Curable compound, curable composition, and method for producing curable composition

Abstract

Provided are: a curable composition, a method for producing the same, and a specific curable compound contained in the curable composition, wherein the curable composition comprises: a branched polyolefin diol having a carbon-carbon double bond in a side chain, at least one selected from an isocyanurate, an adduct, and a biuret of an aliphatic diisocyanate having a total carbon number of 6 or more and 10 or less, and a hydroxyl saturated C 1 ~C 4 The urethanization reaction products of alkyl (meth)acrylates.

Description

[0001] Cross-reference to related applications

[0002] This application claims the priority of Japanese Patent Application Nos. 2020-124356 and 2020-203305, and these applications are incorporated into the description of the present application specification by reference. Technical Field

[0003] The present invention relates to a curable compound, a curable composition containing the curable compound, and a method for producing the curable composition. Background Art

[0004] In the past, curable compositions that are cured by light irradiation, water (moisture), etc. are known. As such a curable composition, for example, a curable composition that is cured by light irradiation is known, which comprises: a urethane acrylate (curable compound) having a number average molecular weight of 1,000 to 20,000 synthesized from hydrogenated polybutadiene diol or hydrogenated polyisoprene diol; a monofunctional (meth)acrylate monomer; and an initiator having an absorption band at a wavelength of 380 nm or more (for example, Patent Document 1).

[0005] In the curable composition described in Patent Document 1, the content of the initiator is 10 to 15 parts by mass based on 100 parts by mass of the total of the curable compound and the monomer.

[0006] The curable composition described in Patent Document 1 is used for covering electronic circuits. For example, after being applied on an electronic circuit and irradiated with light, the curable composition is cured by the reaction between the curable compound and the monomer.

[0007] The curable composition described in Patent Document 1 is cured even by light from an LED light source and has excellent moisture resistance, electrical insulation, and the like.

[0008] Prior art literature

[0009] Patent Literature

[0010] Patent Document 1: Japanese Patent Application Publication No. 2018-024761 Summary of the invention

[0011] Problem that the invention aims to solve

[0012] However, for the reasons such as the above-mentioned curable compound contained in the curable composition recorded in patent document 1 does not have unsaturated bonds by hydrogenation, the cured solid of the curable composition recorded in patent document 1 may not necessarily suppress the viscosity (micro-adhesion) of the surface. In this case, the following problems may arise: foreign matter (for example, the electrical insulation of the solid can be reduced) is attached to the surface of the solid, or the traces of objects such as packaging materials contacting the solid remain on the surface of the solid. In addition, there is a problem that the surface viscosity of the solid is suppressed, and the solid does not have appropriate elasticity. Therefore, it is desired that the surface viscosity of the solid after curing is suppressed and the solid has appropriate elasticity.

[0013] In view of the above problems and desires, an object of the present invention is to provide a curable compound and a curable composition that can provide a cured product having suppressed surface tackiness and appropriate stretchability.

[0014] Another object of the present invention is to provide a method for producing a curable composition comprising the curable compound.

[0015] Solutions for solving problems

[0016] In order to solve the above-mentioned problems, the curable compound of the present invention is characterized by being represented by the following general formula (I).

[0017]

[0018] [In the general formula (I), X represents a branched polyolefin structure containing a carbon-carbon double bond in the side chain, two Ys each independently represent any of the following general formula (II) or the following general formula (III), in the general formulas (II) and (III), each T independently represents any of the following general formulas (a) to (d), a plurality of Zs each independently represent a molecular structure represented by the following general formula (α) or any of -NCO, and in the general formula (III), two Ls each independently represent a diol residue.]

[0019]

[0020] [In the general formula (a), R a1 , R a2 , R a3 Each independently represents an organic group.]

[0021]

[0022] [In the general formula (b), R b1 , R b2 , R b3 , R c Each independently represents an organic group.]

[0023]

[0024] [In general formula (c), R d1 , R d2 , R d3 Each independently represents an organic group.]

[0025]

[0026] [In the general formula (d), R e1 , R e2 , R e3 Each independently represents an organic group.]

[0027]

[0028] [In the general formula (α), Q represents a saturated hydrocarbon group having 2 or more and 4 or less carbon atoms, and M represents H or CH 3 . ]

[0029] The curable composition of the present invention comprises: a branched polyolefin diol having a carbon-carbon double bond in a side chain; at least one selected from an isocyanurate, an adduct and a biuret of an aliphatic diisocyanate having a total carbon number of 6 or more and 10 or less; and a hydroxyl saturated C 1 ~C 4 The urethanization reaction products of alkyl (meth)acrylates.

[0030] The method for producing a curable composition of the present invention is characterized in that a branched polyolefin diol having a carbon-carbon double bond in a side chain, at least one selected from the group consisting of an isocyanurate form, an adduct and a biuret form of an aliphatic diisocyanate having a total carbon number of 6 or more and 10 or less, and a hydroxyl saturated C 1 ~C 4 The urethanization reaction in the presence of the alkyl (meth)acrylate produces a curable composition containing a reaction product of the urethanization reaction. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 This is a schematic diagram schematically showing an example of a urethanization reaction product. DETAILED DESCRIPTION

[0032] [Curing compound]

[0033] Hereinafter, one embodiment of the curable compound of the present invention will be described.

[0034] The curable compound of this embodiment is represented by the following general formula (I).

[0035]

[0036] [In the general formula (I), X represents a branched polyolefin structure containing a carbon-carbon double bond in the side chain, two Ys each independently represent any of the following general formula (II) or the following general formula (III), in the general formulas (II) and (III), each T each independently represents any of the following general formulas (a) to (d), a plurality of Zs each independently represents a molecular structure represented by the following general formula (α) or any of -NCO, and in the general formula (III), two Ls each independently represent a diol residue.]

[0037]

[0038] [In the general formula (a), R a1 , R a2 , R a3 Each independently represents an organic group.]

[0039] It should be noted that the part represented by (Z or NHCOO-) in the general formula (a) is not included in T in the general formula (II) or (III) (described for reference). The same applies to the following general formulas (b) to (d).

[0040]

[0041] [In the general formula (b), R b1 , R b2 , R b3 , R c Each independently represents an organic group.]

[0042]

[0043] [In general formula (c), R d1 , R d2 , R d3 Each independently represents an organic group.]

[0044]

[0045] [In the general formula (d), R e1 , R e2 , R e3 Each independently represents an organic group.]

[0046]

[0047] [In the general formula (α), Q represents a saturated hydrocarbon group having 2 or more and 4 or less carbon atoms, and M represents H or CH 3 . ]

[0048] In the case of double wavy lines in the above formulae, the solid double wavy lines represent those closer to X in the formula (I), and the dotted double wavy lines represent those farther from X in the formula (I).

[0049] The curable compound of the present embodiment contains at least one of the acryloyl group of (meth)acrylate or the isocyanate group (-NCO) in the molecule. In detail, as shown in Z in the general formula (II) and (III), the curable compound of the present embodiment has at least one of the (meth)acryloyl group or the isocyanate group (-NCO) that participates in the curing reaction in the molecule. Therefore, curing can be performed by irradiation with light such as ultraviolet rays, and also by moisture (humidity, etc.) in the air.

[0050] For example, by irradiation with light such as ultraviolet rays, the (meth)acryloyl groups in the above compounds cause a polymerization reaction. The compounds polymerize to form a polymer (curing reaction). In addition, for example, water (H2O) contained in the moisture in the air can be used to cure the polymer. 2 O) The -NCO groups of the above compounds react with each other, and the compounds are bonded to each other. This bonding can also lead to polymerization (curing reaction).

[0051] Therefore, the curable compound of the present embodiment can be sufficiently cured by light or moisture. The surface tackiness of the cured product after curing is suppressed, and the cured product has appropriate elasticity.

[0052] In addition, when the curable compound of this embodiment contains both a (meth)acryloyl group and an isocyanate group (—NCO) in a molecule, the curable compound of this embodiment can be sufficiently cured by both light and moisture.

[0053] In the general formula (I), X is a branched polyolefin structure containing a carbon-carbon double bond in the side chain. The above-mentioned polyolefin structure is preferably a polyolefin structure in which the main chain is a saturated hydrocarbon (alkylene) and the side chain contains a carbon-carbon double bond. The above-mentioned polyolefin structure preferably contains a carbon-carbon double bond in the front end portion of the side chain. Examples of the above-mentioned branched polyolefin include polybutadiene (1,2-polybutadiene, 1,2-polybutadiene containing a 1,4-polybutadiene structure), polyisoprene (1,2-polyisoprene, 3,4-polyisoprene), etc. It should be noted that a part of the side chains in X can be composed of saturated hydrocarbons. In other words, a part of the side chains in the plurality of side chains can be composed of saturated hydrocarbons (alkyl groups). Preferably, more than 5% (for example, particularly more than 10%) of the total number (number of moles) of side chains in X contain carbon-carbon double bonds.

[0054] The molecular weight in the polyolefin structure in the general formula (I) is preferably 1000 or more and 6000 or less. By making the above molecular weight 1000 or less, the reduction of the mechanical properties of the cured product can be further suppressed. In addition, by making the above molecular weight 6000 or less, the situation that the cured product phase separation becomes uneven can be further suppressed.

[0055] The molecular weight in the polyolefin structure can be determined from a standard polystyrene conversion value measured by GPC (gel permeation chromatography) before synthesizing the curable compound of the general formula (I).

[0056] In the general formula (I), two Ys each independently represent any of the general formula (II) or the general formula (III). In the general formula (I), two Ys may have the same molecular structure or different molecular structures.

[0057] In the general formula (II) and the general formula (III), each T independently represents a structure of a part of an isocyanurate, an adduct, or a biuret of an aliphatic diisocyanate having a total carbon number of 6 or more and 10 or less. In other words, each T is equivalent to a structure in which -NCO is removed from an isocyanurate, an adduct, or a biuret as described above. For example, 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 structure, and the structure represented by the general formula (c) or (d) is a biuret structure. In the curable compound represented by the general formula (I), multiple Ts may be the same as or different from each other.

[0058] It should be noted that in the general formulae (a) to (d), the expression "Z or NHCOO-" in the brackets does not include T in the general formulae (II) or (III).

[0059] The aliphatic diisocyanate having a total carbon number of 6 or more and 10 or less before forming the above-mentioned isocyanurate structure, adduct structure, or biuret structure has an isocyanate group at both ends of a linear alkylene group having a carbon number of 4 or more and 8 or less. T contained in Y is composed of, for example, an isocyanurate structure, an adduct structure, or a biuret structure of an aliphatic diisocyanate, and therefore, does not contain a benzene ring structure or a saturated cycloalkyl structure (a saturated structure in which the ring consists only of carbon atoms).

[0060] Since T is composed of an isocyanurate structure, an adduct structure, or a biuret 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 becomes good.

[0061] Examples of the aliphatic diisocyanate having a total carbon number of 6 to 10 include hexamethylene diisocyanate (HMDI) and the like.

[0062] The isocyanurate is a trimer of the aliphatic diisocyanate. For example, the structure of the trimer excluding the terminal -NCO group corresponds to the structure represented by the general formula (a).

[0063] The adduct is a product of the aliphatic diisocyanate and a triol having a carbon number of 3 or more and 6 or less. For example, the structure of the product excluding the terminal -NCO group corresponds to the structure represented by the general formula (b).

[0064] The triol having 3 or more 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 and 6 or less carbon atoms include trimethylolpropane (CH 3 -CH 2 -C(CH 2 -OH) 3 ), propylene glycol, etc.

[0065] The biuret compound is a product of the aliphatic diisocyanate and water or a tertiary alcohol. For example, the structure of the inner portion of the terminal -NCO of the product corresponds to the structure represented by the general formula (c) or the general formula (d).

[0066] When Y is represented by the general formula (III), the two Ls in the general formula (III) are each independently a residue of a glycol optionally containing an ether bond. Each L is preferably a glycol residue having a carbon number of 2 or more and 6 or less. L is, for example, a residue of ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol (1,2-butanediol, 1,3-butanediol, 1,4-butanediol, etc.), pentanediol (1,2-pentanediol, 1,5-pentanediol, etc.), neopentyl glycol, etc.

[0067] L is the residue after the urethanization reaction of each hydroxyl group (-OH) of the diol compound with -NCO. Therefore, for example, if L is the residue of dipropylene glycol, L is represented by -C 3 H 6 -OC 3 H 6 -express.

[0068] In view of the good solubility of the curable compound and the good heat resistance of the cured product, L is preferably a residue of dipropylene glycol or neopentyl glycol.

[0069] The two L in the general formula (III) may be the same or different from each other independently. In other words, the plurality of L contained in the curable compound represented by the general formula (I) may be the same or different from each other.

[0070] In the general formulas (II) and (III), the plurality of Zs each independently represent a molecular structure represented by the general formula (α) or -NCO. At least one of the plurality of Zs in the curable compound represented by the general formula (I) may be a molecular structure represented by the general formula (α), and at least one is -NCO. In other words, the curable compound represented by the general formula (I) may have at least one molecular structure represented by the general formula (α) and -NCO in the molecule.

[0071] On the other hand, all of the plurality of Zs in the curable compound represented by the general formula (I) may be a molecular structure represented by the general formula (α) above, or all of the plurality of Zs may be -NCO.

[0072] The multiple Zs represented by the general formulae (II) and (III) may be the same or different from each other in the curable compound represented by the general formula (I). It should be noted that the two Ys represented by the general formula (I) each contain multiple Zs (2 Zs or 4 Zs), so the general formula (I) contains 4 or more and 8 or less Zs. In the general formula (I) containing the general formulae (II) and (III), the multiple Zs are defined individually and independently.

[0073] In the general formulae (a) to (d), R a1 ~R a3 , R b1 ~R b3 , R c , R d1 ~R d3 , R e1 ~R e3 is an organic group containing at least carbon atoms. a1 ~R a3 , R b1 ~R b3 , R c , R d1 ~R d3 , R e1 ~R e3 It may contain a urea bond, a biuret bond, or an allophanate bond. a1 ~R a3 , R b1 ~R b3 , R d1 ~R d3 , R e1 ~R e3 Preferably, it is a saturated hydrocarbon having 4 to 8 carbon atoms, more preferably a straight-chain saturated hydrocarbon having 6 carbon atoms, but it may contain heteroatoms (N, O, S, P, etc.) and may be a branched structure. Rc is preferably a saturated hydrocarbon having 4 to 8 carbon atoms, more preferably a branched saturated hydrocarbon having 6 carbon atoms, but it may contain heteroatoms (N, O, S, P, etc.) and may be a straight-chain structure.

[0074] In the general formula (α), the saturated hydrocarbon group having 2 to 4 carbon atoms in Q is preferably a linear saturated hydrocarbon group. In other words, Q is preferably a linear saturated hydrocarbon group having 2 to 4 carbon atoms. The saturated hydrocarbon group in Q preferably has 2 carbon atoms.

[0075] As the molecular structure represented by the general formula (α), the one represented by the following formula (α-1) is preferred. The molecular structure represented by the following formula (α-1) has the advantage of having an ethylene group with less steric hindrance, and the polymerization rate based on irradiation with ultraviolet rays is improved. It should be noted that if the carbon number of Q in the general formula (α) is 1 (i.e., a methylene group), it becomes slightly easier to decompose during curing.

[0076]

[0077] As the curable compound (curing compound) represented by the general formula (I), compounds represented by the following general formulae (IA) to (IG) are exemplified.

[0078]

[0079] [Among them, R a1 , R a2 , R a3 Each independently represents a linear saturated hydrocarbon having 4 to 8 carbon atoms, p represents 15 to 300, and M represents H or CH 3 . ]

[0080]

[0081] [Among them, R a1 , R a2 , R a3 Each independently represents a linear saturated hydrocarbon having 4 to 8 carbon atoms, p represents 15 to 300, and M represents H or CH 3 . ]

[0082]

[0083] [Among them, R a1 , R a2 , R a3 Each independently represents a linear saturated hydrocarbon having 4 to 8 carbon atoms, p represents 15 to 300, and M represents H or CH 3 . ]

[0084]

[0085] [Among them, R a1 , R a2 , R a3Each independently represents a linear saturated hydrocarbon having 4 to 8 carbon atoms, p represents 15 to 300, and M represents H or CH 3 . ]

[0086]

[0087] [Among them, R a1 , R a2 , R a3 Each independently represents a linear saturated hydrocarbon having 4 to 8 carbon atoms, and p is 15 to 300.]

[0088]

[0089] [Among them, R b1 , R b2 , R b3 Each independently represents a linear saturated hydrocarbon having 4 to 8 carbon atoms, p represents 15 to 300, and M represents H or CH 3 . ]

[0090] When Y is represented by the general formula (III), the curable compound of the present embodiment is represented by, for example, the following general formula (IG).

[0091]

[0092] [Among them, R a1 , R a2 , R a3 Each independently represents a linear saturated hydrocarbon having 4 to 8 carbon atoms, X is as described above, and the plurality of Zs (8 Zs) are as described above.]

[0093] [Curable composition]

[0094] Next, one embodiment of the curable composition of the present invention is described. The curable composition of this embodiment contains the curable compound, and therefore, for the same reason as above, the surface tackiness of the cured product after curing is suppressed, and the cured product can have appropriate elasticity.

[0095] The curable composition of the present embodiment comprises a branched polyolefin diol having a carbon-carbon double bond in a side chain (hereinafter, also referred to as <component A>), at least one selected from isocyanurate forms, adduct forms and biuret forms of aliphatic diisocyanates having a total carbon number of 6 to 10 (hereinafter, also referred to as <component B>), and a saturated C 1 ~C 4 A urethanization reaction product of an alkyl (meth)acrylate (hereinafter, also simply referred to as <component C>).

[0096] The curable composition of the present embodiment includes the above-mentioned urethanization reaction product, and therefore, includes at least the curable compound represented by the above-mentioned general formula (I). In addition, the curable composition of the present embodiment includes other products generated by the urethanization reaction in addition to the curable compound represented by the above-mentioned general formula (I). In addition, the curable composition of the present embodiment also includes a trace amount of urethanization reaction catalyst compounded for the urethanization reaction. It should be noted that the urethanization reaction product will be described in detail later.

[0097] The curable composition of the present embodiment contains at least the curable compound represented by the above general formula (I), and can be cured at least by light irradiation. In addition, it can be cured by moisture in some cases.

[0098] In addition, the curable composition of the present embodiment also contains other products generated by the above-mentioned urethanization reaction, and the above-mentioned other products can also cause a curing reaction by light irradiation or moisture.

[0099] <Component A>

[0100] Component A is a branched polyolefin diol containing a carbon-carbon double bond in the side chain. The polyolefin diol has a hydroxyl group at each end of the molecule. The olefin part does not contain polar groups such as ether groups and ester groups, and is composed only of hydrocarbons. Component A 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 part contains a carbon-carbon double bond.

[0101] As component A, polybutadiene diol (1,2-polybutadiene diol, 1,2-polybutadiene diol containing 1,4-polybutadiene structure), polyisoprene diol (1,2-polyisoprene diol, 3,4-polyisoprene diol), etc. As component A, polybutadiene diol (1,2-polybutadiene diol) is preferred in that it can impart sufficient mechanical flexibility to the cured product (film) after curing.

[0102] The molecular weight of the component A is preferably 1,000 or more and 6,000 or less.

[0103] <Ingredient B>

[0104] The component B is a polyisocyanate, which is at least one selected from aliphatic diisocyanates having a total carbon number of 6 or more and 10 or less, isocyanurate bodies, adducts, and biuret bodies. The component B has 3 or 4 isocyanate groups in the molecule. The component B preferably does not have a benzene ring structure (aromatic ring structure) and a saturated cycloalkyl structure (saturated structure in which the ring consists only of carbon atoms) in the molecule.

[0105] The isocyanurate form as the component B is, for example, a trimer of the above-mentioned hexamethylene diisocyanate (HMDI), and has three isocyanate groups in the molecule.

[0106] The adduct as component B is, for example, a product of trimethylolpropane and an aliphatic diisocyanate (such as the above-mentioned HMDI) having a total carbon number of 6 to 10. The above-mentioned adduct has three isocyanate groups in the molecule.

[0107] As component B, an adduct formed by the reaction of hexamethylene diisocyanate (HMDI) and trimethylolpropane, or an isocyanurate (trimer) of hexamethylene diisocyanate (HMDI) is preferred because it does not contain a benzene ring and thus has good weather resistance after curing, and when a diluent is coexistent in the urethanization reaction, it has good solubility in the diluent.

[0108] <Ingredient C>

[0109] The component C is (meth)acrylic acid. 1 ~C 4 The saturated alkyl ester has one hydroxyl group bonded to any carbon in a saturated hydrocarbon moiety having 1 to 4 carbon atoms and has one (meth)acryloyl group. 1 ~C 4 The expression "saturated alkyl" means the number of carbon atoms (1 or more and 4 or less) of the hydrocarbon part bonded to (meth)acrylic acid via an ester bond. The C component is preferably a hydroxyl saturated C 2 ~C 3 Alkyl (meth)acrylate (the carbon number of the saturated hydrocarbon part is 2 or more and 3 or less) In addition, the expression "(meth)acrylic acid" in this specification is meant to include both "acrylic acid" and "methacrylic acid".

[0110] Examples of the component C include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. In terms of better polymerizability by light irradiation, the component C is preferably 2-hydroxyethyl (meth)acrylate, and more preferably 2-hydroxyethyl acrylate.

[0111] The molar ratio (B / A) of component B to component A in the urethanization reaction is preferably 2.0 or more, more preferably 4.0 or more. In addition, the molar ratio (B / A) is preferably 8.0 or less. By making the molar ratio (B / A) 2.0 or more, the curability of the curable compound and the curable composition is further improved, and by making the molar ratio (B / A) 8.0 or less, the storage stability of the curable compound and the curable composition is further improved.

[0112] The molar ratio (C / B) of the component C to the component B in the urethanization reaction is preferably 0.2 or more, more preferably 0.4 or more. In addition, the molar ratio (C / B) is preferably 1.2 or less, more preferably 1.0 or less. By setting the molar ratio (C / B) to 0.2 or more, the photocurability of the curable compound and the curable composition is further improved, and by setting the molar ratio (C / B) to 1.2 or less, the moisture curability of the curable compound and the curable composition is further improved.

[0113] The molar ratio (C / A) of the component C to the component A in the urethanization reaction is preferably 2.0 or more. In addition, the molar ratio (C / A) is preferably 8.0 or less, and more preferably 4.0 or less. By setting the molar ratio (C / A) to 2.0 or more, the photocurability of the curable compound and the curable composition is further improved, and by setting the molar ratio (C / A) to 8.0 or less, the storage stability of the curable compound and the curable composition is further improved.

[0114] As described above, 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 that undergoes urethanization reaction.

[0115] Specifically, by relatively increasing the amount of component C blended, the curing reactivity (polymerization reactivity) of the curable compound by light irradiation or the like can be enhanced.

[0116] For example, by adding components A and C in amounts sufficient to allow all isocyanate groups of component B to undergo urethanization reaction and adding an excess amount of component C, a curable compound that cures (polymerizes) only by light irradiation or the like can be obtained.

[0117] In addition, by relatively increasing the amount of component B, the curing reactivity of the curable compound due to moisture or the like (reactivity of isocyanate groups with each other) can be increased.

[0118] For example, by blending the component B in an excessive amount of isocyanate groups relative to the total amount of hydroxyl groups contained in the components A and C, a curable compound that cures even in moisture or the like can be obtained.

[0119] 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.

[0120] For example, the curable composition of the present embodiment may include a urethanization reaction product of the above-mentioned components A, B, and C, and further the following component D. In other words, the urethanization reaction product may be obtained by reacting the above-mentioned components A, B, and C with the following component D.

[0121] In addition, the curable composition of the present embodiment may include a urethanization reaction product obtained by reacting, in addition to the above-mentioned components A, B and C, a component A' similar to component A. Specifically, the curable composition may include a urethanization reaction product obtained by using a branched polyolefin diol having a side chain composed only of saturated hydrocarbons as the above-mentioned component A' and further reacting the above-mentioned component A'.

[0122] <Ingredient D>

[0123] The component D is a glycol having a carbon number of 10 or less, and may contain an ether bond. The component D is preferably a glycol having a carbon number of 2 or more and 6 or less. The component D is preferably at least one selected from the group consisting of ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol (1,2-butanediol, 1,3-butanediol, 1,4-butanediol, etc.), pentanediol (1,2-pentanediol, 1,5-pentanediol, etc.) and neopentyl glycol.

[0124] The component D is preferably at least one of dipropylene glycol and neopentyl glycol, in that the generated urethanization reaction product becomes more soluble in an alkyl (meth)acrylate monomer (described later) and the cured product has better moisture resistance and heat resistance.

[0125] The molar ratio (D / B) of the D component to the B component in the urethanization reaction is preferably 0.3 or more, more preferably 0.5 or more. In addition, the molar ratio (D / B) is preferably 0.8 or less, more preferably 0.7 or less. By setting the molar ratio (D / B) to 0.3 or more, there is an advantage that the elasticity of the cured product is further improved, and by setting the molar ratio (D / B) to 0.8 or less, there is an advantage that the moisture resistance of the cured product and the storage stability of the curable compound and the curable composition are further improved.

[0126] Examples of the urethanization reaction product in which the D component also reacts include a curable compound represented by the general formula (IG), and Figure 1 The reaction products are shown schematically. Figure 1 In FIG. 1 , an example of a reaction product (curable compound) when Y in the general formula (I) is represented by the general formula (III) is schematically shown.

[0127] Examples of the urethanization reaction product include compounds represented by the general formula (I) such as the general formulas (IA) to (IG).

[0128] From another viewpoint, examples of the urethanization reaction product include a compound having only an isocyanate group as a reactive group and a compound having only a (meth)acryloyl group as a reactive group.

[0129] From another viewpoint, examples of the above-mentioned carbamate reaction product include a compound which is a carbamate reaction product of component A and component B and in which component C is not introduced into the molecule, and a compound which is a carbamate reaction product of component B and component C and in which component A is not introduced into the molecule.

[0130] The curable composition of this embodiment may further include a compound that does not undergo a carbamate reaction. The above-mentioned compound may be a photopolymerizable monomer that produces a polymerization reaction product based on light irradiation (described in detail later). As such a photopolymerizable monomer, for example, a saturated cycloalkyl (meth)acrylate monomer having a saturated cyclic hydrocarbon structure and a (meth)acryloyl group in the molecule, or a saturated chain alkyl (meth)acrylate monomer having a saturated chain hydrocarbon structure and a (meth)acryloyl group in the molecule, etc. may be cited. For such a compound, in order to reduce the viscosity in the carbamate reaction system, it can be mixed as a diluent before the carbamate reaction, and in order to make the cured solid have the desired physical properties, it can also be mixed after the carbamate reaction (described in detail later).

[0131] The curable composition of the present embodiment may contain unreacted components A, B, and C that have not undergone the urethanization reaction. The curable composition of the present embodiment may contain a urethanization reaction catalyst blended to promote the urethanization reaction.

[0132] Thus, the curable composition of the present embodiment includes various reaction products and unreacted products. Therefore, it is generally not practical to specify the molecular structure of all the compounds contained. In other words, it is generally not practical to directly specify the structure or characteristics of all the compounds contained in the curable composition of the present embodiment. Among them, by specifying the molecular structure of the compound before the urethanization reaction, the product based on the urethanization reaction can be fully predicted, and the molecular structure of the reaction product can be fully predicted.

[0133] The curable composition of the present embodiment may contain a photopolymerizable monomer, an isocyanate monomer, a photopolymerization initiator, etc. which are further added after the urethanization reaction. The curable composition of the present embodiment preferably does not contain a compound having a benzene ring (an aromatic hydrocarbon consisting of 6 cyclic carbon atoms) in the molecule as a urethanization reaction product (curable compound), a photopolymerizable monomer, or an isocyanate monomer.

[0134] As the photopolymerizable monomer, for example, a monofunctional photopolymerizable monomer can be cited. As the monofunctional photopolymerizable monomer, an alkyl (meth) acrylate monomer having a hydrocarbon group (alkyl group) with a carbon number of 18 or less can be cited. Specifically, as the monofunctional photopolymerizable monomer, 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 alkyl (meth) acrylate monomer having a saturated chain hydrocarbon structure and one (meth) acryloyl group in the molecule can be cited.

[0135] Specifically, the curable composition of the present embodiment may contain at least one of the saturated cycloalkyl (meth)acrylate monomer or the saturated linear alkyl (meth)acrylate monomer as a photopolymerizable monomer that does not undergo urethanization reaction. These (meth)acrylate monomers are compounds that produce polymerization reaction products based on light irradiation.

[0136] 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 preferably does not contain a benzene ring, an ether bond (—CH 2 -O-CH 2 -), -OH group, and -COOH group and other polar groups. In the saturated cycloalkyl (meth) acrylate monomer, the saturated cycloalkyl structure can be a saturated hydrocarbon structure composed of more than 4 and less than 8 carbon atoms and does not contain heteroatoms. The saturated cycloalkyl (meth) acrylate monomer can be monocyclic, bicyclic, or polycyclic. The bicyclic or polycyclic saturated cycloalkyl structure can have more than 2 carbon atoms in total. It should be noted that in the bicyclic or polycyclic saturated cycloalkyl (meth) acrylate monomer, as long as at least one ring structure is a saturated alkyl structure, for example, all ring structures can be saturated alkyl structures. In the saturated cycloalkyl (meth) acrylate monomer, a methyl or ethyl group can be further bonded to the carbon of the saturated cyclic hydrocarbon structure.

[0137] Specifically, examples of the saturated cycloalkyl (meth)acrylate monomer include isobornyl (meth)acrylate (containing a norbornane structure), dicyclopentadienyloxyethyl (meth)acrylate (containing a norbornane structure), dicyclopentanyl (meth)acrylate (containing a norbornane structure), dicyclopentenyloxyethyl (meth)acrylate (containing a norbornane structure), and adamantyl (meth)acrylate. Among them, a saturated cycloalkyl (meth)acrylate monomer containing a norbornane structure is preferred.

[0138] The curable composition may improve moisture resistance of a cured product after curing by including a saturated cycloalkyl (meth)acrylate monomer.

[0139] The saturated chain alkyl (meth)acrylate monomer is preferably a (meth)acrylate monomer having a saturated chain hydrocarbon with a carbon number of 8 or more and 15 or less in the molecule. The saturated chain alkyl (meth)acrylate monomer preferably does not contain a benzene ring or an ether bond (—CH 2 -O-CH 2 In the saturated chain alkyl (meth)acrylate monomer, the saturated chain hydrocarbon structure may be a saturated chain hydrocarbon structure composed of 7 or more and 11 or less carbon atoms and containing no atoms other than C and H.

[0140] The curable composition may further improve the flexibility of a cured product obtained by curing the curable composition by including a saturated chain alkyl (meth)acrylate monomer.

[0141] In the saturated chain alkyl (meth) acrylate monomer, the saturated chain hydrocarbon structure may be linear or branched. In other words, the saturated chain hydrocarbon structure may be a saturated linear hydrocarbon structure or a saturated branched hydrocarbon structure. In further other words, the saturated chain alkyl (meth) acrylate monomer may be a saturated linear alkyl (meth) acrylate monomer or a saturated branched alkyl (meth) acrylate monomer.

[0142] As the saturated chain alkyl (meth) acrylate monomer, a saturated branched chain alkyl (meth) acrylate monomer is preferred in that the urethanization reaction product can be more fully dissolved in the curable composition. Thus, a more uniform cured film can be obtained without being greatly affected by the substrate supporting the cured product, the thickness of the cured product, or the curing reaction conditions.

[0143] The hydrocarbon structure of the saturated linear alkyl (meth)acrylate monomer may be a saturated linear alkyl structure.

[0144] Specifically, examples of the saturated linear alkyl (meth)acrylate monomer include n-heptyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate, n-decyl (meth)acrylate, tridecyl (meth)acrylate, lauryl (meth)acrylate, and stearyl (meth)acrylate.

[0145] The hydrocarbon structure of the saturated branched alkyl (meth)acrylate monomer may be a saturated branched alkyl structure, and may be an iso structure, a sec structure, a neo structure, or a tert structure.

[0146] Specifically, examples of the saturated branched alkyl (meth)acrylate monomer include isoheptyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, isodecyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate.

[0147] As the saturated branched alkyl (meth)acrylate monomer, at least one of isononyl (meth)acrylate and isodecyl (meth)acrylate is preferred in terms of better solubility in the urethanization reaction product and easier acquisition of a more uniform cured film.

[0148] The above-mentioned monofunctional photopolymerizable monomers may be used alone or in combination of two or more.

[0149] The curable composition of the present embodiment preferably contains both the above-mentioned saturated cycloalkyl (meth)acrylate monomer and the above-mentioned saturated chain alkyl (meth)acrylate monomer as photopolymerizable monomers, and more preferably contains: a saturated cycloalkyl (meth)acrylate monomer containing a norbornane structure and a saturated branched alkyl (meth)acrylate monomer.

[0150] In the curable composition of the present embodiment, the mass ratio (η / θ) of the saturated cycloalkyl (meth)acrylate monomer (η) to the saturated linear alkyl (meth)acrylate monomer (θ) is preferably 1 or more and 8 or less, more preferably 5 or less, and further preferably 3 or less. In the case of the saturated linear alkyl (meth)acrylate monomer, particularly a saturated branched alkyl (meth)acrylate monomer, the above-mentioned mass ratio (η / θ) is preferably within the range.

[0151] When the mass ratio (η / θ) is 1 or more, the elasticity of the cured product is further improved, and when the mass ratio (η / θ) is 8 or less, the electrical properties (electrical insulation properties) of the cured product are further improved. Therefore, when the mass ratio (η / θ) is within the above range, there is an advantage that a cured product having both electrical insulation properties and elastic properties in a better balance can be obtained.

[0152] As the photopolymerizable monomer, it is preferred that the photopolymerizable monomer does not contain a benzene ring or an ether bond (—CH 2 -O-CH 2 -), -OH and -COOH groups.

[0153] It should be noted that the curable composition of the present embodiment may include a multifunctional photopolymerizable monomer. As a multifunctional (meth)acrylate monomer, for example, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, dicyclopentyl di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, polypropylene glycol di(meth)acrylate, ethylene oxide-modified bisphenol A di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethylene oxide-modified trimethylolpropane tri(meth)acrylate, ethylene oxide-modified pentaerythritol tetra(meth)acrylate, tris[(meth)acryloyloxyethyl]isocyanurate, ethylene oxide-modified dipentaerythritol hexa(meth)acrylate, epoxy (meth)acrylate, etc. can be cited.

[0154] Examples of the isocyanate monomer include aromatic diisocyanate monomers, alicyclic diisocyanate monomers, aliphatic diisocyanate monomers, etc. These monomers may have two or more and four or less isocyanate groups in the molecule.

[0155] Examples of the aromatic diisocyanate monomer include tolylene diisocyanate, diphenylmethane diisocyanate, diphenylpropane diisocyanate, triphenylmethane diisocyanate, phenylene diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, and tolidine diisocyanate.

[0156] Examples of the alicyclic diisocyanate monomers include hydrogenated toluene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, cyclohexylene diisocyanate, 3-isocyanatomethylene-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), 3-isocyanatoethylene-3,5,5-trimethylcyclohexyl isocyanate, and 3-isocyanatoethylene-3,5,5-triethylcyclohexyl isocyanate.

[0157] As an aliphatic diisocyanate monomer, a hexamethylene diisocyanate monomer etc. are mentioned, for example.

[0158] It should be noted that the isocyanate monomer may be an adduct, a biuret form, an isocyanurate form, or a polymer of at least any one of the above-mentioned monomers.

[0159] These monomers can be used alone or in combination of two or more.

[0160] As the isocyanate monomer, a monomer containing no benzene ring and no unsaturated bond is preferred because the weather resistance of the cured product after curing becomes better.

[0161] The photopolymerization initiator is not particularly limited as long as it is a compound that generates free radicals by irradiated light (ultraviolet rays, etc.). Examples of the photopolymerization initiator include acetophenone-based photoinitiators, benzoin-based photoinitiators, benzophenone-based photoinitiators, thioxanthone-based photoinitiators, and acylphosphine oxide-based photoinitiators.

[0162] As the photopolymerization initiator, a commercially available product can be used.

[0163] In addition, the curable composition of this embodiment can contain a photosensitizer, a polymerization inhibitor, an antioxidant, a dye (fluorescent dye), a pigment, etc. as needed.

[0164] The curable composition of this embodiment preferably contains 10% by mass or more of the compound represented by the general formula (I). This further suppresses the surface tackiness of the cured product after curing and allows the cured product to have appropriate elasticity.

[0165] In addition, the curable compound of this embodiment may contain 90 mass % or less of the compound represented by general formula (I).

[0166] The curable composition of the present embodiment may contain 10% by mass or more, or 85% by mass or less, of the photopolymerizable monomer that does not undergo urethanization reaction, such as an alkyl (meth)acrylate monomer.

[0167] The curable composition of the present embodiment may contain 2% by mass or more and 20% by mass or less of an isocyanate monomer other than the curable compound.

[0168] [Method for producing curable composition]

[0169] Next, one embodiment of the method for producing a curable composition of the present invention is described. According to the method for producing a curable composition of this embodiment, a curable composition containing the above-mentioned curable compound can be obtained.

[0170] In the method for producing a curable composition of the present embodiment, a branched polyolefin diol having a carbon-carbon double bond in a side chain (the above-mentioned component A), at least one selected from the group consisting of an isocyanurate form, an adduct and a biuret form of an aliphatic diisocyanate having a total carbon number of 6 to 10 (the above-mentioned component B), and a hydroxyl saturated C 1 ~C 4 The urethanization reaction is carried out in the presence of an alkyl (meth)acrylate (the above-mentioned component C) to produce a curable composition containing a reaction product of the urethanization reaction.

[0171] Specifically, the method for producing a curable composition according to the present embodiment includes a reaction step of synthesizing a urethanization reaction product containing the curable compound by a urethanization reaction in the presence of at least the components A, B, and C and a urethanization reaction catalyst.

[0172] The method for producing a curable composition according to the present embodiment further includes an adding step of adding a photopolymerizable monomer, an isocyanate monomer, and a photopolymerization initiator after the reaction step.

[0173] The component A, the component B, the component C, the urethanization reaction catalyst, and the component D which can be further used in the above-mentioned production method are as described above.

[0174] In the above-mentioned production method, the above-mentioned components are mixed, and the air in the reaction container is usually replaced with nitrogen to prevent reaction with moisture, and then the reaction step is carried out.

[0175] In the reaction step, general reaction conditions suitable for urethanization reaction can be adopted. Preferably, in the reaction step, the temperature of 50 to 70° C. is maintained for 0.5 to 3 hours to carry out the urethanization reaction.

[0176] In the reaction step, the preferred blending ratio (molar ratio) of the component A, the component B, the component C, and the component D which is reacted as necessary is as described above.

[0177] In the reaction step, a compound which is not involved in the urethanization reaction and generates a polymerization reaction product by light irradiation may be allowed to coexist. Examples of the compound include the photopolymerizable monomers described above.

[0178] In the adding step, after the urethanization reaction, the above-mentioned photopolymerizable monomer, isocyanate monomer, and photopolymerization initiator may be further added. The further added photopolymerizable monomer and isocyanate monomer have low viscosity, and therefore play a role like a solvent for diluting the above-mentioned curable compound. On the other hand, they themselves are cured by light and moisture, and therefore also play a role in making the cured product more fully cured. When the photopolymerizable monomer and isocyanate monomer are further compounded, the viscosity of the curable composition used for curing becomes lower, and the process of applying the curable composition can be simplified.

[0179] In the adding step, a photosensitizer, a polymerization inhibitor, an antioxidant, a dye such as a fluorescent dye, a pigment, and the like may be further blended as necessary.

[0180] The curable composition containing the curable compound of the present embodiment can be cured by irradiation with light such as ultraviolet rays to form a cured product for use, or can be cured by moisture (humidity) in the air to form a cured product for use.

[0181] Specifically, after applying the curable composition on the electronic circuit to be covered, the composition is cured by irradiating with light such as ultraviolet rays to form a cured cover film. Furthermore, the curing reaction caused by moisture in the air can be promoted by leaving it in the air for several hours to several days.

[0182] In addition, the curable composition containing the curable compound of this embodiment is preferably cured by both a curing reaction by light and a curing reaction by moisture, and may be cured by either curing reaction.

[0183] As the light for promoting the curing reaction, ultraviolet rays can be used. As the light source, a high-pressure mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, an LED lamp, etc. can be used. As the irradiation intensity, for example, 10 to 10000 mW / cm 2 .

[0184] The temperature of the air for promoting the moisture-based curing reaction is preferably 20 to 40° C., and the humidity of the air is preferably 40 to 90 RH %.

[0185] Examples of the objects to be covered by applying the curable composition include electronic circuits or terminals on mounting substrates used in precision equipment, electronic circuits or terminals on mounting substrates mounted on automobiles, bicycles, railways, airplanes, ships, etc., electronic circuits or terminals on mounting substrates used in mobile devices (mobile phones, digital cameras, digital video cameras, etc.), electronic circuits or terminals on substrates used in outdoor equipment (water heaters, air conditioner outdoor units, etc.), and electronic circuits or terminals on mounting substrates used in water-using equipment such as washing machines, warm water toilets, dishwashers and dryers.

[0186] The curable compound, curable composition, and method for producing the composition according to the present embodiment are as exemplified above, but the present invention is not limited to the curable compound, curable composition, and method for producing the composition exemplified above.

[0187] That is, various aspects used in general curable compounds, curable compositions, and methods for producing the compositions can be adopted within a range that does not impair the effects of the present invention.

[0188] The features disclosed in this specification include the following features.

[0189] (1-1)

[0190] A curable compound represented by the above general formula (I).

[0191] (1-2)

[0192] The curable compound according to (1-1) above, wherein in the general formula (I), two Ys each independently represent any of the general formula (II) or the general formula (III), and in the general formulas (II) and (III), each T represents the general formula (a).

[0193] (1-3)

[0194] The curable compound according to the above (1-1), wherein in the general formula (I), two Ys represent the general formula (III), and in the general formula (III), each T represents the general formula (a).

[0195] (1-4)

[0196] The curable compound according to the above (1-1), wherein the general formula (I) is at least one selected from the group consisting of the general formulas (IA), (IB), (IC), (ID), (IE), (IF) and (IG).

[0197] (2-1)

[0198] A curable composition comprising:

[0199] A branched polyolefin diol having a carbon-carbon double bond in a side chain,

[0200] at least one selected from the group consisting of isocyanurate forms, adduct forms and biuret forms of aliphatic diisocyanates having a total carbon number of 6 or more and 10 or less, and

[0201] Hydroxyl saturated C 1 ~C 4 Alkyl (meth) acrylate

[0202] The urethanization reaction product.

[0203] (2-2)

[0204] The curable composition according to the above (2-1), wherein the urethanization reaction product is a urethanization reaction product further comprising a diol compound.

[0205] (2-3)

[0206] The curable composition according to (2-1) or (2-2) above, comprising:

[0207] The above-mentioned carbamate reaction product,

[0208] A saturated cycloalkyl (meth)acrylate monomer having a saturated cyclic hydrocarbon structure and a (meth)acryloyl group in the molecule, and

[0209] A saturated chain alkyl (meth)acrylate monomer having a saturated chain hydrocarbon structure and a (meth)acryloyl group in the molecule.

[0210] (2-4)

[0211] The curable composition according to the above (2-3), wherein the mass ratio of the saturated cycloalkyl (meth)acrylate monomer to the saturated linear alkyl (meth)acrylate monomer is 1 to 8.

[0212] (2-5)

[0213] The curable composition according to any one of (2-2) to (2-4) above, wherein the diol compound is a glycol having 2 to 6 carbon atoms.

[0214] (2-6)

[0215] The curable composition according to any one of (2-3) to (2-5) above, wherein

[0216] The aforementioned saturated cycloalkyl (meth)acrylate monomer contains a norbornane structure in the molecule.

[0217] The saturated chain alkyl (meth)acrylate monomer contains a saturated branched alkyl structure in the molecule.

[0218] (2-7)

[0219] The curable composition according to any one of (2-1) to (2-6) above, comprising:

[0220] Polybutadiene diol as the polyolefin diol,

[0221] The aforementioned isocyanurate of the aforementioned aliphatic diisocyanate having a total carbon number of 6 or more and 10 or less, and

[0222] As the aforementioned hydroxyl saturated C 1 ~C 4 Alkyl (meth)acrylate Hydroxyethyl (meth)acrylate

[0223] The urethanization reaction product.

[0224] (3-1)

[0225] A method for producing a curable composition, comprising: preparing a branched polyolefin diol having a carbon-carbon double bond in a side chain;

[0226] at least one selected from the group consisting of isocyanurate forms, adduct forms and biuret forms of aliphatic diisocyanates having a total carbon number of 6 or more and 10 or less, and

[0227] Hydroxyl saturated C 1 ~C 4 Alkyl (meth) acrylate

[0228] A curable composition containing a reaction product of the urethanization reaction is produced by a urethanization reaction in the presence of

[0229] (3-2)

[0230] The method for producing a curable composition according to the above (3-1), wherein the urethanization reaction is further carried out in the presence of a diol compound.

[0231] (3-3)

[0232] The method for producing a curable composition according to (3-1) or (3-2), comprising:

[0233] The aforementioned isocyanurate of the aforementioned aliphatic diisocyanate having a total carbon number of 6 or more and 10 or less, and

[0234] As the aforementioned hydroxyl saturated C 1 ~C 4 Alkyl (meth)acrylate Hydroxyethyl (meth)acrylate

[0235] A curable composition containing a reaction product of the urethanization reaction is produced by a urethanization reaction in the presence of

[0236] (3-4)

[0237] The method for producing a curable composition according to any one of (3-1) to (3-3), wherein during or after the urethanization reaction,

[0238] A saturated cycloalkyl (meth)acrylate monomer having a saturated cyclic hydrocarbon structure and a (meth)acryloyl group in the molecule, and

[0239] At least one of saturated chain hydrocarbon structure and (meth)acryloyl group in the molecule coexists.

[0240] Example

[0241] Next, the present invention will be further described based on experimental examples, but the present invention is not limited to these.

[0242] As described below, (A) to (C) are mixed, and (D) and (E) are further mixed as necessary to carry out urethanization reaction, thereby producing a curable composition containing a curable compound represented by the general formula (I).

[0243] <Raw materials in the reaction process>

[0244] (A ingredient)

[0245] (A-1) Branched polyolefin diol containing a carbon-carbon double bond in the side chain

[0246] 1,2-Polybutadiene glycol (average molecular weight 3000)

[0247] Product name: NISSO-PB G-3000 Made by Nippon Soda Co., Ltd.

[0248] : Hydroxyl value (KOHmg / g=29.5)

[0249] (A-2) a branched polyolefin diol having a carbon-carbon double bond in the main chain and the side chain

[0250] ·1,2-Polybutadiene diol containing 1,4-addition polybutadiene structure (average molecular weight 2800)

[0251] 1,4-addition / 1,2-addition=8 / 2 (molar ratio)

[0252] Product name: Poly bd R45TH Made by Idemitsu Kosan Co., Ltd.

[0253] : Hydroxyl value (KOHmg / g=46.6)

[0254] (A') Similar components to the above (A-1) (side chain is a saturated hydrocarbon group)

[0255] Hydrogenated polybutadiene glycol (average molecular weight 3100)

[0256] Product name: NISSO-PB GI-3000 Made by Nippon Soda Co., Ltd.

[0257] : Hydroxyl value (KOHmg / g=29.3)

[0258] (Component B) a derivative of an aliphatic diisocyanate having a total carbon number of 6 or more and 10 or less

[0259] ·Isocyanurate derivatives of hexamethylene diisocyanate (HMDI) (trifunctional)

[0260] Product name: DURANATE TPA-100: Isocyanate group content 23% Made by Asahi Kasei Corporation

[0261] (Used only in Example 8) Product name: "Coronate HXLV: isocyanate group content 23.2%"

[0262] (Component C) Hydroxyl saturated C 1 ~C 4 Alkyl (meth) acrylate

[0263] ·2-Hydroxyethyl acrylate (commercially available)

[0264] (Component D) Diol compound

[0265] ·Dipropylene glycol (commercially available)

[0266] (other)

[0267] Photopolymerizable monomer a (reaction solvent / diluent) (commercially available isobornyl acrylate)

[0268] Photopolymerizable monomer b (reaction solvent / diluent) (commercially available isononyl acrylate)

[0269] Carbamate reaction catalyst (commercially available dibutyltin dilaurate)

[0270] <Raw materials in the addition process>

[0271] Photopolymerizable monomer a (commercially available isobornyl acrylate)

[0272] Photopolymerizable monomer b (commercially available isononyl acrylate)

[0273] · Photopolymerizable monomer c (commercially available lauryl acrylate)

[0274] Photopolymerizable monomer d (commercially available isodecyl acrylate)

[0275] · Photopolymerizable monomer e (commercial product of trimethylolpropane triacrylate) crosslinkable trifunctional

[0276] ·Multifunctional isocyanate

[0277] Isocyanurate derivatives of hexamethylene diisocyanate (HMDI)

[0278] Product name "DURANATE TPA-100" Manufactured by Asahi Kasei Co., Ltd.

[0279] ·Multifunctional isocyanate b

[0280] Isocyanurate derivatives of hexamethylene diisocyanate (HMDI)

[0281] Product name: "Coronate HXLV" Made by Tosoh Corporation

[0282] · Photopolymerization initiator Product name: "IRGACURE 907" manufactured by IGM Resins

[0283] Photosensitizer (2,4-diethylthioxanthone)

[0284] Product name: KAYACURE DETX-S Made by Nippon Kayaku Co., Ltd.

[0285] · Fluorescent dye Product name: "Tinopal OB" Made by BASF Japan Co., Ltd.

[0286] (Example 1)

[0287] The reaction step was carried out by performing a urethanization reaction at 60° C. for 1 hour in the presence of the above (A) to (D) and the like, a reaction solvent, and a catalyst in the amounts shown in Table 1. Next, the above raw materials were added to the composition after the reaction step in the amounts shown in Table 1 and mixed to carry out an addition step.

[0288] In this manner, a curable composition containing a curable compound represented by the general formula (I) is produced.

[0289] (Examples 2 to 9, Comparative Examples 1 and 2)

[0290] The curable composition was prepared in the same manner as in Example 1 except that the compounding amounts shown in Tables 1 and 2 were changed. It should be noted that in each reaction step of Examples 3 to 9, the relative molar ratio of component (B) was set to 6.0. However, it was confirmed that gelation occurred during the reaction. Therefore, in order to suppress the above-mentioned gelation, in the actual reaction step, the above-mentioned relative molar ratio was set to 8.0, etc.

[0291] The products produced by the reaction steps of Examples 1 to 3 were analyzed by FT-IR. As a result, it was confirmed that compounds represented by the general formula (I) including the general formula (a) were synthesized.

[0292] The compounding composition of the curable composition (curable compound) used to manufacture each embodiment is shown in Table 1 and Table 2. The numerical values ​​in brackets in each table respectively represent the relative molar ratio of the molecules of each component. The above molar ratio is calculated based on the hydroxyl value of component (A) (or component (A')). It should be noted that in all embodiments, the total amount of hydroxyl groups contained in component A and component C is mixed, and the isocyanate group becomes an excessive amount of component B. Thus, a curable composition that is cured not only by light irradiation but also by moisture is manufactured.

[0293] [Table 1]

[0294] () indicates relative molar ratio. Unit: parts by mass

[0295]

[0296] [Table 2]

[0297] () indicates relative molar ratio. Unit: parts by mass

[0298]

[0299] The curable compositions prepared in Examples and Comparative Examples were evaluated as follows: Specifically, the surface tack, elongation, and volume resistivity of the cured products (cured films) obtained by curing the prepared curable compositions were examined.

[0300] It should be noted that, generally, a higher volume resistivity means that curing has proceeded more fully.

[0301] <Curing treatment>

[0302] Each composition was applied to a 0.3×130×180 mm flexible plate (for surface viscosity evaluation / volume resistance measurement) or a 50 μm thick PET film (for elongation measurement) after mold release so that the thickness of the cured product after curing was 100 μm. Then, a 500 W UV lamp was used to obtain a cumulative light intensity of 3000 mJ / cm 2 Furthermore, the film was left to stand in a constant temperature and humidity chamber set at 40°C / 90%RH for 72 hours to perform a moisture-based curing process.

[0303] <Surface adhesion of cured product (cured film)>

[0304] After obtaining a cured film on the flexible board by the above method, a 50 μm thick PET film (without demolding treatment) cut into a size of 10 mm square is overlapped with the cured film. Next, at room temperature, the PET film is arranged on the lower side and the flexible board is arranged on the upper side, and it is confirmed whether the PET film falls within 30 seconds. If the PET film falls, it is judged that there is no surface stickiness, and if it does not fall, it is judged that there is surface stickiness.

[0305] <Elongation of Cured Product (Cured Film)>

[0306] After obtaining a cured film on a 50 μm thick PET film by the above method, it was punched out with a Thomson knife in a dumbbell No. 2 shape specified in JIS K6251. Then, the cured film was peeled off from the PET film and a tensile test was performed at room temperature according to the method specified in the above JIS regulations. It should be noted that the tensile speed was set to 300 mm / min, and the elongation was calculated as a percentage according to the calculation formula of elongation = (length increase of the cured film at break) / (original length of the cured film).

[0307] <Volume resistivity>

[0308] On each cured product cured as described above, apply a paste of silver conductive paint in a circular shape (30 mm in diameter). Dry at 60°C for 30 minutes to form an upper electrode. On the other hand, a flexible plate disposed on the opposite side of each cured product is used as a lower electrode. At room temperature, a voltage of DC100V is applied to determine the resistance value after 60 seconds. Then, the electrode area is multiplied by the resistance value and divided by the thickness of the cured product (cured film) to determine the volume resistivity.

[0309] Tables 1 and 2 show the evaluation results of the cured products after curing.

[0310] From the evaluation results shown in Tables 1 and 2, it can be understood that the cured products obtained by curing the curable compositions of the examples have reduced surface tackiness and have appropriate stretchability compared to the cured products of the compositions of the comparative examples.

[0311] It should be noted that the appropriate elongation is, for example, about 30 to 150%. If the elongation is too large, the material will flow at high temperatures, which may cause problems such as reduced solder resistance. On the other hand, if the elongation is too small, the cured material cannot absorb the shrinkage difference with the substrate under hot and cold conditions (repeated high and low temperature conditions), which may cause problems such as cracks in the cured material.

[0312] Comparative Example 2 is an example in which a crosslinkable trifunctional acrylate monomer is blended into the composition to obtain a cured product. The cured product obtained by accelerating the crosslinking reaction has surface tackiness and has an excessively low elongation.

[0313] In the past, in order to reduce the surface viscosity of the cured product, a method of mixing a multifunctional acrylate monomer into the pre-curing composition to increase the crosslinking density during curing has been gradually adopted. According to the above method, as a multifunctional acrylate monomer, as in Comparative Example 2, trimethylolpropane triacrylate is used, and as a result, not only the elongation of the cured product becomes too low (the cured product becomes too hard), but also the surface viscosity cannot be reduced.

[0314] In contrast, in the cured product formed by curing the composition of each embodiment, the suppression of surface viscosity and appropriate elasticity can be taken into account. The composition of each embodiment comprises a curable compound of the above-mentioned general formula (I), and the curable compound comprises the above-mentioned (A) component. It is believed that (A) component can make the physical property of the cured product soft in molecular structure. It is thus believed that even if the surface viscosity of the cured product is reduced by sufficient curing, the physical property cured product based on the softness of the (A) component also has appropriate elasticity.

[0315] Industrial Applicability

[0316] The curable compound and curable composition of the present invention can be used as a cured product to cover an electronic circuit, for example, and after being applied to the electronic circuit, it is cured by light irradiation or moisture (humidity) in the air to form a cured product. The curable composition of the present invention can be used as a curable composition for an insulating coating, for example.

Claims

1. A curable composition comprising: a urethanization reaction product, isobornyl (meth)acrylate and isononyl (meth)acrylate, The urethanization reaction product is a branched polyolefin diol containing a carbon-carbon double bond in the side chain and At least one selected from the group consisting of isocyanurate forms, adduct forms and biuret forms of aliphatic diisocyanates having a total carbon number of 6 or more and 10 or less; Hydroxyl saturated C 1 ~C 4 Urea-forming reaction products of alkyl (meth)acrylates, The mass ratio of the isobornyl (meth)acrylate to the isononyl (meth)acrylate is 1 or more and 3 or less.

2. The curable composition according to claim 1, in, The urethanization reaction product is a product of further urethanization reaction with a diol compound.

Images