JP2021161136A - Curable resin composition - Google Patents

Abstract

To provide a curable resin composition which is excellent in mechanical strength, weather resistance and dimensional stability after being cured.SOLUTION: A curable resin composition is provided, containing an active energy ray-curable polyurethane resin and a radical reactive diluent. In the curable resin composition, the active energy ray-curable polyurethane resin includes a reaction product of an a resin raw material including isocyanate group-terminated prepolymer and a hydroxy group-containing unsaturated compound, the radical reactive diluent contains a reactive compound having an alicyclic ether skeleton, and a compound containing both a (meth)acryloyl group and a vinyl group. With respect to 100 pts.mass of the total amount of the active energy ray-curable polyurethane resin and the radical reactive diluent, a content ratio of the radical reactive diluent is 50 pts.mass or less. With respect to 100 pts.mass of the total amount of the reactive compound having the alicyclic ether skeleton and the compound containing both the (meth)acryloyl group and the vinyl group, a content ratio of the reactive compound having the alicyclic ether skeleton is 10 pts.mass or more and 90 pts.mass or less.SELECTED DRAWING: None

Description

The present invention relates to a curable resin composition, and more particularly to a curable resin composition containing an active energy ray-curable polyurethane resin.

Polyurethane resin that is cured by irradiation with active energy rays (hereinafter referred to as active energy ray-curable polyurethane resin) is a polyurethane resin containing an ethylenically unsaturated group, and is used in various industrial fields such as adhesives, coating agents, and elastomers. , Widely used.

It is also known that the active energy ray-curable polyurethane resin is used in combination with a radically polymerizable compound, for example, 5.0 parts by mass of an aliphatic urethane acrylate and methyl α-allyloxymethylacrylate (MeAMA). ) A curable composition obtained by mixing 5.0 parts by mass and a cured product obtained by curing the curable composition with ultraviolet rays have been proposed (for example, Patent Document 1 (Example 7)). reference.).

Japanese Unexamined Patent Publication No. 2014-40585

On the other hand, a curable composition containing an active energy ray-curable polyurethane resin is required to further improve mechanical strength and weather resistance after curing.

Further, in recent years, it has been studied to use a curable composition containing an active energy ray-curable polyurethane resin as a molding resin in a 3D printer.

Molding resins for 3D printers are required to have excellent dimensional stability.

The present invention is a curable resin composition having excellent mechanical strength, weather resistance and dimensional stability after curing.

The present invention [1] is a curable resin composition containing an active energy ray-curable polyurethane resin and a radical reactive diluent, wherein the active energy ray-curable polyurethane resin contains an isocyanate group-terminated prepolymer and The radical reactive diluent contains a reaction product of a resin raw material containing a hydroxy group-containing unsaturated compound, and the radical reactive diluent includes a reactive compound having an alicyclic ether skeleton and a compound having a (meth) acryloyl group and a vinyl group. The content ratio of the radical reactive diluent is 50 parts by mass or less with respect to 100 parts by mass of the total amount of the active energy ray-curable polyurethane resin and the radical reactive diluent, and the alicyclic ether skeleton is formed. The content ratio of the (meth) acryloyl group and the vinyl group compounding compound is 10 parts by mass or more and 90 parts by mass or less with respect to the total amount of 100 parts by mass of the reactive compound and the (meth) acryloyl group and the vinyl group coexisting compound. Contains a curable resin composition.

In the present invention [2], a (meth) acryloyl group and a vinyl group are coexisted with respect to a total amount of 100 parts by mass of a reactive compound having an alicyclic ether skeleton and a compound having a (meth) acryloyl group and a vinyl group. The curable resin composition according to the above [1], wherein the content ratio of the compound exceeds 50 parts by mass.

In the present invention [3], the reactive compound having an alicyclic ether skeleton comprises the reactive compound having a six-membered alicyclic ether skeleton containing two or more oxygen atoms, as described above [1] or [3]. 2] contains the curable resin composition according to.

In the curable resin composition of the present invention, the radical reactive diluent contains a reactive compound having an alicyclic ether skeleton and a compound having a (meth) acryloyl group and a vinyl group.

Further, in the curable resin composition of the present invention, the content ratio of the radical reactive diluent is within a predetermined range, and the reactive compound having an alicyclic ether skeleton and the compound having a (meth) acryloyl group and a vinyl group are present. And are included in a predetermined ratio.

Therefore, the curable resin composition is excellent in mechanical strength, weather resistance and dimensional stability after curing.

The curable resin composition of the present invention contains an active energy ray-curable polyurethane resin and a radically reactive diluent.

The active energy ray-curable polyurethane resin is a polyurethane resin that is cured by irradiation with active energy rays (described later).

The active energy ray-curable polyurethane resin contains a reaction product of a resin raw material.

The resin raw material contains an isocyanate group-terminated prepolymer and a hydroxy group-containing unsaturated compound.

The isocyanate group-terminated prepolymer is a polyurethane prepolymer having two or more free isocyanate groups at the molecular ends, and contains a reaction product of a prepolymer raw material.

The prepolymer raw material contains a polyisocyanate component and a polyol component.

The polyisocyanate component contains a polyisocyanate monomer and / or a polyisocyanate derivative.

Examples of the polyisocyanate monomer include polyisocyanates such as aromatic polyisocyanates, aromatic aliphatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates.

Examples of the aromatic polyisocyanate include tolylene diisocyanate (2,4- or 2,6-toluene diisocyanate or a mixture thereof) (TDI), phenylenediisocyanate (m-, p-phenylenediocyanate or a mixture thereof), 4, 4'-Diphenyldiisocyanate, 1,5-naphthalenediocyanate (NDI), diphenylmethane diisocyanate (4,4'-, 2,4'-or 2,2'-diphenylmethane diisocyanate or a mixture thereof) (MDI), Examples thereof include aromatic diisocyanates such as 4,4'-toluene diisocyanate (TODI) and 4,4'-diphenyl ether diisocyanate.

Examples of the aromatic aliphatic polyisocyanate include xylylene diisocyanate (1,3- or 1,4-xylylene diisocyanate or a mixture thereof) (XDI) and tetramethylxylylene diisocyanate (1,3- or 1,4-tetra). Examples thereof include methylxylylene diisocyanate (or a mixture thereof) (TMXDI), aromatic aliphatic diisocyanates such as ω, ω'-diisocyanate-1,4-diethylbenzene and the like.

Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, 1,2-propylene diisocyanate, butylene diisocyanate (tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate), and 1 , 5-Pentamethylene diisocyanate (PDI), 1,6-hexamethylene diisocyanate (also known as hexamethylene diisocyanate) (HDI), 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6- Examples thereof include aliphatic diisocyanates such as diisocyanate methyl caproate.

Examples of the alicyclic polyisocyanate include 1,3-cyclopentanediisocyanate, 1,3-cyclopentenediisocyanate, cyclohexanediisocyanate (1,4-cyclohexanediisocyanate, 1,3-cyclohexanediisocyanate), and 3-isocyanatomethyl-3. , 5,5-trimethylcyclohexylisocyanate (also known as isophorone diisocyanate) (IPDI), hydrogenated xylylene diisocyanate (also known as bis (isocyanatomethyl) cyclohexane) (1,3- or 1,4-hydrogenated xylylene diisocyanate or The mixture) (H ₆ XDI), hydrogenated diphenylmethane diisocyanate (also known as bis (isocyanatocyclohexyl) methane, methylenebis (cyclohexylisocyanate)) (4,4'-, 2,4'-or 2,2'- Methylenebis (cyclohexylisocyanate) These Trans, Trans-form, Trans, Cis-form, Cis, Cis-form, or a mixture thereof) (H ₁₂ MDI), Methylcyclohexanediisocyanate (Methyl-2,4-Cyclohexanediisocyanate, Methyl- 2,6-Cyclohexanediisocyanate), norbornan diisocyanate (various isomers or mixtures thereof) (NBDI), alicyclic diisocyanates and the like can be mentioned.

These polyisocyanate monomers can be used alone or in combination of two or more.

Examples of the polyisocyanate derivative include multimers of the above-mentioned polyisocyanate monomers (for example, dimer and trimerate (for example, isocyanurate modified product and iminooxadiazinedione modified product), pentameric and 7-mer. A body, etc.), an allophanate modified product (for example, an allophanate modified product produced by reacting the polyisocyanate monomer with a known monovalent alcohol and / or a known divalent alcohol), a polyol modified product (for example, the above-mentioned product). A polyol modified product (alcohol adduct) produced by the reaction of a polyisocyanate monomer with a known trivalent or higher valent alcohol, etc.), a biuret modified product (for example, the above polyisocyanate monomer, water or amines) Biuret modified product produced by reaction), urea modified product (for example, urea modified product produced by reaction between the polyisocyanate monomer and diamine), oxadiazine trione modified product (for example, polyisocyanate single amount). Oxaziazine trione produced by the reaction between the body and carbon dioxide gas), carbodiimide modified product (carbodiimide modified product produced by the decarbonate condensation reaction of the above polyisocyanate monomer, etc.), uretdione modified product, uretonimine modified product, etc. Can be mentioned.

These polyisocyanate derivatives can be used alone or in combination of two or more.

The polyisocyanate component preferably contains a polyisocyanate monomer, and more preferably consists of a polyisocyanate monomer.

The polyisocyanate monomer preferably does not contain an aromatic polyisocyanate, more preferably an aromatic aliphatic polyisocyanate, an alicyclic polyisocyanate, and further preferably an alicyclic polyisocyanate. More preferably, isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate can be mentioned, and particularly preferably, hydrogenated xylylene diisocyanate can be mentioned.

The polyol component contains, for example, a high molecular weight polyol.

The high molecular weight polyol is a compound having two or more hydroxy groups and having a number average molecular weight of 300 or more and 20000 or less. For example, a polyether polyol, a polyester polyol, a polycarbonate polyol, a polyurethane polyol, an epoxy polyol, a vegetable oil polyol, a polyolefin polyol, etc. Examples thereof include silicone polyols and fluorine polyols, and preferred examples include polyether polyols, polyester polyols, polycarbonate polyols, and polyurethane polyols.

Examples of the polyether polyol include a polyoxyalkylene (C2-3) polyol and a polytetramethylene ether polyol.

The polyoxyalkylene (C2-3) polyol is, for example, an addition polymerization of an alkylene oxide using a low molecular weight polyol or a low molecular weight polyamine as an initiator.

The low molecular weight polyol is a compound having two or more hydroxy groups and having a number average molecular weight of 40 or more and less than 300, and is, for example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butylene glycol, 1, 3-butylene glycol, 1,2-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,2,2-trimethylpentanediol , 3,3-Dimethylol heptane, alcohol (C7-20) diol, 1,3- or 1,4-cyclohexanedimethanol and mixtures thereof, 1,3- or 1,4-cyclohexanediol and mixtures thereof, Dihydric alcohols such as hydride bisphenol A, 1,4-dihydroxy-2-butene, 2,6-dimethyl-1-octene-3,8-diol, bisphenol A, diethylene glycol, triethylene glycol, dipropylene glycol, for example. , Trihydric alcohols such as glycerin, trimethylolpropane, triisopropanolamine, eg tetrahydric alcohols such as tetramethylolmethane (pentaerythritol), diglycerin, eg pentahydric alcohols such as xylitol, eg sorbitol, mannitol, alitol , Hexyl alcohols such as iditol, darsitol, altritor, inositol, dipentaerythritol, for example, heptahydric alcohols such as propylene glycol, for example, octahydric alcohols such as sucrose.

Examples of low molecular weight polyamines include ethylenediamine, 1,3-propanediamine, 1,3- or 1,4-butanediamine, 1,6-hexamethylenediamine, 1,4-cyclohexanediamine, and 3-aminomethyl-3. , 5,5-trimethylcyclohexylamine (isophoronediamine), 4,4'-dicyclohexylmethanediamine, 2,5 (2,6) -bis (aminomethyl) bicyclo [2.2.1] heptane, 1,3- Low molecular weight diamines such as bis (aminomethyl) cyclohexane, hydrazine, o, m or p-tolylene diamine (TDA, OTD), such as low molecular weight triamines such as diethylenetriamine, such as triethylenetetramine, tetraethylenepentamine, etc. Examples thereof include low molecular weight polyamines having 4 or more amino groups.

These initiators can be used alone or in combination of two or more. Preferred examples of the initiator include low molecular weight polyols.

Examples of the alkylene oxide include alkylene oxides having 2 to 3 carbon atoms, and more specifically, for example, ethylene oxide (IUPAC name: oxylan) and propylene oxide (1,2-propylene oxide (IUPAC name: methyloxylan)). ), Triethylene oxide (1,3-propylene oxide) and the like. In addition, these alkylene oxides can be used alone or in combination of two or more. Of these, ethylene oxide and propylene oxide are preferable, and propylene oxide is more preferable.

Specific examples of such polyoxyalkylene (C2-3) polyols include polyoxyethylene glycol, polyoxypropylene glycol, polyoxytriethylene glycol, and polyoxyethylene / polyoxypropylene glycol (random or block copolymers). ) And other polyalkylene oxides with an average number of functional groups of 2, for example, polyoxyethylene triol, polyoxypropylene triol, polyoxytriethylene triol, polyoxyethylene / polyoxypropylene triol (random or block copolymer) and the like. Examples thereof include polyalkylene oxides having a group number of 3.

These polyoxyalkylene (C2-3) polyols can be used alone or in combination of two or more.

The polyoxyalkylene (C2-3) polyol is produced by a known method using, for example, a hydroxide catalyst, a phosphazene catalyst, a double metal cyanide complex catalyst, or the like. From the viewpoint of suppressing side reactions, the polyoxyalkylene polyol is preferably produced using a catalyst capable of suppressing side reactions such as a phosphazene catalyst and a compound metal cyanide complex catalyst.

In the side reaction in the production of polyoxyalkylene polyol, monool having an unsaturated bond is produced. Therefore, the degree of suppression of side reactions can be evaluated by calculating the degree of unsaturation (unit: meq./g) of the polyoxyalkylene polyol.

The degree of unsaturation (unit: meq./g) of the polyoxyalkylene polyol preferably satisfies the following formula (1).

Degree of unsaturation ≤ 4 × ^10-5 × (Mn / f) ^0.83 +0.011
In the above formula (1), Mn indicates the number average molecular weight of the polyoxyalkylene polyol, and f indicates the average number of functional groups (average number of hydroxyl groups) of the polyoxyalkylene polyol. Mn and f can be measured by a known method, and can also be calculated from, for example, the hydroxyl value measured according to JIS K 1557-1 (2007) (the same applies hereinafter).

More specifically, the degree of unsaturation (unit: meq./g) of the polyoxyalkylene (C2-3) polyol is, for example, 0.001 or more, for example, 0.07 or less, preferably 0. It is 05 or less, more preferably 0.03 or less, still more preferably 0.025 or less.

Examples of the polytetramethylene ether polyol include polytetramethylene ether glycol, and specifically, for example, a crystalline polytetramethylene ether glycol obtained by cationic polymerization of tetrahydrofuran, for example, in a polymerization unit such as tetrahydrofuran. Examples thereof include alkyl-substituted tetrahydrofuran and amorphous (non-crystalline) polytetramethylene ether glycol obtained by copolymerizing the above-mentioned divalent alcohol.

In addition, amorphous (amorphous) means that it is liquid at room temperature (25 ° C.).

The amorphous polytetramethylene ether glycol is, for example, a copolymer of tetrahydrofuran and alkyl-substituted tetrahydrofuran (for example, 3-methyltetrahydrofuran) (tetrahydrofuran / alkyl-substituted tetrahydrofuran (molar ratio) = 15 / 85-85 /). 15, number average molecular weight 500 to 4000, preferably 800 to 3500) or a copolymer of, for example, tetrahydrofuran and branched glycol (eg, neopentyl glycol) (tetrahydrofuran / branched glycol (molar ratio) = It can be obtained as 15 / 85-85 / 15, a number average molecular weight of 500 to 4000, preferably 800 to 3500).

Examples of the polyester polyol include a polycondensate obtained by reacting the above-mentioned low molecular weight polyol with a polybasic acid under known conditions.

Examples of the polybasic acid include oxalic acid, malonic acid, succinic acid, methylsuccinic acid, glutaric acid, adipic acid, 1,1-dimethyl-1,3-dicarboxypropane, and 3-methyl-3-ethylglutaric acid. , Azelaic acid, sebacic acid, other saturated aliphatic dicarboxylic acids (C11-13), such as maleic acid, fumaric acid, itaconic acid, other unsaturated aliphatic dicarboxylic acids, such as orthophthalic acid, isophthalic acid, terephthalic acid. , Toluenedicarboxylic acid, naphthalenedicarboxylic acid, other aromatic dicarboxylic acids, such as hexahydrophthalic acid, other alicyclic dicarboxylic acids, for example, other carboxylic acids such as dimer acid, hydrogenated dimer acid, het acid, etc. And acid anhydrides derived from these carboxylic acids, such as oxalic acid anhydride, succinic acid anhydride, maleic anhydride, phthalic acid anhydride, 2-alkyl anhydride (C12-C18) succinic acid, tetrahydrophthalic acid anhydride, trihydride. Merit acids and acid halides derived from these carboxylic acids and the like, such as oxalic acid dichloride, adipate dichloride, sebacic acid dichloride and the like can be mentioned.

Further, as the polyester polyol, for example, a plant-derived polyester polyol, specifically, the above-mentioned low molecular weight polyol as an initiator, a hydroxyl group-containing vegetable oil fatty acid (for example, lysinoleic acid-containing castor oil fatty acid, 12-hydroxystearic acid). Examples thereof include vegetable oil-based polyester polyols obtained by subjecting a hydroxycarboxylic acid such as (hydrogenated castor oil fatty acid, etc.) containing the above to a condensation reaction under known conditions.

Further, as the polyester polyol, for example, using the above-mentioned low molecular weight polyol (preferably dihydric alcohol) as an initiator, lactones such as ε-caprolactone and γ-valerolactone, for example, L-lactide, D- Examples thereof include polycaprolactone polyols and polyvalerolactone polyols obtained by ring-opening polymerization of lactides such as lactide, and lactone-based polyester polyols obtained by copolymerizing them with the above-mentioned divalent alcohol.

Examples of the polycarbonate polyol include a ring-opening polymer of ethylene carbonate using the above-mentioned low molecular weight polyol (preferably a dihydric alcohol) as an initiator, and for example, 1,4-butanediol and 1,5-pentanediol. Examples thereof include an amorphous polycarbonate polyol obtained by copolymerizing a dihydric alcohol such as 3-methyl-1,5-pentanediol or 1,6-hexanediol with a ring-opening polymer.

Further, the polyurethane polyol is a ratio of the polyester polyol, the polyether polyol and / or the polycarbonate polyol obtained above at a ratio of the equivalent ratio (OH / NCO) of the hydroxy group (OH) to the isocyanate group (NCO) exceeding 1. , Polyisocyanate can be obtained as a polyester polyurethane polyol, a polyether polyurethane polyol, a polycarbonate polyurethane polyol, a polyester polyether polyurethane polyol, or the like.

These high molecular weight polyols can be used alone or in combination of two or more.

The high molecular weight polyol preferably includes a polyether polyol, more preferably a polyoxyalkylene (C2-3) polyol, further preferably a polyoxypropylene polyol, and more preferably a polyoxypolyol. Examples include propylene glycol.

From the viewpoint of mechanical strength and dimensional stability, the number average molecular weight of the high molecular weight polyol is, for example, 1000 or more, preferably 2000 or more, more preferably 3000 or more, still more preferably 5000 or more, still more preferably 6000 or more. More preferably 7,000 or more, further preferably 8,000 or more, still more preferably 9000 or more, particularly preferably 10000 or more, for example, 20000 or less, preferably 15000 or less, still more preferably 12000 or less, further. Preferably, it is 11000 or less.

The average number of functional groups of the high molecular weight polyol is, for example, 1.5 or more, preferably 2 or more, for example, 3 or less, preferably 2.5 or less, and more preferably 2.0.

The hydroxyl value of the high molecular weight polyol is, for example, 9 mgKOH / g or more, preferably 10 mgKOH / g or more, and for example, 210 mgKOH / g or less, preferably 150 mgKOH / g or less, more preferably 100 mgKOH / g or less. ..

Further, the polyol component can contain a low molecular weight polyol as an optional component.

Examples of the low molecular weight polyol include the above-mentioned low molecular weight polyol.

When the polyol component contains a low molecular weight polyol, the content ratio thereof is appropriately set as long as the excellent effects of the present invention are not impaired.

Preferably, the polyol component does not contain low molecular weight polyols, only high molecular weight polyols. More preferably, the polyol component contains only a polyoxyalkylene polyol.

The number average molecular weight of the polyol component (total amount) is, for example, 1000 or more, preferably 2000 or more, more preferably 3000 or more, still more preferably 5000 or more, still more preferably 6000 or more, still more preferably 7000 or more. It is more preferably 8000 or more, still more preferably 9000 or more, particularly preferably 10000 or more, for example, 20000 or less, preferably 15000 or less, still more preferably 12000 or less, still more preferably 11000 or less. The average number of functional groups of the polyol component (total amount) is, for example, 1.5 or more, preferably 2 or more, for example, 3 or less, preferably 2.5 or less, and more preferably 2.0. Is.

The hydroxyl value of the polyol component (total amount) is, for example, 9 mgKOH / g or more, preferably 10 mgKOH / g or more, for example, 210 mgKOH / g or less, preferably 150 mgKOH / g or less, more preferably 100 mgKOH / g. It is less than or equal to g.

The isocyanate group-terminated prepolymer can be obtained by reacting the prepolymer raw material containing the above polyisocyanate component and the above polyol component by a known method.

More specifically, in this method, the prepolymer raw material is blended at a ratio of more than 1 in the equivalent ratio (isocyanate group / hydroxy group) of the isocyanate group of the polyisocyanate component to the hydroxy group of the polyol component. The equivalent ratio (isocyanate group / hydroxy group) in the prepolymer raw material is preferably 1.1 or more, more preferably 3 or more, still more preferably 6 or more, preferably 20, more preferably 15. Hereinafter, it is more preferably 10 or less.

Then, the above-mentioned prepolymer raw material is reacted by a known polymerization method such as bulk polymerization or solution polymerization. Preferably, the above prepolymer raw materials are reacted by bulk polymerization.

In bulk polymerization, for example, the above prepolymer raw materials are blended in a nitrogen atmosphere and reacted at a reaction temperature of 75 to 85 ° C. for about 1 to 20 hours.

In solution polymerization, for example, the above prepolymer raw material is mixed with a known organic solvent under a nitrogen atmosphere and reacted at a reaction temperature of 20 to 80 ° C. for about 1 to 20 hours.

Further, in the above polymerization, a known urethanization catalyst can be added, if necessary. The addition ratio of the urethanization catalyst is appropriately set according to the purpose and application.

Thereby, an isocyanate group-terminated prepolymer can be obtained, and as a result, a composition containing an isocyanate group-terminated prepolymer and an unreacted polyisocyanate component (hereinafter referred to as a crude prepolymer product) can be obtained.

The average number of functional groups of the isocyanate groups of the isocyanate group-terminated prepolymer is, for example, 1.5 or more, preferably 2.0 or more, and for example, 3.0 or less, preferably 2.5 or less.

The isocyanate group concentration of the prepolymer crude product (including the isocyanate group-terminated prepolymer and the unreacted polyisocyanate component) is, for example, 0. 3% by mass or more, preferably 0.5% by mass or more, more preferably 1.0% by mass or more, and for example, 15% by mass or less, preferably 12% by mass or less, more preferably 10% by mass or more. It is less than or equal to mass%.

In addition, the crude prepolymer product (including an isocyanate group-terminated prepolymer and an unreacted polyisocyanate component) is preferably purified by distillation from the viewpoint of improving mechanical strength and dimensional stability.

The distillation method is not particularly limited, and examples thereof include a batch distillation method and a continuous distillation method, and examples of the continuous distillation method include a thin film distillation method (Smith type thin film distillation method). As the distillation method, a thin film distillation method (Smith type thin film distillation method) is preferable.

When the thin film distillation method is adopted, the distillation conditions are such that the distillation temperature is, for example, 120 ° C. or higher, preferably 150 ° C. or higher, and for example, 250 ° C. or lower, preferably 200 ° C. or lower. The distillation pressure (absolute pressure) is, for example, 1 Pa or more, preferably 10 Pa or more, more preferably 50 Pa or more, and for example, 300 Pa or less, preferably 200 Pa or less, more preferably 100 Pa or less.

The feed amount of the isocyanate group-terminated prepolymer is, for example, 0.1 g / min or more, preferably 1.0 g / min or more, more preferably 2.0 g / min or more, and for example, 100 g / min. Hereinafter, it is preferably 50 g / min or less, and more preferably 10 g / min or less.

As a result, the unreacted polyisocyanate component is removed from the crude prepolymer product, and a purified product of the isocyanate group-terminated prepolymer (hereinafter referred to as the purified prepolymer) is obtained.

The prepolymer purified product consists of an isocyanate group-terminated prepolymer or contains an isocyanate group-terminated prepolymer and a trace amount (10000 ppm or less) of an unreacted polyisocyanate component.

In the prepolymer purified product, the content ratio of the isocyanate group-terminated prepolymer is, for example, 99.5% by mass or more, preferably 99.9% by mass or more, based on the total amount of the prepolymer purified product, for example, 100. It is less than or equal to mass%.

The isocyanate group concentration of the prepolymer purified product is, for example, 0.0001% by mass or more, preferably 0.0005% by mass or more, based on the total amount (solid content equivalent) of the prepolymer purified product. For example, it is 0.020% by mass or less, preferably 0.013% by mass or less, and more preferably 0.010% by mass or less.

Then, an active energy ray-curable polyurethane resin is obtained by reacting the above-mentioned isocyanate group-terminated prepolymer (preferably a purified prepolymer) with a hydroxy group-containing unsaturated compound.

A hydroxy group-containing unsaturated compound is a compound having one or more ethylenically unsaturated groups and one or more hydroxy groups.

More specifically, the hydroxy group-containing unsaturated compound includes, for example, one or more ethylenically unsaturated group-containing groups such as a (meth) acryloyl group, a vinylphenyl group, a propenyl ether group, an allyl ether group, and a vinyl ether group. , It also has one or more hydroxy groups.

In addition, (meth) acryloyl means acryloyl and / or methacrylic acid, similarly, (meth) acrylic means acrylic and / or methacrylic, and (meth) acrylate means acrylate and / or methacrylate. show.

The ethylenically unsaturated group-containing group preferably includes a (meth) acryloyl group, and more preferably an acryloyl group.

When the ethylenically unsaturated group-containing group is a (meth) acryloyl group, examples of the hydroxy group-containing unsaturated compound include hydroxy group-containing (meth) acrylate.

As the hydroxy group-containing (meth) acrylate, for example, a monohydroxymono (meth) acrylate having one hydroxy group in one molecule and one (meth) acryloyl group, for example, a hydroxy group in one molecule. Polyhydroxyl mono (meth) acrylate having a plurality of (meth) acryloyl groups, for example, monohydroxyl poly (meth) having one hydroxy group in one molecule and having a plurality of (meth) acryloyl groups. ) Acrylic, for example, polyhydroxyl poly (meth) acrylate having a plurality of hydroxy groups and a plurality of (meth) acryloyl groups in one molecule.

Examples of the monohydroxyl mono (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 2-. Hydroxyalkyl (meth) acrylates such as phenoxypropyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, such as 3-chloro-2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth). ) Acrylate, 2- (meth) acryloyloxyethyl-2-hydroxyethylphthalic acid, 2-hydroxyalkyl (meth) acryloyl phosphate, pentanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, polyethylene glycol mono Examples thereof include (meth) acrylate and polypropylene glycol mono (meth) acrylate.

Examples of the polyhydroxyl mono (meth) acrylate include trimethylolpropane mono (meth) acrylate, glycerin mono (meth) acrylate, and pentaerythritol mono (meth) acrylate.

Examples of the monohydroxyl poly (meth) acrylate include trimethylolpropane di (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and 2-hydroxy-3. -(Meta) acryloyloxypropyl (meth) acrylate (for example, 2-hydroxy-3-acryloyloxypropyl methacrylate (trade name: NK ester 701A, manufactured by Shin-Nakamura Chemical Co., Ltd.)) can be mentioned.

Examples of the polyhydroxyl poly (meth) acrylate include pentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, and dipentaerythritol tetra (meth) acrylate.

When the ethylenically unsaturated group-containing group is a vinylphenyl group, examples of the hydroxy group-containing unsaturated compound include 4-vinylphenol, 2-hydroxyethyl-4-vinylphenyl ether, and (2-hydroxypropyl). Examples thereof include -4-vinylphenyl ether, (2,3-dihydroxypropyl) -4-vinylphenyl ether, 4- (2-hydroxyethyl) styrene and the like.

When the ethylenically unsaturated group-containing group is a propenyl ether group, examples of the hydroxy group-containing unsaturated compound include propenyl alcohol, 2-hydroxyethyl propenyl ether, and 2,3-dihydroxypropyl pro. Nenyl ether and the like can be mentioned.

When the ethylenically unsaturated group-containing group is an allyl ether group, examples of the hydroxy group-containing unsaturated compound include allyl alcohol, 2-hydroxyethyl allyl ether, and 2-hydroxypropyl allyl alcohol. And so on.

When the ethylenically unsaturated group-containing group is a vinyl ether group, examples of the hydroxy group-containing unsaturated compound include 2-hydroxyethyl vinyl ether and 2-hydroxypropyl vinyl ether. ..

These hydroxy group-containing unsaturated compounds can be used alone or in combination of two or more.

The hydroxy group-containing unsaturated compound is preferably a hydroxy group-containing (meth) acrylicate, more preferably a monohydroxyl mono (meth) acrylicate, a monohydroxyl poly (meth) acrylate, and even more preferably a monohydroxyl mono. (Meta) acrylates, more preferably hydroxyalkyl (meth) acrylates, and particularly preferably 2-hydroxyethyl (meth) acrylates.

Then, in the reaction between the isocyanate group-terminated prepolymer (preferably the purified isocyanate group-terminated prepolymer) and the hydroxy group-containing unsaturated compound, for example, in an inert gas atmosphere, the above-mentioned isocyanate group-terminated prepolymer is used. The hydroxy group-containing unsaturated compound is blended so as to have a predetermined equivalent ratio, and a urethanization reaction is carried out.

The equivalent ratio (isocyanate group / hydroxy group) of the isocyanate group in the isocyanate group-terminated prepolymer to the hydroxy group in the hydroxy group-containing unsaturated compound is, for example, 0.7 or more, preferably 0.9 or more. For example, it is 1.5 or less, preferably 1.2 or less.

The reaction conditions are not particularly limited, but the reaction temperature is, for example, 40 ° C. or higher, preferably 50 ° C. or higher, more preferably 60 ° C. or higher, and for example, 120 ° C. or lower, preferably 100 ° C. or lower. , More preferably 80 ° C. or lower. The reaction time is, for example, 0.5 hours or more, preferably 1.0 hours or more, and for example, 24 hours or less, preferably 10 hours or less.

Further, in the above reaction, a known urethanization catalyst may be added, if necessary. The addition ratio of the urethanization catalyst is appropriately set according to the purpose and application.

This gives an active energy ray-curable polyurethane resin containing a reaction product of an isocyanate group-terminated prepolymer and a hydroxy group-containing unsaturated compound.

More specifically, the active energy ray-curable polyurethane resin is obtained by a urethanization reaction of an isocyanate group of an isocyanate group-terminated prepolymer and a hydroxy group of a hydroxy group-containing unsaturated compound, and is a hydroxy group-containing unsaturated compound. It is a polyurethane resin having an unsaturated bond derived from.

The number average molecular weight of the active energy ray-curable polyurethane resin (standard polystyrene-equivalent molecular weight measured by GPC) is, for example, 1000 or more, preferably 2000 or more, and for example, 12000 or less, preferably 11000 or less.

The viscosity of the active energy ray-curable polyurethane resin at 25 ° C. is, for example, 10,000 mPa · s or more, preferably 14,000 mPa · s or more, more preferably 1.6, from the viewpoint of moldability. 10,000 mPa · s or more, more preferably 18,000 mPa · s or more, particularly preferably 20,000 mPa · s or more, and from the viewpoint of handleability and moldability, for example, 100,000 mPa · s or less, It is preferably 80,000 mPa · s or less, more preferably 60,000 mPa · s or less, still more preferably 50,000 mPa · s or less, and particularly preferably 40,000 mPa · s or less.

When the viscosity is in the above range, the handleability at the time of molding can be improved.

The viscosity of the active energy ray-curable polyurethane resin is adjusted by purification of the isocyanate group-terminated prepolymer or the like.

The radical-reactive diluent is a compound that undergoes radical polymerization by irradiation with active energy rays (described later), and is a diluent for diluting the above-mentioned active energy ray-curable polyurethane resin.

The radically reactive diluent contains, as an essential component, a reactive compound having an alicyclic ether skeleton and a compound having a (meth) acryloyl group and a vinyl group.

Examples of the reactive compound having an alicyclic ether skeleton include (meth) acrylate having an alicyclic ether skeleton such as cyclic trimethylolpropane formal (meth) acrylate, for example, 4- (meth) acryloylmorpholine and the like. Can be mentioned. These can be used alone or in combination of two or more.

Examples of the reactive compound having an alicyclic ether skeleton include a reactive compound having a six-membered ring alicyclic ether skeleton containing two or more oxygen atoms, and more preferably two or more oxygens. Examples thereof include (meth) acrylates having an alicyclic ether skeleton of a six-membered ring containing an atom. Among the above-mentioned reactive compounds having an alicyclic ether skeleton, cyclic trimethylolpropane formal (meth) acrylate is a reactive compound having a six-membered ring alicyclic ether skeleton containing two or more oxygen atoms. Can be mentioned.

Examples of the compound having a (meth) acryloyl group and a vinyl group include methyl 2- (allyloxymethyl) acrylate, 2-vinyloxyethyl (meth) acrylate, 3-vinyloxypropyl (meth) acrylate, and (meth). 1-Methyl-2-vinyloxyethyl acrylate, 2-vinyloxypropyl (meth) acrylate, 4-vinyloxybutyl (meth) acrylate, 4-vinyloxycyclohexyl (meth) acrylate, 5-vinyloxy (meth) acrylate Pentyl, 6-vinyloxyhexyl (meth) acrylate, 4-vinyloxymethylcyclohexylmethyl (meth) acrylate, p-vinyloxymethylphenylmethyl (meth) acrylate, 2- (vinyloxyethoxy) (meth) acrylate ) Ethyl, 2- (vinyloxyethoxyethoxyethoxy) ethyl (meth) acrylate and the like. These can be used alone or in combination of two or more.

As the compound having a (meth) acryloyl group and a vinyl group, methyl 2- (allyloxymethyl) acrylate is preferable.

The ratio of the reactive compound having an alicyclic ether skeleton to the compound having a (meth) acryloyl group and a vinyl group is such that the reactive compound having an alicyclic ether skeleton and a compound having a (meth) acryloyl group and a vinyl group are present. The content ratio of the reactive compound having an alicyclic ether skeleton to 100 parts by mass of the total amount of the compound is 10 parts by mass or more, preferably 15 parts by mass or more, more preferably from the viewpoint of mechanical strength and weather resistance. Is 20 parts by mass or more, 90 parts by mass or less, preferably 70 parts by mass or less, more preferably 50 parts by mass or less, still more preferably less than 50 parts by mass, and particularly preferably 30 parts by mass or less. Further, from the viewpoint of mechanical strength and weather resistance, the (meth) acryloyl group and vinyl group compound compound is 10 parts by mass or more, preferably 30 parts by mass or more, more preferably 50 parts by mass or more, still more preferably. , 50 parts by mass or more, particularly preferably 70 parts by mass or more, 90 parts by mass or less, preferably 85 parts by mass or less, and more preferably 80 parts by mass or less.

The radical-reactive diluent is a radical-reactive diluent excluding other radical-reactive diluents (reactive compounds having an alicyclic ether skeleton and compounds having a (meth) acryloyl group and a vinyl group, as optional components. Diluent) can be contained.

Examples of other radical reactive diluents include a reactive compound having an aromatic hydrocarbon skeleton, a reactive compound having an alicyclic hydrocarbon skeleton, a reactive compound having a chain ether skeleton, and a reaction having an amide skeleton. Examples thereof include a sex compound, a reactive compound having an oxyalkylene skeleton, a poly (meth) acrylate, and an unsaturated carboxylic acid allyl ester.

Examples of the reactive compound having an aromatic hydrocarbon skeleton include (meth) acrylates having an aromatic hydrocarbon skeleton such as 3-phenoxybenzyl (meth) acrylate, such as styrene, vinyltoluene, divinylbenzene, and α-methyl. Examples include styrene.

Examples of the reactive compound having an alicyclic hydrocarbon skeleton include isobornyl (meth) acrylate, 3,3,5-trimethylcyclohexyl (meth) acrylate, 4-tert-butylcyclohexyl (meth) acrylate, and dicyclopentanyl. Examples thereof include (meth) acrylate having an alicyclic hydrocarbon skeleton such as (meth) acrylate.

Examples of the reactive compound having a chain ether skeleton include 2-ethylhexyl-diglucol (meth) acrylate.

Examples of the reactive compound having an amide skeleton include N, N-diethyl (meth) acrylamide and the like.

Examples of the reactive compound having an oxyalkylene skeleton include 2-ethylhexyl-diglycol (meth) acrylate.

Examples of the polyol poly (meth) acrylate include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, pentanediol di (meth) acrylate, and neopentyl glycol di (meth). Polyol di (meth) acrylates such as acrylates, hexanediol di (meth) acrylates, nonanediol di (meth) acrylates, oligoethylene glycol di (meth) acrylates, such as trimethylolpropanthry (meth) acrylates, glycerintri (meth). ) Polypolymer tri (meth) acrylate such as acrylate, for example, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like can be mentioned.

Examples of the unsaturated carboxylic acid allyl ester include allyl (meth) acrylate, diallyl maleate, diallyl fumarate, and diallyl itaconate.

Other radical reactive diluents can be used alone or in combination of two or more.

The ratio of the other radical-reactive diluent is not particularly limited, and is appropriately set according to the purpose and application as long as the excellent effect of the present invention is not impaired.

The radical-reactive diluent is preferably another radical-reactive diluent (a radical-reactive diluent excluding a reactive compound having an alicyclic ether skeleton and a compound having a (meth) acryloyl group and a vinyl group). It is composed of a reactive compound having an alicyclic ether skeleton and a compound having a (meth) acryloyl group and a vinyl group.

In the curable resin composition, the blending ratio of the active energy ray-curable polyurethane resin and the radical reactive diluent is such that the active energy ray-curable polyurethane resin has mechanical strength and weather resistance with respect to 100 parts by mass of the total amount thereof. 50 parts by mass or more, preferably 55 parts by mass or more, more preferably 60 parts by mass or more, for example, from the viewpoint of improving the above, suppressing the shrinkage of the cured product, and improving the dimensional stability. , 90 parts by mass or less, preferably 80 parts by mass or less, more preferably 70 parts by mass or less. Further, the radical reactive diluent is, for example, 10 parts by mass or more, preferably 20 parts by mass or more, more preferably 30 parts by mass or more, to improve mechanical strength and weather resistance, and further, a cured product. From the viewpoint of suppressing shrinkage and improving dimensional stability, the amount is 50 parts by mass or less, preferably 45 parts by mass or less, and more preferably 40 parts by mass or less.

The method of blending the active energy ray-curable polyurethane resin and the radical reactive diluent is not particularly limited, and a known method is adopted. As a result, a curable resin composition is obtained.

In addition, the curable resin composition may contain a photopolymerization initiator, if necessary.

Examples of the photopolymerization initiator include known photopolymerization initiators, for example, diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2-. Benzyl-2- (dimethylamino) -4'-morpholinobtyrophenone, 1,2-octanedione 1- [4- (phenylthio) phenyl] -2- (o-benzoyloxime), etanone-1- [9-ethyl -6- (2-methylbenzoyl) -9H-carbazole-3-yl] -1- (O-acetyloxime), 1-hydroxyticlohexyl-phenylketone, 2-hydroxy-2-methyl-1-phenylpropanone And so on.

In addition, the photopolymerization initiator is available as a commercially available product. Examples of such commercially available products include TPO (trade name, manufactured by Tokyo Kasei Kogyo), Irgacure819 (BAPO, trade name, manufactured by BASF), Irgacure369 (Omnirad369, trade name, manufactured by BASF), and IrgacureOXE01 (trade name, manufactured by BASF). ), IrgacureOXE02 (trade name, manufactured by BASF), IrgacureOXE03 (trade name, manufactured by BASF), IrgacureOXE04 (trade name, manufactured by BASF), Irgacure184 (trade name, manufactured by BASF), Omnirad 184, trade name, manufactured by BASF (BASF), NCI-831 (trade name, manufactured by ADEKA), NCI-930 (trade name, manufactured by ADEKA) and the like. These can be used alone or in combination of two or more.

The amount of the photopolymerization initiator added is not particularly limited, and is appropriately set according to the purpose and application.

Further, the curable resin composition may contain a known sensitizer or the like, if necessary, in order to promote the photopolymerization reaction by the photopolymerization initiator.

Examples of the sensitizer include 9,10-bis (octanoyloxy) anthracene, 9,10-dibutoxyanthracene, and 1,4-diethoxynaphthalene. These can be used alone or in combination of two or more.

The sensitizer is also available as a commercial product. Examples of such commercially available products include Antracure UVS-581 (trade name, manufactured by Kawasaki Kasei Chemicals), Antracure UVS-1331 (trade name, manufactured by Kawasaki Kasei Chemicals), and Antracure UVS-2171 (trade name, manufactured by Kawasaki Kasei Chemicals). (Made by Kasei Chemicals), etc.

In addition, the curable resin composition, if necessary, is an antioxidant, an ultraviolet absorber, an optical brightener, and further, for example, a plastic agent, a blocking inhibitor, a heat stabilizer, an active energy ray stabilizer. Known additives such as (light-resistant stabilizers, etc.), mold release agents, catalysts, pigments, dyes, lubricants, fillers, and antioxidants can be contained in appropriate proportions. The amount of these additives added and the timing of addition are appropriately set according to the purpose and application.

Examples of the antioxidant include hindered phenol compounds (specifically, Irganox 1135, Irganox 245, Irganox 1076, Irganox 1726, Irganox 1520L, all manufactured by BASF, specifically ADEKA. ADEKA STAB AO-80 manufactured by BASF Corporation, organic phosphorus compounds (specifically, JP-302, JP-308, JP-308E, JP-310, JP-312L, JP-333E, JP-318O, JPS-312, JPP-13R, JP-318E, all manufactured by Johoku Chemical Co., Ltd., specifically IRGAFOS 38, IRGAFOS P-EPQ, all manufactured by BASF, specifically, ADEKA STAB PEP-4C, ADEKA STAB PEP-8, ADEKA STAB. 1500, ADEKA STAB 3010, all manufactured by ADEKA), thioether compounds (specifically, IRGANOX PS800FL, IRGANOX PS802FL, all manufactured by BASF, specifically, ADEKA STAB AO-412S, ADEKA STAB AO-503, all. ADEKA Corporation, specifically, Yoshitomi DLTP, Yoshitomi DSTP, Yoshitomi DMTP, all manufactured by API Corporation), hydroxylamine compounds (specifically, IRGASTAB FS 042 manufactured by BASF) and the like. These can be used alone or in combination of two or more. The amount and timing of addition of the antioxidant are appropriately set according to the purpose and application.

Examples of the ultraviolet absorber include 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2,2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl, and 2- (2'-). Hydroxy-5'-methyl-phenyl) benzotriazole, 2- (2'-hydroxy-3', 5'-di-t-butyl-phenyl) benzotriazole, 2- (2'-hydroxy-3'-t- Butyl-5'-methyl-phenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5'-di-t-butyl-phenyl) -5-chlorobenzotriazole, 2-( 2'-Hydroxy-4'-n-octoxy-phenyl) benzotriazole-based ultraviolet absorbers such as benzotriazole, for example, 2,4-dihydroxy-benzophenone, 2-hydroxy-4-methoxy-benzophenone, 2,2'- Dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sulfobenzophenone, 2-hydroxy-4- Methoxy-2'-carboxy benzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone trihydrate, 2-hydroxy-4-n-octoxy benzophenone, 2-hydroxy-4-octadesiloxy benzophenone, 2 -Hydroxy-4-n-dodecyloxy-benzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2,2', 4,4'-tetrahydroxy-benzophenone, 2-hydroxy-4-dodecyloxy-benzophenone, 2-hydroxy- Benzophenone-based UV absorbers such as 4- (2-hydroxy-3-methacryloxy) propoxybenzophenone, such as 2'-ethylhexyl-2-cyano-3,3-diphenylacrylate, ethyl-2-cyano-3- (3'). , 4'-Methylenedioxyphenyl) -acrylate and other cyanoacrylate-based ultraviolet absorbers and the like. As commercially available products, for example, Tinuvin328, TinuvinPS (manufactured by Ciba Geigy), SEESORB709 (manufactured by Shiraishi Calcium), Uvinul 490 (manufactured by GAF), Permyl B-100 (manufactured by Ferro), Uvinul3035, Uvinul3039, Uvinul30 (Made by BASF) and the like. These can be used alone or in combination of two or more. The amount and timing of addition of the ultraviolet absorber are appropriately set according to the purpose and application.

Examples of the fluorescent whitening agent include 7- (dimethylamino) -4-methylcoumarin, 2,5-bis (5-tert-butyl-2-benzoxazolyl) thiophene, and 4,4'-bis (2). − Benzoxazolyl) Stilbene and the like. Moreover, as a commercial product, for example, "TINOPAL OB" (manufactured by BASF) and the like can be mentioned. These can be used alone or in combination of two or more. The amount of the fluorescent whitening agent added and the timing of the addition are appropriately set according to the purpose and application.

In such a curable resin composition, the radical reactive diluent contains a reactive compound having an alicyclic ether skeleton and a compound having a (meth) acryloyl group and a vinyl group.

Further, in the above-mentioned curable resin composition, a reactive compound having a radical reactive diluent in a predetermined range and having an alicyclic ether skeleton, and a compound having a (meth) acryloyl group and a vinyl group are used. Is included in a predetermined ratio.

Therefore, the curable resin composition is excellent in mechanical strength, weather resistance and dimensional stability after curing.

Therefore, the above-mentioned curable resin composition is suitably used in various industrial fields as, for example, an adhesive, a coating agent, an elastomer, a molding material, and the like. In particular, the curable resin composition is preferably used as a molding material, more specifically, as a molding material in a 3D printer.

In order to obtain a molded product (cured product) of the curable resin composition, for example, the curable resin composition is molded into a desired shape and then irradiated with active energy rays to cure the curable resin composition.

Examples of the active energy ray include ultraviolet rays and electron beams. The irradiation amount (integrated light amount) of the active energy ray is, for example, 10 × 10 ^-3 J / cm ² or more, preferably 15 × 10 ^-3 J / cm ² or more, and for example, 6 J / cm ² or less, preferably. Is 4 J / cm ² or less.

The curing by the active energy ray may be a batch curing or a divided curing. That is, the curable resin composition may be cured by irradiating with one active energy ray, or the curable resin composition may be cured by irradiating with two or more active energy rays.

As a result, a molded product (cured product) made of a curable resin composition can be obtained.

In addition, after irradiation with active energy rays, it can be cured if necessary.

The curing conditions are not particularly limited, but the temperature conditions are, for example, 10 to 150 ° C., preferably 10 to 100 ° C. The humidity condition is, for example, 20 to 80%, preferably 30 to 70%. The curing time is, for example, 0.5 to 10 days, preferably 1 to 7 days.

As a result, a molded product (cured product) made of a curable resin composition can be obtained.

The obtained molded product (cured product) is excellent in mechanical strength, weather resistance and dimensional stability.

Next, the present invention will be described with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. In addition, "part" and "%" are based on mass unless otherwise specified. In addition, specific numerical values such as a compounding ratio (content ratio), a physical property value, and a parameter used in the following description are described in the above-mentioned "mode for carrying out the invention", and the corresponding compounding. Percentage (content ratio), physical property value, parameter, etc. Upper limit value (value defined as "less than" or "less than") or lower limit value (value defined as "greater than or equal to" or "excess") ) Can be substituted.

Examples 1-9 and Comparative Examples 1-17
(1) Synthesis of isocyanate group-terminated prepolymer An isocyanate group-terminated prepolymer was synthesized according to the formulations shown in Tables 1 to 5.

More specifically, according to the formulations shown in Tables 1 to 5, the polyol component was put into a glass separable flask under a nitrogen atmosphere, and then the polyisocyanate component was added to Tables 1 to 5. The mixture was charged at an equivalent ratio (NCO / OH), and then the temperature was raised to 80 ° C. Then, stannoct (tin (II ethylcaproate)) as a urethanization catalyst was added to the mixture at a ratio of 10 ppm and reacted for 4 hours, whereby the isocyanate group-terminated prepolymer and unreacted poly were added. A crude product containing an isocyanate component was obtained.

(2) Purification of isocyanate group-terminated prepolymer A crude product containing an isocyanate group-terminated prepolymer is set in a Smith-type thin film distillation apparatus, and the isocyanate group-terminated prepolymer and an unreacted polyisocyanate component are mixed under the following conditions. It was separated and the isocyanate group-terminated prepolymer was purified.

Temperature conditions: 160-170 ° C
Pressure condition: 70-100Pa
Supply flow rate: 3.5-4 g / min
(3) Synthesis of active energy ray-curable polyurethane resin Purified isocyanate group-terminated prepolymer (prepolymer purified product) is placed in a separable flask in the air (under dry air) according to the formulations shown in Tables 1 to 5. Then, the hydroxy group-containing unsaturated compound was added at a ratio such that the equivalent ratio (NCO / OH) of the isocyanate group of the isocyanate group-terminated prepolymer to the hydroxy group of the hydroxy group-containing unsaturated compound was 1.0. The temperature was raised to 70 ° C.

Then, stanoct (tin (II ethylhexanoate) as a urethanization catalyst was added to the isocyanate group-terminated prepolymer at a ratio of 200 ppm, and the reaction was carried out for 4 hours until the isocyanate group concentration became 0.01% or less. I let you.

As a result, an active energy ray-curable polyurethane resin was obtained.

(4) Preparation of Curable Resin Composition According to the formulations shown in Tables 1 to 5, a total of 100 g of the active energy ray-curable polyurethane resin, the radical reactive diluent, the photopolymerization initiator, and the additive were added. It was put into a brown bottle so as to be, and stirred at 60 ° C.

As a result, a curable resin composition was obtained.

Further, the viscosity of the obtained curable resin composition at 25 ° C. was measured with an E-type viscometer (TV25 type viscometer manufactured by Toki Sangyo Co., Ltd., rotor angle: 1 ° 34', rotor radius 2.4 cm). bottom.

(5) Curing of Curable Resin Composition The curable resin composition was cured by the methods shown in Tables 1 to 5 to obtain a molded product (cured product). The curing conditions in each method are shown below.

(A) UV
26 g of the curable resin composition was poured into a polypropylene mold (100 × 100 × 20 mm). Then, in a nitrogen atmosphere, one surface of the curable resin composition was irradiated with UV for 3 minutes by a UV irradiator (UV light ultraviolet irradiator 36W manufactured by Pajico). Then, the cured product of the curable resin composition was taken out from the mold, and the other surface was further irradiated with UV for 3 minutes.

(B) 26 g of the curable resin composition was poured into a high-pressure mercury lamp / polypropylene mold (100 × 100 × 20 mm). Then, with a high-pressure mercury lamp (high-pressure mercury lamp manufactured by Heleus (custom product)), only one surface of the curable resin composition was irradiated with active energy rays.

The illuminance was set to 630 mW / cm ² (measured with an illuminance meter (UVICURE Plus II (UVA 320 to 390 nm) manufactured by EIT), and the irradiation time was adjusted so that the ^{integrated light intensity was 4 J / cm 2.}

(C) 3D Printer Using a commercially available 3D printer (Phrosen shuffle 4K manufactured by Phrozen), the curable resin composition is cured by irradiation with active energy rays (first curing (precure)), and a layer having a film thickness of 100 μm. Was laminated to obtain a plate having a size of 100 × 50 × 20 mm. The output of the active energy ray is 0.6 mW / cm ² (measured with a luminometer (measured with a 3664 optical power meter manufactured by Hioki Electric Co., Ltd. (measurement wavelength 405 nm)), and the irradiation time is 90 for the first 10 layers. Seconds, 40 seconds for subsequent layers.

Then, the obtained plate was further cured.

In the second curing (post-cure), a high-pressure mercury lamp (high-pressure mercury lamp manufactured by Heleus (custom product)) was used to irradiate only one surface of the above plate with active energy rays.

The illuminance was set to 630 mW / cm ² (measured with an illuminance meter (UVICURE Plus II (UVA 320 to 390 nm) manufactured by EIT), and the irradiation time was adjusted so that the ^{integrated light intensity was 4 J / cm 2.}

<Evaluation>
(1) Mechanical properties The tensile strength (MPa) and elongation at break (%) of the molded product were measured according to the description of JIS K-6251 (2010).

Further, the tear strength (N / mm) of the molded product was measured according to the description of JIS K-6252 (2007).

(2) Light resistance The molded product was subjected to a light resistance test under the following conditions, and the b value difference (Δb value) before and after the test was measured with a color difference meter (Color Ace MODEL TC-1 manufactured by Tokyo Denshoku Co., Ltd.).

Testing machine: Atlas Ci4000
Irradiance: 44 W / m ²
Wavelength range: 300-400 nm
Black panel temperature: 57 ° C
Rainfall conditions: None Test humidity: No control Filter (inside / outside): Delight filter Test time: 40h
(3) Appearance of cured product (dimensional stability)
The appearance of the cured product (molded product) was visually observed to evaluate the dimensional stability. Those in which shrinkage was confirmed were indicated as "with shrinkage" in the table.

The details of the abbreviations in the table are shown below.

1, 3-H6XDI: 1,3 hydrogenated xylylene diisocyanate, made by Mitsui Chemicals, IPDI: isophorone diisocyanate, trade name VESTANAT IPDI, Evonik Ltd. H12MDI: 4,4'-methylenebis (cyclohexyl isocyanate), trade name VESTANAT H ₁₂ MDI , Evonik D3000: Polyoxypropylene polyol, average number of functional groups 2, number average molecular weight 3000, degree of unsaturation 0.05 meq. / G, Mitsui Chemicals SKC Polyurethane DL10000: Polyoxypropylene polyol, average number of functional groups 2, number average molecular weight 10000, degree of unsaturation 0.01meq. / G, Mitsui Kagaku SKC Polyurethane HEA: Hydroxyethyl acrylate POB-A: Radical reactive diluent, 3-phenoxybenzyl acrylate (also known as m-phenoxybenzyl alcohol), reactive compound with aromatic hydrocarbon skeleton, Kyoeisha Kagaku 4HBA: 4-Hydroxybutyl acrylate EHDG-AT: Radical reactive diluent, 2-ethylhexyl-diglucol acrylate, Reactive compound with chain ether skeleton, Kyoeisha Chemicals ACMO-LI: Radical reactive diluent, 4 -Acryloylmorpholine, reactive compound with alicyclic ether skeleton, Viscoat 200 manufactured by KJ Chemicals: radical reactive diluent, cyclic trimethylolpropanformal acrylate (also known as 5-ethyl-1,3-dioxane-5-yl) ) Methylacryllate), reactive compound having an alicyclic ether skeleton, Biscort 196 manufactured by Osaka Organic Chemical Industry Co., Ltd .: radical reactive diluent, 3,3,5-trimethylcyclohexyl acrylate, reaction having an alicyclic hydrocarbon skeleton Sex compound, AOMA manufactured by Osaka Organic Chemical Industry, radical reactive diluent, methyl 2- (allyloxymethyl) acrylate, compound containing (meth) acryloyl group and vinyl group, FA-513AS manufactured by Nippon Catalyst, FA-513AS: radical reactive diluent Agent, dicyclopentanyl acrylate, reactive compound having an alicyclic hydrocarbon skeleton, Hitachi Kasei TBCHA: radical reactive diluent, 4-tert-butylcyclohexyl acrylate, reactive compound having an alicyclic hydrocarbon skeleton , KJ Chemicals DEAA: Radical Reactive Diluting Agent, N, N-diethylacrylamide, Reactive Compound with Amid Skeleton, KJ Chemicals TMPTA: Radical Reactive Diluting Agent, Trimethylol Propanetriacrylate, Poly (meth) Acrylate, TPO manufactured by Osaka Organic Chemical Industry Co., Ltd .: Photopolymerization initiator, diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, manufactured by Tokyo Kasei Kogyo Co., Ltd.

Claims (3)

A curable resin composition containing an active energy ray-curable polyurethane resin and a radically reactive diluent.
The active energy ray-curable polyurethane resin contains a reaction product of a resin raw material containing an isocyanate group-terminated prepolymer and a hydroxy group-containing unsaturated compound.
The radical reactive diluent is
Reactive compounds with an alicyclic ether skeleton and
Contains (meth) acryloyl group and vinyl group compound compound,
The content ratio of the radical reactive diluent is 50 parts by mass or less with respect to 100 parts by mass of the total amount of the active energy ray-curable polyurethane resin and the radical reactive diluent.
The content ratio of the (meth) acryloyl group and the vinyl group compound is 10% by mass with respect to 100 parts by mass of the total amount of the reactive compound having an alicyclic ether skeleton and the (meth) acryloyl group and the vinyl group compound. A curable resin composition, characterized in that it is 90 parts by mass or more. The content ratio of the (meth) acryloyl group and the vinyl group compound is 50 with respect to 100 parts by mass of the total amount of the reactive compound having an alicyclic ether skeleton and the (meth) acryloyl group and the vinyl group compound. The curable resin composition according to claim 1, wherein the amount exceeds parts by mass. Reactive compounds with an alicyclic ether skeleton
The curable resin composition according to claim 1 or 2, which comprises a reactive compound having a six-membered alicyclic ether skeleton containing two or more oxygen atoms.