JP2011052227A - Cured product of active energy ray-curable resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cured product having excellent stain resistance which can be formed from an active energy ray-curable resin composition. <P>SOLUTION: There is provided a method for producing a urethane(meth)acrylate (UA) including reacting tricyclodecanedimethanol (A), represented by formula (I), a polyisocyanate (B) and a (meth)acrylate containing a hydroxy group (C) to obtain a urethane(meth)acrylate (UA), wherein the reaction of the tricyclodecanedimethanol (A) with the polyisocyanate (B) is carried out by adding the tricyclodecanedimethanol (A) into the polyisocyanate (B) at 50-130°C to react and form a urethane isocyanate prepolymer, and then reacting the urethane isocyanate prepolymer with the (meth)acrylate containing a hydroxy group (C) to form the urethane (meth)acrylate (UA). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a cured product excellent in stain resistance obtained by curing an active energy ray-curable resin composition containing a urethane (meth) acrylate obtained by using a specific diol and a photopolymerization initiator. The product is used as a curable resin component in paints, inks, adhesives, and coating agents.

Conventional urethane (meth) acrylate resins are known, for example, as described in JP-A-48-25095, JP-A-49-133491, JP-A-57-83562, and the like. However, a cured product obtained by curing a resin composition containing a urethane (meth) acrylate resin described therein is not satisfactory with respect to stain resistance.
JP-A-4-323275 discloses that an active energy ray-curable resin composition containing urethane acrylate similar to the urethane (meth) acrylate resin used in the present invention is used as a composition for printing ink. However, there is no suggestion that the obtained ink cured product is excellent in stain resistance.

JP-A-48-25095 (Claims, Examples) JP-A-49-133491 (Claims, Examples) JP-A-57-83562 (Claims, Examples) JP-A-4-323275 (Claims, Examples)

  The objective of this invention is providing the manufacturing method of urethane (meth) acrylate (UA) which gives the hardened | cured material excellent in stain resistance, and the manufacturing method of this hardened | cured material.

で示されるトリシクロデカンジメタノール（Ａ）とポリイソシアネート（Ｂ）とヒドロキシ基含有（メタ）アクリレート（Ｃ）とを反応させて、ウレタン（メタ）アクリレート（ＵＡ）を製造する方法であって、該ヒドロキシ基含有（メタ）アクリレート（Ｃ）がβ−ヒドロキシエチル(メタ)アクリレート、β−ヒドロキシプロピル（メタ）アクリレート、ε−カプロラクトン変性β−ヒドロキシエチル(メタ)アクリレート、ペンタエリスリトールトリアクリレート、及びジペンタエリスリトールペンタアクリレートから成る群から選択される少なくとも１種の化合物であり、トリシクロデカンジメタノール（Ａ）及びポリイソシアネート（Ｂ）を、５０℃〜１３０℃の反応温度下、ポリイソシアネート（Ｂ）中にトリシクロデカンメタノール（Ａ）を加えることにより反応させてウレタンイソシアネートプレポリマーを形成させた後、該ウレタンイソシアネートプレポリマーと該ヒドロキシ基含有（メタ）アクリレート（Ｃ）とを反応させることを特徴とするウレタン（メタ）アクリレート（ＵＡ）の製造方法を提供する。
好ましくは、トリシクロデカンジメタノール（Ａ）及びポリイソシアネート（Ｂ）を、反応液中のイソシアネート基濃度が、反応器に仕込んだポリイソシアネート（Ｂ）のイソシアネート基のモル数から反応器に加えたトリシクロデカンジメタノール（Ａ）の水酸基のモル数分だけ減少した時の濃度に達するまで反応させてウレタンイソシアネートプレポリマーを形成させる。
また、本発明の第２は、上記発明１に記載の方法によりウレタン（メタ）アクリレート（ＵＡ）を製造し、このウレタン（メタ）アクリレート（ＵＡ）を含む活性エネルギー線硬化型樹脂組成物を調製し、該活性エネルギー線硬化型樹脂組成物に活性エネルギー線を照射して硬化物を得ることを特徴とする硬化物の製造方法を提供する。また、上記発明２に記載の硬化物の製造方法では、上記活性エネルギー線硬化型樹脂組成物を支持体上に塗布後、活性エネルギー線を照射してもよい。さらに、硬化物は、好ましくはフィルムである。 Therefore, the present inventor has intensively studied to solve the above problems, and as a result, an active energy ray-curable resin composition containing a urethane (meth) acrylate obtained by using a specific diol and a photopolymerization initiator. It discovered that hardened | cured material could have stain resistance and came to this invention.
That is, the first of the present invention is the following formula (I)

A process for producing urethane (meth) acrylate (UA) by reacting tricyclodecane dimethanol (A), polyisocyanate (B) and hydroxy group-containing (meth) acrylate (C) represented by: The hydroxy group-containing (meth) acrylate (C) is β-hydroxyethyl (meth) acrylate, β-hydroxypropyl (meth) acrylate, ε-caprolactone-modified β-hydroxyethyl (meth) acrylate, pentaerythritol triacrylate, and di- At least one compound selected from the group consisting of pentaerythritol pentaacrylate, and tricyclodecane dimethanol (A) and polyisocyanate (B) are reacted with polyisocyanate (B) at a reaction temperature of 50 ° C. to 130 ° C. Tricyclodecane methanol ( ) To form a urethane isocyanate prepolymer, and then the urethane isocyanate prepolymer and the hydroxy group-containing (meth) acrylate (C) are reacted. A method for manufacturing UA) is provided.
Preferably, tricyclodecane dimethanol (A) and polyisocyanate (B) are added to the reactor based on the number of moles of isocyanate groups of the polyisocyanate (B) charged in the reactor. The urethane isocyanate prepolymer is formed by reacting until the concentration reached when the number of moles of the hydroxyl group of tricyclodecane dimethanol (A) is reduced by the number of moles.
The second aspect of the present invention is to produce urethane (meth) acrylate (UA) by the method described in the above-mentioned invention 1, and prepare an active energy ray-curable resin composition containing this urethane (meth) acrylate (UA). And providing a cured product by irradiating the active energy ray-curable resin composition with active energy rays to obtain a cured product. Moreover, in the manufacturing method of the hardened | cured material of the said invention 2, after apply | coating the said active energy ray hardening-type resin composition on a support body, you may irradiate an active energy ray. Furthermore, the cured product is preferably a film.

  A cured product formed from an active energy ray-curable resin composition containing a urethane (meth) acrylate obtained by using a specific diol and a photopolymerization initiator is excellent in stain resistance.

The present invention will be described in detail below.
Tricyclodecane dimethanol, which is a specific diol used in the present invention, has the structure of the following formula (I). Although isomers depending on the position of the methylol group may exist, each isomer may be used alone or in any mixture.

Next, the polyisocyanate that is the component (B) will be described. Examples of the polyisocyanate (B) used in the present invention include known polyisocyanates such as aromatic, aliphatic, cycloaliphatic or alicyclic polyisocyanates or mixtures thereof, addition products, modified products, and polymers. Can be used. Among them, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hydrogenated diphenylmethane diisocyanate (H ₁₂ MDI), polyphenylmethane polyisocyanate (crude MDI), modified diphenylmethane diisocyanate (modified MDI), xylylene diisocyanate (XDI) , Polyisocyanates such as hydrogenated xylylene diisocyanate (H-XDI), hexamethylene diisocyanate (HMDI), trimethylhexamethylene diisocyanate (TMXDI), isophorone diisocyanate (IPDI), norbornene diisocyanate (NDI), or trimers of the above isocyanates Compound or trimethylolpropane of the above isocyanate or burette modification of the above isocyanate Sexual products are listed.

Next, the hydroxy group containing (meth) acrylate which is (C) component is demonstrated.
Hydroxy group-containing (meth) acrylate is a (meth) acrylate having 1 mol of hydroxyl group in the molecular skeleton. Specific examples thereof include β-hydroxyethyl (meth) acrylate, β-hydroxypropyl (meth) acrylate, and ε-caprolactone. Examples thereof include modified β-hydroxyethyl (meth) acrylate (for example, PCL-F series manufactured by Daicel Chemical Industries, Ltd.), pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and the like.

  As a manufacturing method of urethane (meth) acrylate (UA) used in the present invention, the above-mentioned tricyclodecane dimethanol (A), polyisocyanate (B), and hydroxy group-containing (meth) acrylate (C) are reacted. If it is a method, it will not specifically limit, It can manufacture with the manufacturing method of a well-known urethane (meth) acrylate.

For example, a method in which (A), (B), and (C) are mixed together and reacted [Method 1], (A), and (B) are reacted to contain one or more isocyanate groups per molecule Method of reacting (C) with the prepolymer after forming the urethane isocyanate prepolymer [Method 2] or reacting (B) and (C) to contain one or more isocyanate groups per molecule Examples thereof include a method [method 3] of reacting the prepolymer with (A) after the urethane isocyanate prepolymer to be formed is formed. Among these, [Method 2] and [Method 3] are preferable, and [Method 3] is more preferable. This is because when obtained by reaction with [Method 2], resulting urethane (meth) acrylate becomes highly viscous, stirring becomes difficult and there is a high probability of partial gelation rate. In addition, when manufactured by [Method 1], various complex compounds are irregularly generated, and therefore, when the product is used as an active energy ray-curable resin composition, quality control becomes difficult.

  The molar ratio of each component in the reaction will be described in the case of [Method 2]. The equivalent ratio of (A) / (B) is 1/2 to 1/3, preferably 1/2 to 1 / 2.2. If the equivalent ratio of (A) / (B) is less than 1/2, a large amount of unreacted tricyclodecane dimethanol will remain, adversely affecting the stain resistance. The content of cyclodecane dimethanol in the urethane (meth) acrylate is reduced, and stain resistance cannot be obtained.

When (C) is reacted with the urethane isocyanate prepolymer produced by reacting (A) and (B) in the molar ratio as described above, in the isocyanate group / hydroxy group-containing (meth) acrylate in the urethane isocyanate prepolymer. The equivalent ratio of the hydroxyl groups is from 1/1 to 1 / 1.5, preferably from 1/1 to 1 / 1.2. If this equivalent ratio is less than 1/1, a large amount of unreacted hydroxy group-containing (meth) acrylate (C) remains in the product urethane (meth) acrylate (UA), and quality control becomes difficult. If the ratio exceeds 1 / 1.5, many isocyanate groups remain in the product urethane (meth) acrylate (UA), which is not preferable. Even when [Method 3] is applied, the equivalent ratio of each component is basically selected so that the same disadvantages as in [Method 2] do not occur.
In addition, when (A) and (B) are reacted, a polyol such as various glycols other than (A) can be present together, but usually a (meth) acryloyl group-containing compound described later is added. In order to produce an active energy ray-curable resin composition, it is preferable to react (A) alone in producing urethane (meth) acrylate (UA) for quality control.

The reaction is preferably performed in the presence of a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, or phenothiazine. The amount of these polymerization inhibitors is 1 to 10000 ppm, preferably 100 to 1000 ppm, more preferably 400 to 500 ppm with respect to the urethane (meth) acrylate to be produced. If the amount of the polymerization inhibitor is less than 1 ppm relative to the urethane (meth) acrylate, a sufficient polymerization inhibition effect may not be obtained, and if it exceeds 10,000 ppm, the physical properties of the product may be adversely affected.
For the same reason, this reaction is preferably performed in a molecular oxygen-containing gas atmosphere. The oxygen concentration is appropriately selected in consideration of safety.

In this reaction, this reaction is preferably performed using a catalyst in order to obtain a sufficient reaction rate. As the catalyst, dibutyltin dilaurate, tin octylate, tin chloride or the like can be used, and dibutyltin dilaurate is preferable from the viewpoint of reaction rate.
The amount of these catalysts is usually 1 to 3000 ppm, preferably 50 to 1000 ppm, based on urethane (meth) acrylate (UA). When the amount of the catalyst is less than 1 ppm, a sufficient reaction rate may not be obtained, and when it is added in an amount of more than 3000 ppm, the physical properties of the product urethane (meth) acrylate (UA) may be adversely affected.

  In any of [Method 1] to [Method 3], the reaction is preferably performed at a temperature of 130 ° C. or less, and more preferably 50 ° C. to 130 ° C. When the temperature is lower than 50 ° C., a practically sufficient reaction rate may not be obtained. When the temperature is higher than 130 ° C., the double bond part derived from the hydroxy group-containing (meth) acrylate is crosslinked by heat-induced radical polymerization, and the gelled product is formed May occur. The reaction is usually carried out while analyzing by gas chromatography, titration method or the like until the residual isocyanate group in urethane (meth) acrylate (UA) is 0.1% or less.

The active energy ray-curable resin composition that provides the cured product of the present invention contains the urethane (meth) acrylate (UA) as a main curable component, and further, if necessary, the urethane ( A (meth) acrylate monomer or oligomer which is a (meth) acryloyl group-containing compound other than (meth) acrylate (UA) can be added.
The (meth) acryloyl group-containing compound added as necessary has a hydroxyl group such as 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate or caprolactone-modified-2-hydroxyethyl (meth) acrylate. (Meth) acrylate, 2-hydroxypropyl (meth) acrylate, isoamyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isooctyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobonyl (meth) Monofunctional monomers such as acrylate, phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, 1,3-butanediol di (meth) acrylate 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene Glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethylol Propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipenta Polyfunctional monomers such as lithitol hexa (meth) acrylate, ε-caprolactone-modified dipentaerythritol hexa (meth) acrylate, trimethylolpropane 6-mol propylene oxide adduct tri (meth) acrylate, glycerin propoxytri (meth) acrylate, etc. Is mentioned. Representative oligomers include urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate, acrylic group-containing acrylic polymerizable oligomer, and the like.

  In the present invention, the compounding amount of the compound having the (meth) acryloyl group added as necessary is preferably 200 parts by weight or less with respect to 100 parts by weight of the urethane (meth) acrylate (UA). It is particularly preferred that the amount is not more than parts. When the compounding quantity of the compound which has another (meth) acryloyl group exceeds 200 weight part, the outstanding stain resistance by the said urethane (meth) acrylate (UA) in hardened | cured material will be reduced.

  When this active energy ray-curable resin composition is cured by electron beam irradiation, it is not always necessary to use a photopolymerization initiator, but when it is cured by ultraviolet irradiation, it is preferable to add a photopolymerization initiator. . Examples of the photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2- Methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, 2-Methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin phenyl ether, benzyldimethyl ketal, benzophenone , Benzo Benzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3'-dimethyl-4-methoxybenzophenone, thioxanthone, 2-chlorothio Xanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, Examples include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, methylphenylglyoxylate, benzyl, camphorquinone and the like. The blending amount of the photopolymerization initiator is 1 to 10% by weight, preferably 1 to 5% by weight, and more preferably about 3% by weight with respect to the entire active energy ray-curable resin composition. If the amount is less than 1% by weight, the curing rate is slow. Conversely, even if an amount exceeding 10% by weight is used, the curing rate is not improved, and the physical properties of the cured product are impaired.

Moreover, other various additives can be mix | blended with the active energy ray hardening-type resin composition used by this invention. Examples of such additives include fillers, dyes and pigments, leveling agents, ultraviolet absorbers, light stabilizers, antifoaming agents, dispersants, and thixotropic agents. The addition amount of these additives is 0 to 10 parts by weight, preferably 0.05 to 5 parts by weight with respect to the active energy ray-curable resin composition.
The active energy ray-curable resin composition is cured by irradiating an active energy ray such as an ultraviolet ray or an electron beam after applying it to an object.

  A high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a xenon lamp, a metal halide lamp, or the like is used as a light source when performing ultraviolet irradiation. The irradiation time varies depending on the type of the light source, the distance between the light source and the coating surface, and other conditions, but it is several tens of seconds at most, and usually several seconds. After the ultraviolet irradiation, heating can be performed as necessary to complete the curing. In the case of electron beam irradiation, it is preferable to use an electron beam having an energy in the range of 50 to 1,000 KeV and set the irradiation amount to 2 to 5 Mrad. Usually, an irradiation source having a lamp output of about 80 to 300 W / cm is used. The thickness of the covering material is usually about 20 to 200 μm.

(Example)
EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited to these. In the examples and comparative examples,% and parts are based on weight.

<Synthesis Example 1>
550 g (2 mol) of hydrogenated diphenylmethane diisocyanate (B) was charged into a 1 liter flask equipped with a stirrer, a thermometer and a condenser, the internal temperature was raised to 70 ° C., and then 206 g (1 mol) of tricyclodecane dimethanol (A). ), And the reaction was carried out to give a residual isocyanate group of 11.7%, 244 g (2 mol) of hydroxyethyl acrylate (C), 0.15 g of dibutyltin laurate (150 ppm, added to urethane acrylate) and hydroquinone monomethyl ether 0.50 g (500 ppm, added amount with respect to urethane acrylate) was added, and the reaction was carried out until the residual isocyanate group was 0.1% or less to obtain urethane acrylate (UA1).

<Synthesis Example 2>
509 g (2 mol) of isophorone diisocyanate (B) was charged into a 1 liter flask equipped with a stirrer, a thermometer and a condenser, and the internal temperature was adjusted to 70 ° C. Then, 225 g (1 mol) of tricyclodecane dimethanol (A) was added. When the residual isocyanate group was 13.1% by reaction, 266 g (2 mol) of hydroxyethyl acrylate (C), 0.15 g of dibutyltin laurate (150 ppm, added to urethane acrylate) and 0.50 g of hydroquinone monomethyl ether (500 ppm, addition amount with respect to urethane acrylate) was added, and the reaction was carried out until the remaining isocyanate group was 0.1% or less to obtain urethane acrylate (UA2).

<Comparative Synthesis Example 3>
Lactone modified hydroxyethyl acrylate (Placcel FA2D, manufactured by Daicel Chemical Industries) (C) 518 g (2 mol) and hydroquinone monomethyl ether 0.50 g (500 ppm, added to urethane acrylate) in a 1 liter flask equipped with a stirrer, thermometer and condenser Amount) was adjusted to an internal temperature of 70 ° C., 334.3 g (2 moles) of isophorone diisocyanate (B) was added, and the reaction was carried out. When the residual isocyanate group reached 7.42%, tricyclodecane dimethanol (A ) 147.8 g (1 mol) and 0.15 g of dibutyltin laurate (150 ppm, added to urethane acrylate) were added, and the reaction was continued until the residual isocyanate group was 0.1% or less to obtain urethane acrylate (UA3). .

(Synthesis Example 4)
Into a 1 L flask equipped with a stirrer, a thermometer and a condenser, 493 g (2 mol) of isophorone diisocyanate (B) was charged, the internal temperature was adjusted to 70 ° C., and 218 g (1 mol) of tricyclodecane dimethanol (A) was added. When the residual isocyanate group was 13.1% by reaction, 289 g (2 mol) of hydroxyethyl methacrylate (C), 0.15 g (150 ppm, added to urethane acrylate) of dibutyltin laurate and 0.50 g of hydroquinone monomethyl ether (500 ppm, addition amount with respect to urethane acrylate) was added, and the reaction was carried out until the residual isocyanate group was 0.1% or less to obtain urethane acrylate (UA4).

(Comparative Synthesis Example 5)
In a 1 L flask equipped with a stirrer, a thermometer and a condenser, lactone-modified hydroxyethyl methacrylate (Placcel FM2D manufactured by Daicel Chemical Industries) (C) 528 g (2 mol) and hydroquinone monomethyl ether 0.50 g (500 ppm, added to urethane acrylate) ) And the internal temperature was raised to 70 ° C., and then 327.4 g (2 moles) of isophorone diisocyanate (B) was added and reacted, and when the residual isocyanate group reached 7.24%, tricyclodecane dimethanol (A) 144.7 g (1 mol) and 0.15 g of dibutyltin laurate (150 ppm, amount added to urethane acrylate) were added, and the reaction was performed until the residual isocyanate group was 0.1% or less to obtain urethane acrylate (UA5).

<Comparative Synthesis Example 1>
The same procedure as in Synthesis Example 1 was conducted except that 298 g (2 mol) of hydrogenated diphenylmethane diisocyanate, 569 g (1 mol) of polypropylene glycol, and 132 g (2 mol) of 2-hydroxyethyl acrylate were used as main raw materials. Urethane acrylate (UA6) was obtained.
Contamination resistance tests were performed on the urethane acrylates (UA1) to (UA6) obtained in Synthesis Examples 1, 2, and 4 and Comparative Synthesis Examples 1, 3, and 5 in the following manner.

(Evaluation methods)
<Curing cured film>
The cured product film used for the stain resistance test was prepared by the following procedure. An active energy ray-curable resin composition is prepared by blending 100 parts of each of the urethane acrylates (UA1) to (UA6) with 3 parts of Darocure 1173, a photopolymerization initiator manufactured by Ciba Specialty Chemicals, and a support. After the coating was applied so that the thickness after curing was about 10 μm, it was cured under curing conditions of a high-pressure mercury lamp 120 W / cm and a conveyor speed of 5 m / min to obtain a cured product film.
Further, 100 parts of each of the urethane acrylates (UA1) to (UA6) are mixed with 20 parts of tripropylene glycol diacrylate (TPGDA) and 3 parts of Darocure 1173, a photopolymerization initiator manufactured by Ciba Specialty Chemicals. An active energy ray-curable resin composition was prepared and applied on a support so that the thickness after curing was about 10 μm, and then cured under curing conditions of a high-pressure mercury lamp 120 W / cm and a conveyor speed of 5 m / min. A cured product film was obtained.
In order to completely cure UA5, it was post-cured at 120 ° C. for 1 hour.

<Contamination resistance test>
Red, blue and black water-based inks (INK-30R, INK-30L, INK-30B manufactured by each pilot company) are dropped on the cured product film, left to stand at 25 ° C. for 24 hours, and then wiped with absorbent cotton containing water. The state of the remaining trace with respect to the dropped part was visually observed.

[Examples 1, 2, 4, 6, 7, 9 and Comparative Examples 1, 2, 3, 5, 8, 10]
Using the cured film obtained by curing each resin composition containing the urethane acrylates (UA1) to (UA6) obtained in Synthesis Examples 1, 2, 4 and Comparative Synthesis Examples 1, 3, 5 A contamination test was conducted and the results are shown in Tables 1 to 3.

Claims (5)

Formula (I)

A process for producing urethane (meth) acrylate (UA) by reacting tricyclodecane dimethanol (A), polyisocyanate (B) and hydroxy group-containing (meth) acrylate (C) represented by: The hydroxy group-containing (meth) acrylate (C) is β-hydroxyethyl (meth) acrylate, β-hydroxypropyl (meth) acrylate, ε-caprolactone-modified β-hydroxyethyl (meth) acrylate, pentaerythritol triacrylate, and di- At least one compound selected from the group consisting of pentaerythritol pentaacrylate, and tricyclodecane dimethanol (A) and polyisocyanate (B) are reacted with polyisocyanate (B) at a reaction temperature of 50 ° C. to 130 ° C. Tricyclodecane methanol ( ) To form a urethane isocyanate prepolymer, and then the urethane isocyanate prepolymer and the hydroxy group-containing (meth) acrylate (C) are reacted. UA) manufacturing method.   Tricyclodecane dimethanol (A) and polyisocyanate (B) were added to the reactor based on the number of moles of isocyanate groups of the polyisocyanate (B) charged in the reactor. The method for producing a urethane (meth) acrylate (UA) according to claim 1, wherein the urethane isocyanate prepolymer is formed by reacting until reaching the concentration when it is reduced by the number of moles of hydroxyl group of candimethanol (A).   A urethane (meth) acrylate (UA) is produced by the method according to claim 1 or 2, an active energy ray-curable resin composition containing the urethane (meth) acrylate (UA) is prepared, and the active energy ray-curable type is prepared. A method for producing a cured product, wherein a cured product is obtained by irradiating an active energy ray to a resin composition.   The manufacturing method of the hardened | cured material of Claim 3 which irradiates an active energy ray after apply | coating the said active energy ray curable resin composition on a support body.   The method for producing a cured product according to claim 3 or 4, wherein the cured product is a film.