JP2023173203A - Urethane (meth)acrylate compound, composition, and cured product - Google Patents

Abstract

To provide a urethane (meth)acrylate compound capable of forming a cured product excellent in flexibility.SOLUTION: The urethane(meth)acrylate compound is represented by the general formula (1) in the figure. (In the general formula (1), X is a divalent linking group in which the number of carbon atoms from hydrocarbons is 2 to 10; R1 and R2 are each independently a hydrocarbon group having 10 to 18 carbon atoms; and Y1 and Y2 are each independently a (meth)acryloyl alkylene carbamoyl group.)SELECTED DRAWING: None

Description

The present invention relates to a urethane (meth)acrylate compound, a composition, and a cured product.

Urethane (meth)acrylate compounds are useful compounds that are widely used as materials constituting inks, paints, films, adhesives, and the like.

In recent years, research has been conducted to synthesize various compounds using bisphenol compounds derived from biomass (eg, cardanol, etc.) as raw materials.

For example, Patent Document 1 describes an invention relating to a bisphenol compound having a specific structure, and discloses the use of a compound derived from cardanol as a raw material for the bisphenol compound having the specific structure.
Further, it is disclosed that the above bisphenol compound is used as a raw material for polycarbonate, polyacrylate, epoxy resin, etc.

However, in Patent Document 1, synthesis of a urethane (meth)acrylate compound using a bisphenol compound using a compound derived from cardanol as a raw material and its characteristics were not sufficiently investigated.

Japanese Patent Application Publication No. 2014-189526

An object of the present invention is to provide a novel urethane (meth)acrylate compound from which a cured product with excellent flexibility can be obtained.

As a result of intensive studies by the present inventors, a novel urethane (meth)acrylate compound represented by the general formula (1) described below was produced. The present inventors have discovered that this new urethane (meth)acrylate compound has excellent flexibility and is useful for the above-mentioned applications, and have completed the present invention.

（一般式（１）中、Ｘは炭化水素に由来する炭素数が２～１０である２価の連結基であり、Ｒ^１及びＲ^２はそれぞれ独立して、炭素数が１０～１８の炭化水素基であり、Ｙ^１及びＹ^２はそれぞれ独立して、一般式（２）で表される置換基である。）

（一般式（２）中、＊は、Ｏ^１又はＯ^２との連結部を表し、Ｒ^３は、炭素数が１～１５の炭化水素基であり、Ｒ^４は、水素原子又はメチル基である。） The present invention is a urethane (meth)acrylate compound represented by the following general formula (1).

(In general formula (1 ⁾ , X is a divalent linking group having 2 to ¹⁰ carbon atoms derived from a hydrocarbon; It is a hydrogen group, and Y ¹ and Y ² are each independently a substituent represented by the general formula (2).)

(In general formula (2), * represents a linkage with O ¹ or O ² , R ³ is a hydrocarbon group having 1 to 15 carbon atoms, and R ⁴ is a hydrogen atom or a methyl group. be.)

In the urethane (meth)acrylate compound of the present invention, R ¹ and/or R ² in the above general formula (1) preferably have 12 to 16 carbon atoms.
In the urethane (meth)acrylate compound of the present invention, each of the two aryl groups connected to X is preferably derived from a cardanol hydrogenated product.
In the urethane (meth)acrylate compound of the present invention, R ¹ and/or R ² in the above general formula (1) are preferably at the meta position with respect to the oxygen atom (O ¹ or O ² ).
In the urethane (meth)acrylate compound of the present invention, R ¹ and/or R ² in the above general formula (1) are preferably at the para position with respect to X.
In the urethane (meth)acrylate compound of the present invention, O ¹ and/or O ² in the above general formula (1) are preferably at the ortho position with respect to X.
In the urethane (meth)acrylate compound of the present invention, in the above general formula (1), X preferably has 3 to 7 carbon atoms.
The composition of the present invention is a composition containing the above-mentioned urethane (meth)acrylate compound.
The cured product of the present invention is a cured product obtained by curing the above-mentioned urethane (meth)acrylate compound.
The cured product of the present invention is a cured product obtained by curing a composition containing the above-mentioned urethane (meth)acrylate compound.

The present invention can provide a novel urethane (meth)acrylate compound from which a cured product with excellent flexibility can be obtained.

FIG. 1 shows an infrared absorption spectrum using 3-pentadecylphenol as a sample. FIG. 2 is an infrared absorption spectrum using the bisphenol compound obtained in Example 1 as a sample. FIG. 3 is an infrared absorption spectrum using the urethane acrylate compound obtained in Example 1 as a sample. FIG. 4 is an infrared absorption spectrum using 2-isocyanatoethyl acrylate as a sample. FIG. 5 is an infrared absorption spectrum using the urethane acrylate compound obtained in Example 2 as a sample.

（一般式（１）中、Ｘは炭化水素に由来する炭素数が２～１０である２価の連結基であり、Ｒ^１及びＲ^２はそれぞれ独立して、炭素数が１０～１８の炭化水素基であり、Ｙ^１及びＹ^２はそれぞれ独立して、一般式（２）で表される置換基である。）

（一般式（２）中、＊は、Ｏ^１又はＯ^２との連結部を表し、Ｒ^３は、炭素数が１～１５の炭化水素基であり、Ｒ^４は、水素原子又はメチル基である。） <Urethane (meth)acrylate compound>
The urethane (meth)acrylate compound of the present invention is represented by the following general formula (1).

(In general formula (1 ⁾ , X is a divalent linking group having 2 to ¹⁰ carbon atoms derived from a hydrocarbon; It is a hydrogen group, and Y ¹ and Y ² are each independently a substituent represented by the general formula (2).)

(In general formula (2), * represents a linkage with O ¹ or O ² , R ³ is a hydrocarbon group having 1 to 15 carbon atoms, and R ⁴ is a hydrogen atom or a methyl group. be.)

In this specification, the urethane (meth)acrylate compound means a urethane acrylate compound and/or a urethane methacrylate compound.

In the above general formula (1), X is a divalent linking group having 2 to 10 carbon atoms derived from a hydrocarbon.
The divalent linking group having 2 to 10 carbon atoms may be linear, branched, or have a cyclic structure. Specific examples include alkylene groups, alkenylene groups, alkynylene groups, and the like.
Among these, from the viewpoint of reactivity with the corresponding aldehyde or ketone, an alkylene group having 3 to 7 carbon atoms is preferred.
The divalent linking group having 2 to 10 carbon atoms may contain a molecule other than carbon, such as an oxygen atom or a nitrogen atom, in the linking group.
The divalent linking group having 2 to 10 carbon atoms may have a substituent, and examples of the substituent include an alkyl group, an alkoxy group, a hydroxyl group, an alkoxy-substituted alkyl group, and a carboxyl group. .

In the above general formula (1), R ¹ and R ² are each independently a hydrocarbon group having 10 to 18 carbon atoms.
The hydrocarbon group having 10 to 18 carbon atoms may be linear or branched. Further, the above hydrocarbon group having 10 to 18 carbon atoms may be saturated or unsaturated. Among these, an alkyl group having 10 to 18 carbon atoms is preferable, and an alkyl group having 11 to 17 carbon atoms is more preferable from the viewpoint of flexibility of the cured product of the urethane (meth)acrylate compound. , more preferably an alkyl group having 12 to 16 carbon atoms.

Among these, it is particularly preferable that the two aryl groups connected to X are each derived from a cardanol hydrogenated product from the viewpoint of flexibility of the cured product of the urethane (meth)acrylate compound and availability of corresponding raw materials.
Further, by being derived from cardanol, it is possible to obtain a urethane (meth)acrylate compound containing components derived from biomass, so that it can suitably contribute to the construction of a recycling-oriented society.
Examples of the structure derived from the above-mentioned cardanol hydrogenated product include those having a cardanol structure in which R ¹ and R ² have 15 carbon atoms and are hydrocarbon groups having 25 to 31 hydrogen atoms. Most preferably, the alkyl group has 31 hydrogen atoms.

In the above general formula (1), R ¹ and/or R ² may be at the ortho position, meta position, or para position with respect to the oxygen atom (O ¹ or O ² ), but the corresponding raw material From the viewpoint of availability, the meta position is preferred.
More preferably, R ¹ is meta to O ¹ and R ² is meta to O ² .

In the above general formula (1), R ¹ and/or R ² may be at the ortho position, meta position, or para position with respect to X, but the reaction between the corresponding aldehyde or ketone and the phenol compound is selected. From the viewpoint of utilizing the sex, the para position is preferable.
More preferably, R ¹ and R ² are at the para position with respect to X.

In the above general formula (1), O ¹ and/or O ² may be at the ortho position, meta position, or para position with respect to X, but the reaction between the corresponding aldehyde or ketone and the phenol compound is selected. From the viewpoint of utilizing the properties, the ortho position is preferable.
More preferably, O ¹ and O ² are at the ortho position to X.

In the above general formula (2), R ³ is a hydrocarbon group having 1 to 15 carbon atoms.
Examples of the hydrocarbon group include a divalent linear aliphatic hydrocarbon group, a divalent branched aliphatic hydrocarbon group having 3 to 15 carbon atoms, and the like.
From the viewpoint of availability and reactivity, R ³ is preferably a hydrocarbon group having 1 to 5 carbon atoms.

In the above general formula (2), R ⁴ is a hydrogen atom or a methyl group.
From the viewpoint of reactivity, R ⁴ is preferably a hydrogen atom.

The urethane (meth)acrylate compound of the present invention preferably has a biomass component ratio of 20% or more, more preferably 30% or more, even more preferably 50% or more, and still more preferably 70% or more. is particularly preferred.
When the biomass component ratio is 20% or more, it can suitably contribute to the construction of a recycling-oriented society.
Note that the above-mentioned biomass component ratio refers to the ratio of biomass-derived components contained in the obtained urethane (meth)acrylate compound, and is expressed by the following formula.
Biomass component ratio (%) = (mass of biomass-derived component / mass of entire urethane (meth)acrylate compound) x 100

[Method for producing urethane (meth)acrylate compound]
The urethane (meth)acrylate compound of the present invention can be produced, for example, by the method below.

（一般式（３）中、Ｒ^ａは、上記一般式（１）中のＲ^１又はＲ^２と同じ置換基である。） First, a compound represented by the following general formula (3) is prepared.

(In general formula (3), R ^a is the same substituent as R ¹ or R ² in general formula (1) above.)

As the compound represented by the above general formula (3), for example, a hydrogenated alkyl-substituted monophenol derived from cardanol is preferable.
The above-mentioned cardanol is a component derived from cashew nut shell liquid, and it is possible to effectively utilize cashew nut shells that were previously treated as waste.

（一般式（４）中、Ｒ^ａは、上記一般式（１）中のＲ^１又はＲ^２と同じ置換基であり、Ｘ^ａは、上記一般式（１）中のＸと同じ置換基である。） Next, a compound represented by the following general formula (4), which is a dimer of the above general formula (3), is created.

(In general formula (4), R ^a is the same substituent as R ¹ or R ² in the above general formula (1), and X ^a is the same substituent as X in the above general formula (1). be.)

The bisphenol compound represented by the above general formula (4) can be obtained, for example, by subjecting the compound represented by the above general formula (3) to a crosslinking reaction with an aldehyde in the presence of a catalyst.

Examples of the aldehyde compounds include acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, pentylaldehyde, hexylaldehyde, heptylaldehyde, octylaldehyde, cyclohexanecarboxaldehyde, benzaldehyde, p-tolualdehyde, cuminaldehyde, 2,4-dimethylbenzaldehyde, etc. can be mentioned.
The aldehyde compound may be linear or branched as long as it has 2 to 10 carbon atoms, or may have a cyclic structure.

The amount of the aldehyde used is preferably 0.15 to 0.35 mol, more preferably 0.20 to 0.35 mol, per 1 mol of the compound represented by the general formula (3).

Examples of the above-mentioned catalysts include organic acid catalysts such as toluenesulfonic acid, xylenesulfonic acid, and oxalic acid, inorganic acid catalysts such as hydrochloric acid and sulfuric acid, and phosphotungstic acid, as well as silicotungstic acid, phosphomolybdic acid, sodium phosphomolybdate, Preferred examples include heteropolyacids such as phosphotungstomolybdic acid and phosphovanadomolybdic acid.
The above catalysts may be used alone or in combination of multiple types.

The amount of the catalyst used is preferably 0.001 to 1 mol, more preferably 0.01 to 0.05 mol, per 1 mol of the compound represented by the general formula (3).

In the reaction for obtaining the bisphenol compound represented by the above general formula (4), a solvent can be used as necessary.
The above-mentioned solvent is not particularly limited as long as it has reactivity with the above-mentioned general formula (3), but in terms of easily dissolving the compound represented by the above-mentioned general formula (3), alcohols, aprotic It is preferable to use polar solvents and aromatic hydrocarbons as the solvent.

Specific examples of the above-mentioned solvents include alcohols such as methanol, ethanol, and isopropyl alcohol, aprotic polar solvents such as dimethylsulfone, dimethylsulfoxide, tetrahydrofuran, acetonitrile, methylene chloride, and dimethylformamide, and carbonated aromatic solvents such as toluene and xylene. Preferred examples include hydrogen, aliphatic hydrocarbons such as hexane, chloroform, carbon tetrachloride, etc., but are not limited thereto.
The above solvents may be used alone or in combination of multiple types.

The amount of the solvent used is not particularly limited, but for example, it can be used in an amount of 10 to 500 parts by mass per 100 parts of the compound represented by the general formula (3).

The reaction temperature for the reaction to obtain the bisphenol compound represented by the above general formula (4) is preferably 10 to 150°C, more preferably 30 to 130°C, and even more preferably 50 to 120°C. preferable.

The reaction time for the reaction to obtain the bisphenol compound represented by the above general formula (4) is preferably 0.5 to 20 hours; This is not the case as there are differences in reactivity depending on the type of compound.

After completion of the reaction to obtain the bisphenol compound represented by the above general formula (4), the catalyst is quenched by a known method. When the above acidic catalyst is used, it may be neutralized with a basic compound or washed with water.
The basic compounds mentioned above are not particularly limited, but include metal hydroxides such as sodium hydroxide, potassium hydroxide, magnesium hydroxide, and calcium hydroxide, metal carbonates such as sodium carbonate and potassium carbonate, sodium phosphate, and phosphoric acid. Preferred examples include phosphates such as sodium hydrogen and pentasodium tripolyphosphate, ion exchange resins, basic solids such as alumina, and ammonia.
At this time, in order to uniformly disperse the basic compound, it is preferable to gradually drop it as an aqueous solution.

After the quenching of the reaction to obtain the bisphenol compound represented by the above general formula (4), when the bisphenol compound represented by the above general formula (4) is to be taken out, extraction is performed from the aqueous layer using an extraction solvent. . The combined organic layers are dried over sodium sulfate and the sodium sulfate is removed by filtration. Subsequently, the solvent is distilled off under reduced pressure to obtain a crude product. The crude product is purified by column chromatography (silica gel/hexane-ethyl acetate) to obtain a compound represented by general formula (4).

Examples of the extraction solvent include, but are not limited to, hexane, heptane, octane, methylcyclohexane, ethylcyclohexane, toluene, ethylbenzene, ethyl acetate, diethyl ether, chloroform, methylene chloride, and the like.
Among these, hexane is preferred from the viewpoint of dissolving ability for the bisphenol compound represented by the above general formula (4) and ease of distillation.

Thereafter, the urethane (meth)acrylate compound of the present invention can be obtained by subjecting the bisphenol compound represented by the above general formula (4) to a urethane (meth)acrylate reaction.

The method for converting the bisphenol compound represented by the above general formula (4) into urethane (meth)acrylate is not particularly limited, and any known method can be appropriately selected and used.
For example, the bisphenol compound represented by the above general formula (4) and the isocyanate group-containing vinyl compound may be reacted in the presence of a catalyst.

Examples of the isocyanate group-containing vinyl compounds include 2-isocyanatoethyl acrylate, 2-isocyanatoethyl methacrylate, 2-(2-acryloyloxyethyloxy)ethyl isocyanate, 2-(2-methacryloyloxyethyloxy)ethyl Examples include isocyanate, 1,1-(bisacryloyloxymethyl)ethyl isocyanate, and the like.

The amount of the isocyanate group-containing vinyl compound is preferably about 5 to 70 parts by weight based on 100 parts by weight of the bisphenol compound represented by the general formula (4).

Examples of the above catalyst include known phosphorus catalysts such as ethylphosphine, propylphosphine, butylphosphine, phenylphosphine, trimethylphosphine, triethylphosphine, tributylphosphine, trioctylphosphine, triphenylphosphine, and benzyltriphenylphosphonium chloride. Known phosphates can be suitably used.

Further, a solvent may be used, and the solvent described in the step of synthesizing the bisphenol compound represented by the above general formula (4) may be appropriately selected.
Furthermore, known additives such as polymerization inhibitors and antioxidants may be added as necessary.
The amount of the catalyst is preferably about 0.1 to 4 parts by weight based on 100 parts by weight of the bisphenol compound represented by the general formula (4).
The amount of the additive used is preferably about 0.01 to 3 parts by weight based on 100 parts by weight of the bisphenol compound represented by the general formula (4).

The reaction of converting the bisphenol compound represented by the general formula (4) into urethane (meth)acrylate is preferably carried out under a nitrogen atmosphere.
Further, the reaction temperature is, for example, about 60 to 120°C. Further, the reaction time is, for example, about 1 to 10 hours.
Note that the desired urethane (meth)acrylate has been obtained by, for example, measuring an infrared absorption spectrum and seeing that the absorption near 2250 cm ^-1 derived from the isocyanate group of the isocyanate group-containing vinyl compound has disappeared. All you have to do is make sure.

Further, the devices used in the above reaction (stirring device, reflux device, etc.) may be appropriately selected from known devices.
After performing the above reaction, the product may be purified by a known method or may not be purified. It is more preferable to purify by a known method.

<Composition>
The composition of the present invention comprises the urethane (meth)acrylate compound of the present invention.

The composition of the present invention may contain additives such as a polymerization initiator, a polymerization inhibitor, a solvent, a curing accelerator, a binder resin, an inorganic filler, and a compounding agent, if necessary.
These additives may be selected from known additives as appropriate.
Moreover, in addition to the urethane (meth)acrylate compound of the present invention, other urethane (meth)acrylate compounds may be mixed.

The content of the above additives and urethane (meth)acrylate is not particularly limited as long as it does not impede the effects of the present invention, but for example, the total content is 0.1 parts per 100 parts by mass of the urethane (meth)acrylate compound of the present invention. ~500 parts by mass.

<Cured product>
The cured product of the present invention is a cured product obtained by curing the urethane (meth)acrylate compound of the present invention or a composition containing the same.
The cured product of the present invention can be obtained by curing the urethane (meth)acrylate compound of the present invention or a composition containing the urethane (meth)acrylate compound of the present invention using a conventionally known method.
For example, the urethane (meth)acrylate compound of the present invention and additives such as a polymerization initiator, a polymerization inhibitor, a solvent, a curing accelerator, a binder resin, an inorganic filler, and a compounding agent are extruded as necessary. A resin composition is obtained by sufficiently mixing the resin composition until it becomes uniform using a machine, kneader, roll, etc., and then the resin composition is potted, melted (without melting in the case of liquid), and then cast or transferred using a molding machine, etc. The cured product of the present invention can be obtained by a method of molding using a molding agent and further irradiating active energy rays.
Moreover, in addition to the urethane (meth)acrylate compound of the present invention, a cured product may be obtained using a resin composition in which another urethane (meth)acrylate compound or urethane resin is mixed.

The polymerization initiator is not particularly limited as long as it generates radicals by the action of light, and examples include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 2-hydroxy-2- Methyl-1-phenylpropan-1-one, 1-(4-isopropylenephenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methyl Propan-1-one, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexylphenylketone, 2-methyl-1-[4-(methylthio)phenyl]-2 -Morpholinopropane-1, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, 4-benzoyl -4'-Methyldiphenyl sulfide, 3,3'-dimethyl-4-methoxybenzophenone, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, camphor Quinone, dibenzosuberone, 2-ethyl anthraquinone, 4',4''-diethylisophthalophenone, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, α-acyloxime ester, Acyl phosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 2-(3-dimethylamino- 2-hydroxypropoxy)-3,4-dimethyl-9H-thioxanthon-9-one methochloride (manufactured by Octel Chemicals, "Quantacure QTX"), and the like.

The amount of the polymerization initiator used is, for example, 1 to 30 parts by weight based on 100 parts by weight of the urethane (meth)acrylate compound of the present invention.

The above-mentioned active energy ray is not particularly limited, and it can be cured by irradiation with known ionizing radiation such as electron beam, ultraviolet ray, or γ ray. When curing with ultraviolet rays, a known ultraviolet irradiation device equipped with a mercury lamp, an excimer lamp, a metal halide lamp, etc. can also be used.
The intensity and irradiation time of the active energy rays may be changed as appropriate depending on the composition, thickness, etc. of the cured product.

[Physical properties of cured product]
The cutting time of the cured product of the present invention is preferably 1.5 seconds or more, more preferably 2 seconds or more, even more preferably 2.5 seconds or more, and particularly preferably 3 seconds or more.

The cutting force of the cured product of the present invention is preferably 600N or less, more preferably 500N or less, even more preferably 400N or less, particularly preferably 300N or less, and preferably 250N or less. Most preferred.

The cured product of the present invention preferably has a tensile strength at break of 18 MPa or less, more preferably 14 MPa or less, even more preferably 11 MPa or less, particularly preferably 9 MPa or less, and 7 MPa or less. is most preferred.

The cured product of the present invention preferably has an elongation at break of 12% or more, more preferably 16% or more, and even more preferably 20% or more.

The cutting time, cutting force, cutting tensile strength, and cutting elongation of the cured product of the present invention can be measured by the tensile test described below.
Note that the tensile measurement can be performed in accordance with JIS K-6251:2017 in one or both of the preparation of the test piece and the tensile test. To prepare a test piece, for example, 100 parts by mass of a urethane (meth)acrylate compound and 10 parts by mass of 1-hydroxycyclohexylphenyl ketone ("Runtecure 1104" manufactured by Runtec) as a polymerization initiator were mixed, and a polypropylene film (Sekisui Molding Co., Ltd.) was mixed. The film was applied to a film thickness of 100 μm on ``Polyseme PC-8162'' (manufactured by Kogyo Co., Ltd., length 125 mm x width 135 mm).
Thereafter, a cured product is produced using a mercury lamp (Unicure System UVX-05016S1MC01 manufactured by Ushio Inc.) under the conditions of lamp strength 120 W, conveyor speed 40 m/min, and 120 seconds.
A dumbbell test piece No. 7 was prepared in accordance with the above JIS standard, and the tensile test was conducted at a standard temperature (27±2°C) at a tensile rate of 1 mm/sec using, for example, Bonding Tester PTR1102 manufactured by Resca Co., Ltd. This can be done under the following conditions.

The pencil hardness of the cured product of the present invention is preferably 4B or less, more preferably 5B or less, and even more preferably 6B or less.
The above pencil hardness was obtained by mixing 100 parts by mass of a urethane (meth)acrylate compound and 10 parts by mass of 1-hydroxycyclohexyl phenyl ketone (Runtec Co., Ltd. "Runtecure 1104") as a polymerization initiator, and using a slide glass (length 125 mm x width 135 mm). Coat on top with a film thickness of 100 μm.
Thereafter, a cured product was produced using a mercury lamp (Unicure System UVX-05016S1MC01 manufactured by Ushio Inc.) under the conditions of lamp intensity 120 W, conveyor speed 40 m/min, and 120 seconds, and JIS K 5600-5-4: Pencil hardness may be measured based on 1999.

The cured product of the present invention has excellent flexibility.
In the above tensile test, the cured product has a cutting time of 1.5 sec or more, a cutting force of 600 N or less, a tensile strength at cutting of 18 MPa or less, an elongation at cutting of 12% or more, and a pencil hardness of 4B. If it is below, it can be judged that the flexibility is excellent.

EXAMPLES The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited to these Examples. In addition, unless otherwise specified, "%" means "% by mass" and "parts" means "parts by mass."

(Example 1)
While purging with nitrogen, 100 parts by mass of cardanol hydrogenate (3-pentadecylphenol) was weighed into a flask equipped with a stirrer, a reflux condenser, and a stirring device, and 1.6 parts by mass of p-toluenesulfonic acid and 6 parts by mass of propionaldehyde were added. Added parts by mass. Thereafter, the reaction solution was heated to 100° C. and stirred for 3 hours under reflux to obtain a reaction mixture.
Then, the reaction temperature was returned to room temperature, and the resulting reaction mixture was neutralized with an aqueous sodium hydroxide solution. After the aqueous layer was extracted three times with hexane (extraction solvent), the organic layer was dehydrated with sodium sulfate. Thereafter, sodium sulfate was removed by filtration, and then hexane was distilled off using an evaporator to obtain a crude product.
The obtained crude product was dissolved in methanol (recrystallization solvent, 300% by mass of recrystallization solvent based on 100% by mass of crude product) at 60°C, and then cooled to 5°C and left for 1 hour. The mixture was recrystallized using the same method, and then filtered to obtain 35 parts by mass of a bisphenol compound represented by the above general formula (4), in which R ^a is linear C15H31 and X ^a is linear C3H6.

The ¹ H-NMR spectrum of the obtained bisphenol compound was measured.
^1H NMR (product name "ECX300", manufactured by JEOL Ltd., 300MHz, _CDCl3 ): δ = 7.17 (d, 2H), 6.71 (d, 2H), 6.58 (s, 2H), 4.24 (t, 1H), 2.44 (t, 4H), 2.13 (quin, 2H), 1.50 (quin, 4H), 1.25 (m, 48H), 0.87 (t+t ,6H+3H)

The infrared absorption spectrum using the 3-pentadecylphenol sample used in the synthesis of the above bisphenol compound and the infrared absorption spectrum using the bisphenol compound obtained in Example 1 as a sample were compared to the product manufactured by Thremo Fisher Scientific. The measurement was carried out using "Nicolet iN10MX".
FIG. 1 is an infrared absorption spectrum using 3-pentadecylphenol as a sample, and FIG. 2 is an infrared absorption spectrum using the obtained bisphenol compound as a sample.
From a comparison between FIG. 1 and FIG. 2, it was confirmed that the absorbance at 1585 cm ⁻¹ and 786 cm ⁻¹ derived from the aromatic skeleton of 3-pentadecylphenol decreased.
The structure of the obtained bisphenol compound was identified from the measurement results of ¹ H NMR and infrared absorption spectrum.

Weigh out 100 parts by mass of the above bisphenol type compound into a flask equipped with a stirrer, a reflux condenser, and a stirring device while purging with nitrogen, and add 2-isocyanatoethyl acrylate (“Karens AOI-VM” manufactured by Showa Denko) 43 Part by weight, 0.2 part by weight of hydroquinone, and 0.8 part by weight of triphenylphosphine were added. By heating the reaction solution to 60° C. and stirring for 1 hour, the urethane acrylate compound (in the above general formula (1), X is linear C ₃ H ₆ , R ¹ and R ² are linear C ₁₅ 144 parts by mass of H ₃₁ ) were obtained.
The biomass component ratio of this urethane acrylate compound was 67.3%.

The ¹ H-NMR spectrum of the obtained urethane acrylate compound was measured.
^1H NMR (product name "ECX300", manufactured by JEOL Ltd., 300MHz, _CDCl3 ): δ = 7.04 (d, 2H), 6.93 (m, 4H), 6.44 (dd, 2H), 6.13 (dd, 2H), 5.85 (dd, 2H), 5.79 (t, 2H), 4.20 (t, 4H), 4.16 (t, 1H), 3.36 (m , 4H), 2.54 (t, 4H), 1.95 (quin, 2H), 1.55 (m, 4H), 1.24 (m, 48H), 0.89 (m, 9H)

FIG. 3 shows an infrared absorption spectrum using the obtained urethane acrylate compound as a sample.
FIG. 4 is an infrared absorption spectrum using 2-isocyanatoethyl acrylate as a sample.
A comparison between FIG. 3 and FIG. 4 confirms that the absorption around 2250 cm ⁻¹ derived from the isocyanate group of 2-isocyanatoethyl acrylate has disappeared.

(Example 2)
The reaction was carried out in the same manner as in Example 1 except that 6 parts by mass of propionaldehyde was changed to ₁₁ parts by mass of n- _{hexylaldehyde} . , R ¹ and R ² are straight-chain C ₁₅ H ₃₁ ).
The biomass component ratio of this urethane acrylate compound was 64.3%.

The ¹ H-NMR spectrum of the obtained urethane acrylate compound was measured.
^1H NMR (product name "ECX300", manufactured by JEOL Ltd., 300MHz, _CDCl3 ): δ = 7.03 (d, 2H), 6.93 (m, 4H), 6.45 (dd, 2H), 6.13 (dd, 2H), 5.85 (dd, 2H), 5.78 (t, 2H), 4.19 (m, 5H), 3.36 (m, 4H), 2.54 (t , 4H), 1.90 (m, 2H), 1.56 (m, 4H), 1.24 (m, 54H), 0.87 (m, 9H)

FIG. 5 shows an infrared absorption spectrum using the obtained urethane acrylate compound as a sample.
A comparison between FIG. 4 and FIG. 5 confirms that the absorption around 2250 cm ⁻¹ derived from the isocyanate group of 2-isocyanatoethyl acrylate has disappeared.

(Comparative example 1)
A reaction was carried out in the same manner as in Example 1 except that the bisphenol compound was changed to commercially available bisphenol A (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) to obtain a bisphenol A urethane acrylate compound.

<Physical properties of cured product>
(Tensile test)
100 parts by mass of the samples obtained in the Examples and Comparative Examples and 10 parts by mass of 1-hydroxycyclohexylphenyl ketone ("Runtecure 1104" manufactured by Runtec) as a polymerization initiator were mixed, and a polypropylene film ("Runtecure 1104" manufactured by Sekisui Seiko Kogyo Co., Ltd.) was mixed. Polysame PC-8162" (length: 125 mm x width: 135 mm) was coated with a film thickness of 100 μm.
Thereafter, a cured product was produced using a mercury lamp (Unicure System UVX-05016S1MC01 manufactured by Ushio Inc.) under the conditions of lamp strength 120 W, conveyor speed 40 m/min, and 120 seconds.
A dumbbell test piece No. 7 was prepared from the obtained cured product according to JIS K-6251:2017.
Thereafter, a tensile test was performed using "Bonding Tester PTR1102" manufactured by Resca Co., Ltd. at a standard temperature (27±2° C.) and a tensile speed of 1 mm/sec.

(Pencil hardness)
100 parts by mass of the samples obtained in Examples and Comparative Examples and 10 parts by mass of 1-hydroxycyclohexylphenyl ketone (Runtec 1104) as a polymerization initiator were mixed, and after vacuum degassing, a slide glass (vertical) was mixed. 125 mm x width 135 mm) with a film thickness of 100 μm, and cured using a mercury lamp (Unicure System UVX-05016S1MC01 manufactured by Ushio Inc.) under the conditions of lamp intensity 120 W, conveyor speed 40 m/min, and 120 seconds. was created.
The pencil hardness of the prepared cured product was measured based on JIS K 5600-5-4:1999.

(Biomass component ratio)
The biomass component ratio of the obtained urethane acrylate compound was calculated.
Here, the biomass component ratio refers to the ratio of biomass-derived components contained in the obtained urethane acrylate compound, and is expressed by the following formula.
Biomass component ratio (%) = (mass of biomass-derived component / mass of entire urethane acrylate compound) x 100

From the results of the examples, it was confirmed that the urethane (meth)acrylate compound represented by the above general formula (1) can provide a cured product with excellent flexibility.

（一般式（１）中、Ｘは炭化水素に由来する炭素数が２～１０である２価の連結基であり、Ｒ^１及びＲ^２はそれぞれ独立して、炭素数が１０～１８の炭化水素基であり、Ｙ^１及びＹ^２はそれぞれ独立して、一般式（２）で表される置換基である。）

（一般式（２）中、＊は、Ｏ^１又はＯ^２との連結部を表し、Ｒ^３は、炭素数が１～１５の炭化水素基であり、Ｒ^４は、水素原子又はメチル基である。）
本開示（２）は、上記一般式（１）中、Ｒ^１及び／又はＲ^２は、炭素数が１２～１６である本開示（１）に記載のウレタン（メタ）アクリレート化合物である。
本開示（３）は、Ｘに連結する２つのアリール基は、それぞれカルダノール水素添加物に由来する本開示（１）又は（２）に記載のウレタン（メタ）アクリレート化合物である。
本開示（４）は、上記一般式（１）中、Ｒ^１及び／又はＲ^２は、酸素原子（Ｏ^１又はＯ^２）に対してメタ位である本開示（１）～（３）の何れかに記載のウレタン（メタ）アクリレート化合物である。
本開示（５）は、上記一般式（１）中、Ｒ^１及び／又はＲ^２は、Ｘに対してパラ位である本開示（１）～（４）の何れかに記載のウレタン（メタ）アクリレート化合物である。
本開示（６）は、上記一般式（１）中、Ｏ^１及び／又はＯ^２は、Ｘに対してオルト位である本開示（１）～（５）の何れかに記載のウレタン（メタ）アクリレート化合物である。
本開示（７）は、上記一般式（１）中、Ｘは、炭素数が３～７である本開示（１）～（６）の何れかに記載のウレタン（メタ）アクリレート化合物である。
本開示（８）は、本開示（１）～（７）の何れかに記載のウレタン（メタ）アクリレート化合物を含む組成物である。
本開示（９）は、本開示（１）～（７）の何れかに記載のウレタン（メタ）アクリレート化合物を硬化してなる硬化物である。
本開示（１０）は、本開示（８）に記載の組成物を硬化してなる硬化物である。 The following items are disclosed in this specification.
The present disclosure (1) is a urethane (meth)acrylate compound represented by the following general formula (1).

(In general formula (1 ⁾ , X is a divalent linking group having 2 to ¹⁰ carbon atoms derived from a hydrocarbon; It is a hydrogen group, and Y ¹ and Y ² are each independently a substituent represented by the general formula (2).)

(In general formula (2), * represents a linkage with O ¹ or O ² , R ³ is a hydrocarbon group having 1 to 15 carbon atoms, and R ⁴ is a hydrogen atom or a methyl group. be.)
The present disclosure (2) is the urethane (meth)acrylate compound according to the present disclosure (1), wherein in the general formula (1), R ¹ and/or R ² have 12 to 16 carbon atoms.
The present disclosure (3) is a urethane (meth)acrylate compound according to the present disclosure (1) or (2), in which the two aryl groups connected to X are each derived from a cardanol hydrogenated product.
The present disclosure (4) is based on the present disclosure (1) to (3), wherein in the general formula (1), R ¹ and/or R ² are meta-positions with respect to the oxygen atom (O ¹ or O ² ). The urethane (meth)acrylate compound described in any of the above.
The present disclosure (5) provides the urethane (meth) according to any one of the present disclosure (1) to (4), wherein in the general formula (1), R ¹ and/or R ² are at the para position with respect to X. ) is an acrylate compound.
The present disclosure (6) provides the urethane (meth) according to any one of the present disclosure (1) to (5), wherein in the general formula (1), O ¹ and/or O ² are ortho to X. ) is an acrylate compound.
The present disclosure (7) is the urethane (meth)acrylate compound according to any one of the present disclosure (1) to (6), wherein in the general formula (1), X has 3 to 7 carbon atoms.
The present disclosure (8) is a composition containing the urethane (meth)acrylate compound according to any one of the present disclosures (1) to (7).
The present disclosure (9) is a cured product obtained by curing the urethane (meth)acrylate compound described in any of the present disclosures (1) to (7).
The present disclosure (10) is a cured product obtained by curing the composition described in the present disclosure (8).

The present invention can provide a urethane (meth)acrylate compound from which a cured product with excellent flexibility can be obtained.

Claims (10)

A urethane (meth)acrylate compound represented by the following general formula (1).

(In general formula (1 ⁾ , X is a divalent linking group having 2 to ¹⁰ carbon atoms derived from a hydrocarbon; It is a hydrogen group, and Y ¹ and Y ² are each independently a substituent represented by the general formula (2).)

(In general formula (2), * represents a linkage with O ¹ or O ² , R ³ is a hydrocarbon group having 1 to 15 carbon atoms, and R ⁴ is a hydrogen atom or a methyl group. be.) The urethane (meth)acrylate compound according to claim 1, wherein in the general formula (1), R ¹ and/or R ² have 12 to 16 carbon atoms. The urethane (meth)acrylate compound according to claim 1 or 2, wherein the two aryl groups connected to X in the general formula (1) are each derived from a cardanol hydrogenated product. The urethane (meth)acrylate compound according to claim 1 or 2, wherein in the general formula (1), R ¹ and/or R ² are at the meta position relative to the oxygen atom (O ¹ or O ² ). The urethane (meth)acrylate compound according to claim 1 or 2, wherein in the general formula (1), R ¹ and/or R ² are at the para position with respect to X. The urethane (meth)acrylate compound according to claim 1 or 2, wherein O ¹ and/or O ² in the general formula (1) are ortho to X. The urethane (meth)acrylate compound according to claim 1 or 2, wherein in the general formula (1), X has 3 to 7 carbon atoms. A composition comprising the urethane (meth)acrylate compound according to claim 1 or 2. A cured product obtained by curing the urethane (meth)acrylate compound according to claim 1 or 2. A cured product obtained by curing the composition according to claim 8.

Images