JP5824884B2 - Method for producing urethane (meth) acrylate - Google Patents

Description

  The present invention relates to a method for producing urethane (meth) acrylate. Moreover, it is related with the manufacturing method of urethane (meth) acrylate with little coloring.

  Since acrylate or methacrylate (hereinafter referred to as “(meth) acrylate”) is cured by irradiation with active energy rays such as ultraviolet rays and electron beams in the presence of a photopolymerization initiator, it is a component of an active energy ray-curable composition. It is used as. The active energy ray-curable composition is cured in a short time by irradiating active energy rays such as ultraviolet rays and electron beams, and has excellent properties such as toughness, flexibility, scratch resistance, weather resistance, chemical resistance, etc. A cured product having can be formed. For this reason, it is used for many industrial applications such as woodworking, PVC flooring, plastic molding, plastic film, optical fiber coating, and optical disk coating.

  As such an active energy ray-curable composition, a composition composed of an acrylic oligomer, a monomer, and a photopolymerization initiator is known. Examples of the acrylic oligomer include urethane (meth) acrylate, epoxy (meth) acrylate, and polyester (meth) acrylate. Among them, urethane (meth) acrylate is widely used as a component of an active energy ray-curable composition because its cured product is excellent in hardness, flexibility, water resistance and substrate adhesion.

  Urethane (meth) acrylate is produced by, for example, urethanizing a polyol compound, a polyisocyanate compound and a hydroxyl group-containing (meth) acrylate in the presence of an organic tin compound such as dibutyltin dilaurate (hereinafter referred to as “DBTDL”). (For example, see Patent Documents 1 and 2).

  However, the organotin compound has been pointed out to be toxic and has a problem of harmfulness to the human body. Also, in the production of urethane (meth) acrylate, the viscosity of the resulting urethane (meth) acrylate is difficult to wash with water, and even if it can be washed with water, liquid-liquid separation is difficult. It remains without being separated or removed. Therefore, a method for producing urethane (meth) acrylate without using an organotin compound is required.

  As a method for producing urethane (meth) acrylate without using an organic tin compound, a method using an amine compound can be mentioned. However, amine compounds generally have a lower reaction activity than organotin compounds. For this reason, in order to increase productivity, the amount of catalyst must be increased. As a result, the obtained urethane (meth) acrylate has a problem that it is colored or the physical properties of the cured product are lowered.

JP-A-63-220240 JP-A-5-306323

  An object of this invention is to provide the method of manufacturing urethane (meth) acrylate, without using an organotin compound. Furthermore, it aims at providing the method of manufacturing urethane (meth) acrylate with little coloring.

  The above-mentioned problems are solved by the following present invention [1] and [2].

  [1] A catalyst represented by formula (1) as a catalyst for urethanization reaction in a method for producing urethane (meth) acrylate using at least a polyisocyanate compound (a) and a hydroxyl group-containing (meth) acrylate (b) as raw materials Method for producing urethane (meth) acrylate using

M (L) n (1)
In the formula (1), M is a central metal and represents Fe, Mn, Cu, Zr, Ti, Ni or Bi, L is a ligand, β-diketone, halogen atom, alkyl group, acyloxy Represents a group, an acyl group or an alkoxy group. n is an integer value determined by the valence of the central metal and the coordination number of the ligand.

  [2] A ligand of the catalyst represented by the formula (1) in the urethane (meth) acrylate-containing material by adding a coordination compound to the urethane (meth) acrylate-containing material obtained by the above method A process for producing a modified urethane (meth) acrylate, wherein L is exchanged with a ligand derived from the coordination compound.

  According to the present invention, urethane (meth) acrylate can be produced without using an organotin compound. Moreover, urethane (meth) acrylate with little coloring can be manufactured.

  Hereinafter, the present invention will be described in detail.

<Catalyst Represented by Formula (1)>
The catalyst represented by the formula (1) is a compound used as a urethanization reaction catalyst. In the formula (1), M is a central metal and represents Fe, Mn, Cu, Zr, Ti, Ni or Bi, L is a ligand, β-diketone, halogen atom, alkyl group, acyloxy Represents a group, an acyl group or an alkoxy group. n is an integer value determined by the valence of the central metal and the coordination number of the ligand. From the viewpoint of reaction activity, M is preferably Fe or Ti, more preferably Fe. From the viewpoint of yellowness, M is preferably Zr.

  Examples of the β-diketone include the following. Acetylacetone, 2,4-hexanedione, 3,5-heptanedione, 2-methylhexane-3,5-dione, 6-methylheptane-2,4-dione, 2,6-dimethylheptane-3,5-dione 4,6-nonanedione, 2,8-dimethylnonane-4,6-dione, 2,2,6,6-tetramethylheptane-3,5-dione, tridecane-6,8-dione, methyl acetoacetate, Ethyl acetoacetate, isopropyl acetoacetate, tert-butyl acetoacetate, methyl propionyl acetate, ethyl propionyl acetate, isopropyl propionyl acetate, propionyl tert-butyl and hexafluoroacetylacetone. From the viewpoint of reaction activity, acetylacetone or hexafluoroacetylacetone is preferred.

  As a halogen atom, a chlorine atom and a bromine atom are mentioned, for example, A chlorine atom is preferable.

  As the alkyl group, for example, an alkyl group having 3 to 20 carbon atoms is preferable, and specific examples include a pentyl group, hexyl group, 2-ethylhexyl group, octyl group, nonyl group, decyl group, dodecyl group, and octadecyl group. Can be mentioned.

  As the acyloxy group, for example, an acyloxy group having 3 to 20 carbon atoms is preferable, and specifically, a pentanoyloxy group, a hexanoyloxy group, a 2-ethylhexanoyloxy group, an octanoyloxy group, a nonanoyloxy group, a decanoyloxy group, a dodecanoyloxy group, and an octanoyloxy group. Examples thereof include a decanoyloxy group.

  As the acyl group, for example, an acyl group having 3 to 20 carbon atoms is preferable, and specifically, a pentanoyl group, a hexanoyl group, a 2-ethylhexanoyl group, an octanoyl group, a nonanoyl group, a decanoyl group, a dodecanoyl group, and an octadecanoyl group. Examples include a noyl group.

  As an alkoxy group, a C1-C10 alkoxy group is preferable, for example, and a methoxy group and an ethoxy group, n-propoxy group, isopropoxy group, butoxy group, 2-ethylhexyloxy group etc. can be mentioned.

  L may be any one of the above, or a combination of two or more. Among these, a β-diketone or a halogen atom is preferable. Furthermore, acetylacetone, hexafluoroacetylacetone, a chlorine atom or a bromine atom are more preferred, and acetylacetone is most preferred from the viewpoint of excellent solubility in a reaction solution or a composition.

The addition amount of the catalyst represented by the formula (1) is preferably between 2.0 × 10 ⁻⁷ molar equivalents and 1.2 × 10 ⁻² molar equivalents relative to 1 molar equivalent of the polyisocyanate compound, It is more preferably between x10 ⁻⁶ molar equivalents and 2.4 × 10 ⁻³ molar equivalents. If the blending amount is 2.0 × 10 ⁻⁷ mole equivalent or more with respect to 1 mole equivalent of the polyisocyanate compound, the reaction rate is increased. If the blending amount is 1.2 × 10 ⁻² molar equivalent or less, the appearance of the paint prepared from the obtained urethane (meth) acrylate is improved.

<Polyisocyanate compound (a)>
Examples of the polyisocyanate compound (a) (hereinafter referred to as “component (a)”) include the following. 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, tetramethyl xylylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate Bis (4-isocyanatocyclohexyl) methane, 1,3-bisisocyanatomethylcyclohexane, 1,4-bisisocyanatomethylcyclohexane, norbornane diisocyanate, or dimer modification or trimer modification of these isocyanates, Furthermore, the isocyanate group terminal prepolymer etc. which are the reaction products of these isocyanates with blocked isocyanates and active hydrogen-containing compounds.

<Hydroxyl group-containing (meth) acrylate (b)>
Examples of the hydroxyl group-containing (meth) acrylate (b) (hereinafter referred to as “component (b)”) include the following. 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5-hydroxypentyl ( (Meth) acrylate, 6-hydroxyhexyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, adduct of 2-hydroxyethyl (meth) acrylate and caprolactone, adduct of 4-hydroxybutyl (meth) acrylate and caprolactone, Trimethylolpropane diacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, or the like.

  In the present invention, urethane (meth) acrylate is produced using at least the above-mentioned component (a) and component (b) as a raw material. The following polyol compound (c) can be further used as the raw material.

<Polyol compound (c)>
Examples of the polyol compound (c) (hereinafter referred to as “component (c)”) include the following. Low molecular weight polyol such as hexamethylene glycol, cyclohexanedimethanol, neopentyl glycol, polyether polyol, polyester polyol, polycarbonate polyol, polybutadiene polyol, acrylic polyol, polyolefin polyol, polyesteramide polyol, polyurethane polyol, epoxy polyol, alkyd modified polyol, Castor oil-modified polyol, fluorine-containing polyol, etc. These polyol compounds may be any one of the above, or a combination of two or more.

  In the present invention, urethane (meth) acrylate is produced, for example, by the following method [1-1], [1-2] or [1-3].

  [1-1] In the process for producing a urethane (meth) acrylate in which the component (c) and the component (a) are urethanated and the reaction product obtained and the component (b) are urethanated, these two steps are performed. The method of performing a urethanation reaction in presence of the catalyst represented by Formula (1).

  In this method, the amount of each raw material used is appropriately set depending on the physical properties required for the urethane (meth) acrylate to be produced. That is, in the first stage urethanization reaction of this method, it is necessary to react the hydroxyl group of component (c) with the isocyanate group of component (a) so that the isocyanate group remains after the reaction is completed. It is preferable to set the usage-amount of (a) component and (c) component so that the number of may exceed the number of hydroxy groups. In the second stage urethanization reaction, the unreacted isocyanate group in the first stage is reacted with the hydroxy group of the component (b), so the number of hydroxy groups in the component (b) is the number of unreacted isocyanate groups. It is preferable to set the amount of the component (b) to be the same as or slightly larger than the number.

  [1-2] Production of urethane (meth) acrylate in which polyisocyanate compound (a) and hydroxyl group-containing (meth) acrylate (b) are subjected to urethanization reaction, and the resultant reaction product and polyol compound (c) are subjected to urethanation reaction In the method, the two-stage urethanization reaction is performed in the presence of a catalyst represented by the formula (1).

  Also in this method, the usage-amount of each raw material is suitably set by the physical property calculated | required by the urethane (meth) acrylate manufactured. That is, in the first stage urethanization reaction of this method, it is necessary to react the isocyanate group of the component (a) with the hydroxy group of the component (b) so that the isocyanate group remains after completion of the reaction. It is preferable to set the usage-amount of (a) component and (b) component so that the number of may exceed the number of hydroxy groups. Further, in the second stage urethanization reaction, the unreacted isocyanate group in the first stage is reacted with the hydroxy group of component (c), so the number of hydroxy groups in component (c) is the number of unreacted isocyanate groups. It is preferable to set the amount of component (c) used so that it is the same as or slightly above.

  [1-3] A method for producing a urethane (meth) acrylate, in which a polyisocyanate compound (a) and a hydroxyl group-containing (meth) acrylate (b) are urethanated in the presence of a catalyst represented by the formula (1).

  Also in this method, the amount of each raw material used is appropriately set depending on the physical properties required for the urethane (meth) acrylate to be produced. That is, it is preferable that the isocyanate group of component (a) and the hydroxy group of component (b) are reacted so that no isocyanate group remains after the reaction is completed. For this purpose, the number of hydroxy groups is the same as the number of isocyanate groups. It is preferable to set the usage amount of the component (a) and the component (b) so as to slightly exceed the above.

  In the production method [1-1], [1-2] or [1-3], the method of adding each raw material component is arbitrary, and may be any of batch charging, split charging, continuous charging, dropping charging, etc. You can choose.

  When the molecular weight of the urethane (meth) acrylate produced by the reaction is increased, the reaction solution becomes highly viscous and stirring may be difficult. Therefore, a diluting component can be added to the reaction solution. As the diluting component, those not involved in the urethanization reaction are preferable, and examples thereof include the following. Monomers having no hydroxyl group such as aromatic compounds such as toluene and xylene, ester compounds such as ethyl acetate and butyl acetate, organic solvents such as dimethylamide, 2-ethylhexyl acrylate and isobornyl acrylate.

<Coordination compound (d)>
The catalyst remains in the urethane (meth) acrylate-containing material obtained by the urethanization reaction of the production method. This residual catalyst colors the urethane (meth) acrylate-containing material. In the present invention, the coordination compound (d) is added to the urethane (meth) acrylate-containing material, and the ligand L of the remaining catalyst in the urethane (meth) acrylate-containing material is converted into the coordination compound (d Can be exchanged with a ligand derived from Thereby, the coloring of the urethane (meth) acrylate-containing material can be reduced or eliminated.

  Examples of the coordination compound (d) include organic acids, inorganic acids, alcohols and amines. That is, carboxylic acid, phosphoric acid, phosphoric acid ester, phosphorous acid, phosphorous acid ester, linear or branched alcohol, and linear or branched amine are mentioned. Among these, phosphoric acid, phosphoric acid ester, phosphorous acid, or phosphorous acid ester is preferable, and phosphoric acid ester is particularly preferable.

  Specific examples of the phosphate ester include phosphoric acid (meth) acrylate, dimethylphosphinic acid, diphenylphosphinic acid, trimethyl phosphate, triethyl phosphate, and triphenyl phosphate. Examples of phosphoric acid (meth) acrylate include Nippon Kayaku Co., Ltd. trade name Kayamar PM-21 and trade name Kayamar PM-2.

  The addition amount of the coordination compound (d) is preferably 1 to 100 molar equivalents, more preferably 1 to 50 molar equivalents, relative to 1 molar equivalent of the urethanization reaction catalyst.

  Next, the present invention will be described in further detail using examples. Evaluation items and evaluation methods in the examples are as follows.

<1. Reaction rate>
In the examples, the time when the preparation of the hydroxyl group-containing (meth) acrylate (b) is completed is defined as 0 hour (T ₀ ), and the time when the reaction rate becomes 97% from that point is defined as the reaction time.
A: Reaction time is 5 hours or less,
○: Reaction time over 5 hours, 10 hours or less,
X: Reaction time exceeds 10 hours.

In this evaluation, to measure the reaction rate by changing the time for appropriate reaction, if the time the reaction rate became 97% from T ₀ of less than 5 hours "◎" reaction rate after 5 hours from T ₀ Is less than 97% and the reaction rate after 10 hours is 97% or more, it is evaluated as “◯”, and when the reaction rate after 10 hours from T ₀ is less than 97%, it is evaluated as “x”.

1-1. Reaction rate measurement The reaction rate is calculated by the following equation.
Reaction rate (%) = (C ₀ −C) ÷ C ₀ × 100
C ₀ : isocyanate group equivalent (mol / g) before reaction,
C: Isocyanate group equivalent (mol / g) after reaction.

1-2. How to obtain C ₀ C ₀ is calculated by the following equation.
C ₀ = x × y ÷ N
x: number of moles of polyisocyanate compound,
y: the number of isocyanate groups in one molecule of the polyisocyanate compound,
N: Total amount (g) of polyol compound, polyisocyanate compound, hydroxyl group-containing (meth) acrylate and other additives.

1-3. C is calculated by the following formula.
C = (A−B) × 0.1 × F ÷ 1000 ÷ S
A: Amount of hydrochloric acid necessary for neutralization in the blank measurement (ml),
B: hydrochloric acid amount (ml) necessary for neutralization of the reaction solution,
F: Factor of the titrant
S: Sample amount (g).

1-4. How to obtain A To a 200 ml Erlenmeyer flask, add 25 ml of chlorobenzene, 25 ml of a 0.1N di-n-butylamine chlorobenzene solution and 2 drops of bromophenol, and stir the mixture uniformly. Titration is performed using 0.1N hydrochloric acid, and A is the point where the color of the solution has changed.

1-5. How to find B Take 0.3 g of urethane (meth) acrylate in a 200 ml Erlenmeyer flask and add 25 ml of chlorobenzene to dissolve. Add 25 ml of 0.1N di-n-butylamine in chlorobenzene and 2 drops of bromophenol and stir to homogeneity. Titration is performed using 0.1N hydrochloric acid, and B is the point where the color of the solution has changed.

<2. Yellowness>
Using a quartz cell having a cell length of 5 cm, the absorbance at 417 nm of urethane (meth) acrylate is measured with a spectrophotometer (manufactured by Hitachi High-Technology Corporation, trade name: Hitachi spectrophotometer U-1900). Thereafter, APHA is calculated using the following equation.
APHA = (absorbance at 417 nm) × 549
The yellowness is evaluated according to the following criteria.
A: APHA is less than 200,
○: APHA is 200 or more and less than 1000,
X: APHA is 1000 or more.

< Reference Example 1> Production of Urethane Acrylate (UA1) In a 2 L four-necked flask, 4,4-dicyclohexylmethane diisocyanate (manufactured by Sumitomo Bayer Urethane Co., Ltd., trade name Desmodur W, molecular weight 264. 8) 424 g (1.6 mol), and iron (III) acetylacetonate (manufactured by Aldrich Co., Ltd., trade name Iron (III) Acetylacetonate, molecular weight 353.18) as a catalyst represented by the formula (1) 095 g (2.69 × 10 ⁻⁴ mol) was charged and heated in a water bath so that the internal temperature became 70 ° C.

  On the other hand, as a component (c), 634 g (0.73 mol) of polytetramethylene ether glycol (manufactured by Hodogaya Chemical Co., Ltd., trade name PTG850SN, average molecular weight 872) was charged into a dropping funnel with a side tube. While stirring the contents in the flask, the liquid in the dropping funnel was dropped into the flask over 2 hours while maintaining the flask internal temperature at 70 ° C., and further stirred for 2 hours to carry out the urethanization reaction. It was.

  The temperature of the flask contents was then raised to 80 ° C. On the other hand, 204 g (1.76 mol) of 2-hydroxyethyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name HEA, molecular weight 116.12) as component (b) and 2,6-ditertiarybutyl- 1.8 g of 4-methylphenol (manufactured by Wako Pure Chemical Industries, Ltd., trade name butylhydroxytoluene, molecular weight 220.36) was charged into another dropping funnel and uniformly mixed and dissolved. This solution was dropped into the flask over 2 hours while keeping the temperature inside the flask at 80 ° C. Thereafter, the temperature of the flask contents was kept at 80 ° C., and a urethanization reaction was performed for 30 minutes to obtain a urethane acrylate-containing material.

  Subsequently, 347 g of 2-ethylhexyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name EHA, molecular weight 184.28) and 2,6-di-tert-butyl-4-methylphenol (Wako Pure Chemical Industries, Ltd.) Manufactured, trade name butylhydroxytoluene, molecular weight 220.36) 0.7 g was uniformly mixed and dissolved. This liquid was added to the flask and stirred at 80 ° C. for 30 minutes to obtain a diluted liquid of urethane acrylate-containing material. This diluted solution was yellowish brown, viscous liquid, and APHA was 1297. Moreover, it was 98% when the reaction rate was measured using this dilution liquid.

< Reference Example 2> Production of Urethane Acrylate (UA2) In a 4-liter flask with 2 L, 4,4-dicyclohexylmethane diisocyanate (manufactured by Sumitomo Bayer Urethane Co., Ltd., trade name Desmodur W, molecular weight 264. as component (a)). 8) 424 g (1.6 mol), polytetramethylene ether glycol (manufactured by Hodogaya Chemical Co., Ltd., trade name PTG850SN, average molecular weight 872) as component (c), 634 g (0.73 mol), and formula (1) ) Was charged with 0.095 g (2.69 × 10 ⁻³ mol) of iron (III) acetylacetonate (manufactured by Aldrich Co., Ltd., trade name Iron (III) Acetylacetonate, molecular weight 353.18). .

  The contents in the flask were heated to 70 ° C. and stirred for 2 hours to conduct a urethanization reaction.

  The temperature of the flask contents was then raised to 80 ° C. On the other hand, as component (b), 2-hydroxyethyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name HEA, molecular weight 116.12) 204 g (1.76 mol) and 2,6-di-tert-butyl-4 -1.8 g of methylphenol was uniformly mixed and dissolved. This liquid was added into the flask. Thereafter, the temperature of the flask contents was kept at 80 ° C., and a urethanization reaction was performed for 30 minutes to obtain a urethane acrylate-containing material.

  Subsequently, 347 g of 2-ethylhexyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name EHA, molecular weight 184.28) and 2,6-di-tert-butyl-4-methylphenol (Wako Pure Chemical Industries, Ltd.) Manufactured, trade name butylhydroxytoluene, molecular weight 220.36) 0.7 g was uniformly mixed and dissolved. This liquid was added to the flask and stirred at 80 ° C. for 30 minutes to obtain a diluted liquid of urethane acrylate-containing material. This diluted liquid was yellowish brown, viscous liquid, and APHA was 1320. Moreover, it was 98% when the reaction rate was measured using this dilution liquid.

<Example 3>
50 parts by mass of a diluted solution of the urethane acrylate-containing product obtained in Reference Example 1, and a phosphate compound as a coordination compound (d) (manufactured by Nippon Kayaku Co., Ltd., trade name Kayamar PM-2)
1, average molecular weight 416.36) A solution obtained by mixing and dissolving 0.024 parts by mass was a pale yellow transparent and viscous liquid, and its APHA was 172. From this, it was confirmed that the color of the diluted solution of the urethane acrylate-containing material was diluted by the phosphate methacrylate compound.

Reference Example 4 Production of Urethane Acrylate (UA3) 1,2-bisisocyanatomethylcyclohexane (manufactured by Mitsui Chemicals Polyurethane Co., Ltd., trade name Takenate 600, molecular weight 194) as a component (a) in a 2 L four-necked flask .2) 242 g (1.25 mol), and iron (III) acetylacetonate (manufactured by Aldrich Co., Ltd., trade name Iron (III) Acetylacetonate, molecular weight 353.18) 0 as a catalyst represented by the formula (1) 0.072 g (2.04 × 10 ⁻⁴ mol) was charged and heated in a water bath so that the internal temperature was 65 ° C.

  Meanwhile, 355 g (2.73 mol) of 2-hydroxypropyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name HPA, molecular weight 130.14) was charged into the dropping funnel as the component (b). The liquid in the dropping funnel was dropped into the flask over 6 hours while maintaining the temperature in the flask at 65 ° C. while stirring the contents in the flask. After completion of dropping, the mixture was stirred at 65 ° C. for 1 hour to carry out a urethanization reaction. The obtained urethane acrylate-containing material was yellowish brown and was a viscous liquid, and its APHA was 1010. Moreover, it was 98% when the reaction rate was measured using this urethane acrylate containing material.

<Example 5>
A urethane acrylate was produced in the same manner as in Example 3 except that the coordination compound shown in Table 1 was used, and the coordination compound was added to evaluate the reaction rate and yellowness. The evaluation results are shown in Table 1.

< Reference Examples 6, 8, 10, 12, and 14 to 32>
The same procedure as in Reference Example 1 was conducted, except that the reaction was carried out by appropriately changing the time until the reaction time was known, using various types and amounts of raw materials shown in Tables 2 to 7 and the catalyst represented by the formula (1). Urethane acrylate was produced and the reaction rate and yellowness were evaluated. The evaluation results are shown in Tables 2-7.

<Examples 7, 9, 11 and Reference Example 13>
Examples except that the reaction was carried out using various raw materials of the types and amounts shown in Table 2 and Table 3, the catalyst represented by the formula (1), and the coordination compound, changing the time appropriately until the reaction time was known. In the same manner as in No. 3, urethane acrylate was produced, a coordination compound was added, and the reaction rate and yellowness were evaluated. The evaluation results are shown in Tables 2 and 3.

Abbreviations in Tables 1 to 7 are as follows.
Fe (acac) ₃ : iron (III) acetylacetonate,
Zr (acac) ₄ : zirconium acetylacetonate,
Ni (acac) ₃ : nickel acetylacetonate,
(I-PrO) ₂ Ti (C ₆ H ₉ O ₃ ) ₂ : Titanium diisopropoxybis (ethyl acetoacetate),
Ti (i-PrO) ₄ : titanium tetraisopropoxide,
Bi (C ₁₀ H ₁₉ O ₂ ) ₃ : bismuth neodecanoate,
PTG850SN: polytetramethylene glycol (made by Hodogaya Chemical Co., Ltd., trade name PTG850SN),
PL205: Polycaprolactone diol (manufactured by Daicel Chemical Industries, Ltd., trade name Plaxel 205),
T5650J: Polycarbonate diol (Asahi Kasei Kogyo Co., Ltd., trade name T5650J),
G-1000: polybutadiene diol (manufactured by Nippon Soda Co., Ltd., trade name G-1000),
H-MDI: 4,4-dicyclohexylmethane diisocyanate,
H-XDI: 1,3-bisisocyanatomethylcyclohexane,
IPDI: Isophorone diisocyanate (Evonik Degussa Japan Co., Ltd., trade name VESTANAT IPDI),
HEA: 2-hydroxyethyl acrylate,
HPA: 2-hydroxypropyl acrylate,
PM-21: Phosphate methacrylate compound (Nippon Kayaku Co., Ltd., trade name Kayamar PM-21),
DPPA: diphenylphosphinic acid,
DBTDL: Dibutyltin dilaurate (trade name ADK STAB BT-11, manufactured by ADEKA Corporation).

Claims (1)

In the method for producing urethane (meth) acrylate using at least the polyisocyanate compound (a) and the hydroxyl group-containing (meth) acrylate (b) as raw materials, the catalyst represented by the formula (1) is used as a catalyst for the urethanization reaction , A coordination compound is added to the urethane (meth) acrylate-containing product obtained by the urethanization reaction, and the ligand L of the catalyst represented by the formula (1) in the urethane (meth) acrylate-containing product is added. A method for producing urethane (meth) acrylate, wherein a ligand is exchanged with another ligand derived from the coordination compound .
M (L) n (1)
[In Formula (1), M is a central metal, represents Fe , L is a ligand, and represents a β-diketone, a halogen atom, an alkyl group, an acyloxy group, an acyl group, or an alkoxy group. n is an integer value determined by the valence of the central metal and the coordination number of the ligand. ].