JPH033691B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a photocurable composition. [Prior Art] Currently, photocurable compositions containing various urethane poly(meth)acrylates are being intensively researched and commercialized in various markets. [Problem to be solved by the invention] However, the photocurable compositions currently available on the market generally contain various types of urethane poly(meth)acrylates with high viscosity, and are therefore insufficiently applicable to various uses. That is the current situation. Therefore, in these markets, new low viscosity urethane poly(meth)
There is a strong need for photocurable compositions containing acrylates. Therefore, providing photocurable compositions containing novel urethane poly(meth)acrylates to these markets is extremely useful for the advancement of various applications. [Means for Solving the Problems] The present invention provides: (A) an ester diol urethane poly(meth)acrylate consisting of a reaction product of the following components (a), (b) and (c); (a) the following: Compound of [] (In formula [], the average values of m and n are each 0
〜10, and the average total value of the sum of m and n is 1〜
Showing the number 20. ) (b) Organic polyisocyanate...[] (c) Compounds of the following [], [] or/and [] (In formula [], R ₁ and R ₂ represent H or CH _3. ) (In formula [], R ₁ and R ₂ represent H or CH ₃ ,
n represents 1 to 20. ) A photocurable composition comprising an esterified product of a polyol and (meth)acrylic acid and having at least one OH group...[] and (B) a photopolymerization initiator; Regarding. The above ester diol urethane (meth)acrylate (A) is produced by converting components (a) and (b) into urethanes, and then converting them into poly(meth)acrylates with component (c). The compound [] used in the present invention is obtained by adding hydroxypivalyl hydroxypivalate and epsilon caprolactone. During the reaction of hydroxypivalyl hydroxypivalate and epsilon caprolactone, a catalytically effective amount of catalyst is preferably used.
The amount used is based on the weight of caprolactone.
0.001-1.0% by weight, preferably 0.01-0.2% by weight. Useful catalysts are known to those skilled in the art of lactone adduct chemistry; examples of useful catalysts include organotitanium compounds such as tetraisopropyl titanate, tetrabutyl titanate, tetraphenyltin, tetraoctyltin diphenyltin dilaurate. and tin compounds such as dilauryltin oxide. The reaction of hydroxypivalyl hydroxypivalate and epsilon caprolactone is carried out at a temperature of 50 to 300°C, preferably 130 to 200°C, for a period of time sufficient to complete the reaction between the charged reactants. The amount of epsilon caprolactone charged in the reaction is about 1 to 20 moles per mole of hydroxypivalyl hydroxypivalate charged. In order to minimize oxidative side reactions, the reaction is preferably carried out under an inert gas atmosphere such as nitrogen. The product consisting of the adduct mixture of hydroxypivalyl hydroxypivalate and epsilon caprolactone can be used as is. Examples of organic polyisocyanates include tolylene diisocyanate, xylylene diisocyanate, diisocyanate, lysine diisocyanate, diphenylmethane-4,4'-diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and dimer acid diisocyanate. Particularly preferred organic polyisocyanates are hexamethylene diisocyanate and isophorone diisocyanate. Examples of the compound [ ] include hydroxyethyl (meth)acrylate and hydroxypropyl (meth)acrylate. Examples of compounds in [] include monohydroxypolycaprolactone with acrylate or methacrylate end groups (Plaxel FA-1, FA-2, FM-1, FM-2, etc. manufactured by Daicel Chemical Industries, Ltd.)
can be mentioned. Examples of compounds in [] include glycerin, trimethylolpropane, 1,2,4-butanetriol, 1,2,5-pentanetriol, 1,
Poly(meth)acrylates having at least one OH group obtained using polyols such as 2,6-hexanetriol, pentaerythritol, dipentaerythritol, sorbitol, mannitol, etc., and also poly(meth)acrylates having at least one OH group added to the above polyols. Examples include poly(meth)acrylate having at least one OH group obtained using polycaprolactone polyol. A particularly preferred compound [ ] is pentaerythritol triacrylate. The above-mentioned urethanization reaction can be carried out in the presence of a known catalyst that promotes urethane formation, such as a tertiary amine, dibutyltin dilaurate, dioctyltin dilaurate, etc., in order to promote the reaction between isocyanate groups and hydroxyl groups. Also,
This urethanization reaction can be carried out in procedures known to those skilled in the art, if desired using a slight excess of either reactant, which under the reaction conditions is inert and also acts as a viscosity-lowering agent. It can be carried out in an organic solvent. These organic solvents include ketones such as acetone, methyl ethyl ketone, and cyclohexane, esters such as ethyl acetate and butyl acetate, aromatic hydrocarbons such as toluene and xylene, and ethers such as isopropyl ether and ethyl ether. There are many suitable solvents. Often the reaction is carried out in an ethylenically unsaturated monomer that can be retained in the formulation, used as a formulation of the photocurable composition, and incorporated into the composition to be cured. be able to. Examples of such ethylenically unsaturated monomers include polyacrylates such as styrene, vinyl alcohol esters, acrylate esters, glycol diacrylates, triols and tetraols. In addition, this urethanization reaction temperature is room temperature to 100℃,
Preferably it is 50-80°C. Then, in the next poly(meth)acrylation reaction, a slight excess of component (c) can be used relative to the compound having terminal isocyanate groups obtained in the urethanization reaction. In this reaction, in order to prevent gelation due to radical polymerization during the reaction, 50 to 2000 ppm (based on the compound having a terminal isocyanate group) of hydroquinone, hydroquinone monomethyl ether,
It is preferable to add a polymerization inhibitor such as p-methoxyphenol, p-benzoquinone, or phenothiazine. The novel ester diol urethane poly(meth)acrylate thus synthesized can be used as a base range for coating and ink compositions or as a base range for other monomers (N-vinyl-2-
pyrrolidone, styrene, 1,6-hexanediol diacrylate, etc.) or polymers (epoxy acrylate, polyester acrylate, etc.),
It can be used as a mixture with fillers and other additives. (B) Photoinitiators are generally known to those skilled in the art and include benzophenone, p-methoxybenzophenone, acetophenone, m-chloroacetophenone, propiophenone, xanthone, benzoin, benzyl, Many types can be mentioned, such as naphthoquinone and anthraquinone. The photoinitiator is incorporated into the composition at a concentration of about 0.1 to about 10% by weight. The composition of the present invention can be applied by conventional means and can be photocured using ultraviolet rays or the like. [Example] Hereinafter, the present invention will be explained in detail with reference to Synthesis Examples and Examples. (Synthesis examples 1 to 4 of adducts of hydroxypivalyl hydroxypivalate and epsilon caprolactone) Synthesis example 1 Equipped with a stirrer, a temperature controller, a thermometer, and a condenser.
In a 1L reactor, 408.5 parts of hydroxypivalyl hydroxypivalate, epsilon caprolactone
228.3 parts of isopropyl titanate and 0.38 parts of isopropyl titanate were charged, heated to 160 to 170°C in nitrogen, and reacted until unreacted epsilon caprolactone became 1% by weight or less. The obtained adduct is a liquid substance with a hydroxyl value of 254.7,
The saponification value was 394.3 and the acid value was 4.09. As a result of molecular weight measurement, it was shown that the adduct of hydroxypivalyl hydroxypivalate and epsilon caprolactone had an average of about 2 epsilon caprolactone adducts in the molecule. Hereinafter, this will be referred to as "adduct of hydroxypivalyl hydroxypivalate and epsilon caprolactone (2M)." Synthesis Example 2 Into the same reactor as in Synthesis Example 1, 204.3 parts of hydroxypivalyl hydroxypivalate, 456.6 parts of epsilon caprolactone, and 0.40 parts of isopropyl titanate were charged, and the mixture was heated until the remaining amount of epsilon caprolactone became 1% by weight or less. The reaction was carried out in the same manner as in Synthesis Example 1. The obtained adduct is a liquid substance with a hydroxyl value
The saponification value was 166.1, the saponification value was 424.8, and the acid value was 1.90. As a result of molecular weight measurement, it was shown that the adduct of hydroxypivalyl hydroxypivalate and epsilon caprolactone had an average of about 4 epsilon caprolactone molecules in the molecule. Hereinafter, this will be referred to as "adduct of hydroxypivalyl hydroxypivalate and epsilon caprolactone (4M)." Synthesis Example 3 Into the same reactor as in Synthesis Example 1, 143 parts of hydroxypivalyl hydroxypivalate, 639.2 parts of epsilon caprolactone, and 0.38 parts of isopropyl titanate were charged, and the mixture was heated until the remaining amount of epsilon caprolactone became 1% by weight or less. The reaction was carried out in the same manner as in Synthesis Example 1. The obtained adduct was a wax-like substance with a hydroxyl value of 95.1, a saponification value of 452.3, and an acid value of 2.73. As a result of molecular weight measurement, it was shown that the adduct of hydroxypivalyl hydroxypivalate and epsilon caprolactone had an average of about 8 epsilon caprolactone adducts in the molecule. Hereinafter, this will be referred to as "adduct of hydroxypivalyl hydroxypivalate and epsilon caprolactone (8M)." Synthesis Example 4 Into the same reactor as in Synthesis Example 1, 123 parts of hydroxypivalyl hydroxypivalate, 684.8 parts of epsilon caprolactone, and 0.41 parts of isopropyl titanate were charged, and the mixture was heated until the remaining amount of epsilon caprolactone became 1% by weight or less. The reaction was carried out in the same manner as in Synthesis Example 1. The obtained adduct was a wax-like substance with a hydroxyl value of 78.7, a saponification value of 458.8, and an acid value of 2.34. The results of molecular weight measurements showed that the adduct of hydroxypivalyl hydroxypivalate and epsilon caprolactone had an average of about 10 epsilon caprolactone molecules in the molecule. Hereinafter, this will be referred to as "adduct of hydroxypivalyl hydroxypivalate and epsilon caprolactone (10M)." (Synthesis examples 5 to 12 of ester diol urethane (meth)acrylate (A)) Synthesis example 5 The above hydroxypivalyl hydroxypivalate was added to a 1L reactor equipped with a stirrer, a temperature controller, a thermometer, and a condenser. 213.5 parts of an adduct of epsilon caprolactone (2M) and 222.3 parts of isophorone diisocyanate were charged. The reaction temperature of this mixture is 70 to 75℃.
I went there while keeping it safe. The reaction was continued until completion as indicated by 9.64% free isocyanate groups. The elapsed time from initial charge of the reactor to completion of the reaction was 8 hours. Then, with stirring, 127.7 parts of hydroxyethyl acrylate, 0.28 parts of hydroquinone monomethyl ether, and di-n-butyltin dilaurate were added.
I prepared 0.11 parts. This reaction was carried out while maintaining the reaction temperature at 75 to 80°C. The reaction was continued until completion as indicated by less than about 0.3% free isocyanate groups. As a reaction product, a hydroxyethyl acrylate adduct of an adduct of hydroxypivalyl hydroxypivalate and epsilon caprolactone (2M) with isophorone diisocyanate was obtained. Synthesis Examples 6 to 12 Ester diol urethane poly(meth)acrylates were synthesized by carrying out reactions in the same manner as in Synthesis Example 5 using the feed component compositions shown in Table 1. Temperature 49 for each ester diol urethane poly(meth)acrylate obtained in Synthesis Examples 5 to 12
Measure the viscosity at °C and use the Thiokol
It is shown in Table 1 along with the viscosity of Uvitane893.

【table】

[Table] Example 1 Monoacrylate obtained by adding 2 moles of epsilon caprolactone to 70 parts of ester diol urethane poly(meth)acrylate obtained in Synthesis Example 5 and 30 parts of tetrahydrofurfuryl alcohol (manufactured by Nippon Kayaku Co., Ltd.)
TC-120S) and phenylglyoxylic acid ester (Viquiure-55 manufactured by Stauffer Japan)
A photocurable composition was prepared by adding 10 parts. This composition was applied onto a steel plate panel, and irradiated with light from a distance of 8 cm using a 2KW high-pressure mercury lamp (ozone-less type). The composition reached a tack-free state by irradiation for 0.42 seconds. In addition, the elongation (%) and tensile strength (Kg/cm 2 ) of the film were measured using a film that was cured by irradiating light for 16.8 seconds from a distance of 8 cm using a 2KW high-pressure mercury lamp (ozone ^type ). was measured. (Measuring temperature 23℃, using JIS-3 damper)
The elongation of this composition is 23.5% and the tensile strength is 205Kg/cm ²
It was hot. Examples 2 to 8, Comparative Example 1 In Example 1, the ester diol urethane poly(meth)acrylate obtained in Synthesis Examples 6 to 12 or Uvitane893 was used instead of the ester diol urethane poly(meth)acrylate obtained in Synthesis Example 5. Using each of these, a photocurable composition was prepared in the same manner as in Example 1, and the curing rate, elongation (%), and tensile strength (Kg/cm ² ) were measured. The results are shown in Table 2.

〔Effect of the invention〕

The composition of the present invention contains a low viscosity ester diol urethane poly(meth)acrylate and is applicable to a variety of applications.

Claims (1)

[Scope of Claims] 1 (A) Ester diol urethane poly(meth)acrylate consisting of a reaction product of the following components (a), (b) and (c) (a) The following compound [] (In formula [], the average values of m and n are each 0
〜10, and the average total value of the sum of m and n is 1〜
Showing the number 20. ) (b) Organic polyisocyanate...[] (c) Compounds of the following [], [] or/and [] (In formula [], R ₁ and R ₂ represent H or CH _3. ) (In formula [], R ₁ and R ₂ represent H or CH ₃ ,
n represents 1 to 20. ) A photocurable composition comprising: a compound that is an esterified product of a polyol and (meth)acrylic acid and has at least one OH group; and (B) a photopolymerization initiator.