  • the ratio (molar ratio) of the amounts of the preferable A component, B component, C component, and the D component to be reacted as needed is as described above.
  • a compound that is not involved in the urethanization reaction and that produces a polymerization reaction product by light irradiation may be further coexisted.
  • examples of such a compound include the above-mentioned photopolymerizable monomer.
  • the above-mentioned photopolymerizable monomer, isocyanate monomer, and photopolymerization initiator may be further added. Since the photopolymerizable monomer and isocyanate monomer to be added have low viscosities, they play a role like a solvent for diluting the above-mentioned curable compound, but they themselves are cured by light or moisture, so that they are cured products. It also plays a role of hardening the material more sufficiently. As the photopolymerizable monomer and the isocyanate monomer are further blended, the viscosity of the curable composition for curing is lowered, and the step of applying the curable composition can be simplified.
  • a photosensitizer if necessary, a photosensitizer, a polymerization inhibitor, an antioxidant, a dye such as a fluorescent dye, a pigment, or the like may be further added.
  • the curable composition containing the curable compound of the present embodiment can be cured by irradiation with light such as ultraviolet rays and used as a cured product. Further, for example, it can be cured by moisture (humidity) in the air and used as a cured product. Specifically, after applying the above-mentioned curable composition to the electronic circuit to be coated, the composition is cured by irradiating it with light such as ultraviolet rays to form a coating film of the cured product. You may. Further, by leaving it in the air for several hours to several days, the curing reaction due to the humidity in the air can be promoted.
  • the curable composition containing the curable compound of the present embodiment is preferably cured by both a curing reaction by light and a curing reaction by moisture, but may be cured by either curing reaction. ..
  • Ultraviolet rays can be used as the light to be irradiated to proceed with the curing reaction.
  • a high-pressure mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, an LED lamp and the like can be used.
  • the irradiation intensity for example, 10 to 10,000 mW / cm 2 can be adopted.
  • the temperature of the air for advancing the curing reaction due to humidity is preferably 20 to 40 ° C., and the humidity of the air is preferably 40 to 90 RH%.
  • Objects to which the above curable composition is coated and coated include, for example, electronic circuits or terminals on a mounting substrate used for precision equipment, mounting on automobiles, bicycles, railroads, aircraft, ships, and the like.
  • the curable compound, the curable composition, and the method for producing the composition of the present embodiment are as illustrated above, but the present invention is the above-exemplified curable compound, the curable composition, and the method for producing the composition. Not limited to. That is, a general curable compound, a curable composition, and various forms used in the method for producing the composition can be adopted as long as the effects of the present invention are not impaired.
  • (1-1) A curable compound represented by the above general formula (I).
  • the two Ys independently represent either the general formula (II) or the general formula (III), and in the general formulas (II) and (III), each T is The curable compound according to (1-1) above, which represents the general formula (a).
  • the two Ys represent the general formula (III), and in the general formula (III), each T represents the general formula (a), according to the above (1-1). Sex compound.
  • the general formula (I) is the above-mentioned general formulas (IA), (IB), (IC), (ID), (IE), (IF), and ( The curable compound according to (1-1) above, which is at least one selected from the group consisting of IG).
  • (2-1) A branched-chain polyolefin diol containing a carbon-carbon double bond in the side chain, At least one selected from isocyanurates, adducts, and biurets of aliphatic diisocyanates having a total carbon number of 6 or more and 10 or less. Hydroxy saturated C 1 ⁇ C 4 alkyl (meth) acrylate, A curable composition comprising the urethanization reaction product of.
  • (2-7) Polybutadiene diol as the polyolefin diol and With the isocyanurate form of the aliphatic diisocyanate having a total carbon number of 6 or more and 10 or less.
  • Hydroxyethyl (meth) acrylates as the hydroxysaturated C 1 to C 4 alkyl (meth) acrylates
  • (3-1) A branched-chain polyolefin diol containing a carbon-carbon double bond in the side chain, At least one selected from isocyanurates, adducts, and biurets of aliphatic diisocyanates having a total carbon number of 6 or more and 10 or less.
  • Hydroxy saturated C 1 ⁇ C 4 alkyl (meth) acrylate A method for producing a curable composition, which comprises producing a curable composition containing a reaction product of the urethanization reaction by a urethanization reaction in the presence of. (3-2) The method for producing a curable composition according to (3-1) above, wherein the urethanization reaction is further carried out in the presence of a diol compound.
  • a saturated cycloalkyl (meth) acrylate monomer having a saturated cyclic hydrocarbon structure and a (meth) acryloyl group in the molecule and The above (3-1) to (3-3), wherein at least one of the saturated chain alkyl (meth) acrylate monomer having a saturated chain hydrocarbon structure and a (meth) acryloyl group in the molecule further coexists.
  • the method for producing a curable composition according to any one.
  • (A) to (C) are mixed as follows, and (D) and (E) are further mixed as necessary to carry out a urethanization reaction, and the curability represented by the general formula (I) is carried out.
  • a curable composition containing the compound was produced.
  • Example 1 The urethanization reaction was carried out at 60 ° C. for 1 hour in the presence of the above-mentioned (A) to (D) and the like and the reaction solvent and catalyst at the blending amounts shown in Table 1, and the reaction step was carried out. Next, the above raw materials were added to and mixed with the composition after the reaction step at the blending amounts shown in Table 1, and the addition step was carried out. In this way, a curable composition containing a curable compound represented by the general formula (I) was produced.
  • Examples 2 to 9, Comparative Examples 1 and 2 A curable composition was produced in the same manner as in Example 1 except that the blending amounts shown in Tables 1 and 2 were changed.
  • the relative molar ratio of the component (B) was set to 6.0. However, it was confirmed that gelation occurred during the reaction. Therefore, in order to suppress such gelation, the relative molar ratio described above was set to 8.0 or the like in the actual reaction step.
  • Tables 1 and 2 show the compounding compositions for producing the curable composition (curable compound) of each example.
  • the numbers in parentheses in each table indicate the relative molar ratio of the molecules of each component. Such a molar ratio was calculated based on the hydroxyl value of the component (A) (or the component (A')).
  • the component B was blended in an amount in which the isocyanate group was excessive with respect to the total amount of the hydroxy groups contained in the component A and the component C. This produced a curable composition that was cured not only by light irradiation but also by moisture.
  • each curable composition produced in Examples and Comparative Examples was evaluated. Specifically, the surface tackiness, elongation rate, and volume resistivity of the cured product (cured film) obtained by curing each of the produced curable compositions were investigated. In general, the higher the volume resistivity, the more sufficiently the curing progresses.
  • ⁇ Hardening process> A tin plate of 0.3 x 130 x 180 mm (for surface tackiness evaluation / volume resistance measurement) or a 50 ⁇ m-thick PET film that has been mold-released so that the thickness of the cured product after curing is 100 ⁇ m (elongation rate). Each composition was coated on (for measurement). Then, ultraviolet rays were irradiated with a 500 W UV lamp so that the integrated light intensity had a light intensity of 3000 mJ / cm 2. Further, it was allowed to stand for 72 hours in a constant temperature and humidity chamber set at 40 ° C./90% RH, and was subjected to a curing treatment with humidity.
  • a paste-like silver conductive paint was applied in a circular shape (diameter 30 mm) on each cured product cured as described above.
  • the upper electrode was formed by drying at 60 ° C. for 30 minutes.
  • the tin plate arranged on the opposite side of each cured product was used as the lower electrode.
  • a voltage of 100 V DC was applied and the resistance value after 60 seconds was determined. Then, the electrode area was multiplied by the resistance value and divided by the thickness of the cured product (cured film) to obtain the volume resistivity.
  • Tables 1 and 2 show the evaluation results of the cured product after curing.
  • the cured product obtained by curing the curable composition of each example has a surface tack property as compared with the cured product of the composition of the comparative example. It was suppressed and had moderate extensibility.
  • the appropriate elongation rate is, for example, about 30 to 150%. If the elongation rate is too large, it will flow at a high temperature, which may cause problems such as deterioration of solder resistance. On the other hand, if the elongation rate is too small, the cured product cannot absorb the shrinkage difference from the substrate under cold conditions (repeated conditions of high temperature and low temperature), which may cause problems such as cracks in the cured product.
  • Comparative Example 2 is an example in which a crosslinkable trifunctional acrylate monomer was blended with the composition to obtain a cured product.
  • the cured product obtained by promoting the crosslinking reaction in this manner had surface tackiness and the elongation rate became excessively small.
  • a method of blending a polyfunctional acrylate monomer into a pre-cured composition to increase the cross-linking density during curing has been adopted.
  • the composition of each example contains the curable compound of the general formula (I), and the curable compound contains the component (A) of the above. It is considered that the component (A) can flexibly make the physical properties of the cured product due to its molecular structure. Therefore, it is considered that the cured product has appropriate extensibility due to the flexible physical properties of the component (A) even if the cured product is sufficiently cured to reduce the surface tackiness of the cured product.
  • the curable compound and the curable composition of the present invention are, for example, applied to an electronic circuit in order to coat the electronic circuit with a cured product, and then cured by light irradiation or moisture (humidity) in the air to cure the cured product. It is preferably used.
  • the curable composition of the present invention is suitably used, for example, as a curable composition for an insulating coating.

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PCT/JP2021/026927 2020-07-21 2021-07-19 硬化性化合物、硬化性組成物、及び、硬化性組成物の製造方法 Ceased WO2022019256A1 (ja)

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EP21846926.0A EP4186933A4 (en) 2020-07-21 2021-07-19 CURABLE COMPOUND, CURABLE COMPOSITION AND METHOD FOR PRODUCING A CURABLE COMPOSITION
KR1020237004405A KR20230035113A (ko) 2020-07-21 2021-07-19 경화성 화합물, 경화성 조성물, 및 경화성 조성물의 제조 방법
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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003266614A (ja) * 2002-03-15 2003-09-24 Toyo Ink Mfg Co Ltd 自動車部材成型加工用材料及び自動車部材
JP2012159736A (ja) * 2011-02-01 2012-08-23 Bridgestone Corp 現像ローラ
JP2015071682A (ja) * 2013-10-02 2015-04-16 三洋化成工業株式会社 活性エネルギー線硬化性樹脂及びそれを含有する活性エネルギー線硬化性樹脂組成物
JP2016050251A (ja) * 2014-08-29 2016-04-11 日本化薬株式会社 ポリウレタン化合物及びそれを含有する樹脂組成物
JP2017521505A (ja) * 2014-05-08 2017-08-03 アルケマ フランス 硬化性ウレタン（メタ）アクリレートポリマー組成物および方法
JP2018024761A (ja) 2016-08-10 2018-02-15 アイカ工業株式会社 Ｌｅｄ硬化型防湿絶縁コート剤
JP2020100814A (ja) * 2018-12-19 2020-07-02 三洋化成工業株式会社 ポリウレタン樹脂水性分散体及びこれを用いてなる印刷インク
JP2020124356A (ja) 2019-02-05 2020-08-20 株式会社藤商事 遊技機
JP2020203305A (ja) 2019-06-18 2020-12-24 株式会社フレックラム パンチ金型及びこのパンチ金型を備えたプレス成形装置

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20100069559A (ko) * 2008-12-15 2010-06-24 히다치 가세고교 가부시끼가이샤 경화성 수지 조성물, 경화성 수지 필름 및 그것을 이용한 도금 방법
JP2010138361A (ja) * 2008-12-15 2010-06-24 Hitachi Chem Co Ltd 硬化性樹脂組成物及びフィルム状接着剤
CN103339571B (zh) 2011-02-01 2016-06-29 株式会社普利司通 显影辊
CN103717632B (zh) * 2011-07-19 2015-12-02 株式会社普利司通 光固化性树脂组合物、及使用其的湿区构件和功能性板
JP6372657B2 (ja) * 2014-07-17 2018-08-15 株式会社スリーボンド 硬化性樹脂組成物
JP6527003B2 (ja) * 2015-04-06 2019-06-05 ダイセル・オルネクス株式会社 層間充填用硬化性樹脂組成物
JP2017057349A (ja) * 2015-09-18 2017-03-23 日本化薬株式会社 ポリウレタン化合物及びそれを含有する樹脂組成物
JP6697306B2 (ja) * 2016-03-31 2020-05-20 ハリマ化成株式会社 湿気硬化併用光硬化型組成物、コンフォーマルコーティング剤及び硬化物
US11773202B2 (en) 2019-01-11 2023-10-03 Nitto Shinko Corporation Curable compound, curable composition, and method for producing curable composition

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003266614A (ja) * 2002-03-15 2003-09-24 Toyo Ink Mfg Co Ltd 自動車部材成型加工用材料及び自動車部材
JP2012159736A (ja) * 2011-02-01 2012-08-23 Bridgestone Corp 現像ローラ
JP2015071682A (ja) * 2013-10-02 2015-04-16 三洋化成工業株式会社 活性エネルギー線硬化性樹脂及びそれを含有する活性エネルギー線硬化性樹脂組成物
JP2017521505A (ja) * 2014-05-08 2017-08-03 アルケマ フランス 硬化性ウレタン（メタ）アクリレートポリマー組成物および方法
JP2016050251A (ja) * 2014-08-29 2016-04-11 日本化薬株式会社 ポリウレタン化合物及びそれを含有する樹脂組成物
JP2018024761A (ja) 2016-08-10 2018-02-15 アイカ工業株式会社 Ｌｅｄ硬化型防湿絶縁コート剤
JP2020100814A (ja) * 2018-12-19 2020-07-02 三洋化成工業株式会社 ポリウレタン樹脂水性分散体及びこれを用いてなる印刷インク
JP2020124356A (ja) 2019-02-05 2020-08-20 株式会社藤商事 遊技機
JP2020203305A (ja) 2019-06-18 2020-12-24 株式会社フレックラム パンチ金型及びこのパンチ金型を備えたプレス成形装置

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP4186933A4

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