JPS6150939A - Acryloyloxypropiophenone derivative and its use - Google Patents

Abstract

NEW MATERIAL:An acryloyloxypropiophenone derivative shown by the formula I (R1 is H, or 1-4C alkyl; R2 is H, or methyl). EXAMPLE:2-(meth)Acryloyloxy-2-methyl-1-phenyl-propan-1-one. USE:Useful as a sensitizer for a composition curable with active energy rays. A curable composition containing the sensitizer has high gel content of cured material, has low loss in weight by thermal degradation test, small change in physical properties, and useful for casting, embedding, immersion, molding, bonding, etc. (meth)acrylate compound is representative as a radically polymerizable compound. PREPARATION:For example, a keto-alcohol shown by the formula II is esterified with acrylic acid, acrylic acid chloride, methacrylic acid, or methacrylic acid chloride, to give a compound shown by the formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to novel alkyloyloxypropiophenone derivatives and their use as sensitizers for active energy ray-curable compositions.

[Background technology]

In recent years, curing methods using active energy rays such as violet Tato rays and electron beams have been used to cure inks, Widely used as coating materials, adhesives, etc.

(Meth)acrylate resin is a typical resin system that polymerizes upon irradiation with ultraviolet rays. However, ultraviolet rays have low energy and do not easily polymerize when simply irradiating (meth)acrylate resin. Therefore, a compound called a sensitizer that absorbs ultraviolet rays and generates radicals is usually used in combination. Various substances are known as this sensitizer.

However, when conventional sensitizers are used, no matter how carefully the curing conditions are selected, when the resin is cured, a relatively large amount of low molecular weight substances remain in the cured product. For example, it cannot be used in food-related applications, and even outside of food-related applications, the properties of the cured product change when administered orally, so its uses have been limited.

[Disclosure of the invention]

An object of the present invention is to provide novel acryloyloxypropiophenone derivatives.

Another object of the present invention is to provide new and improved sensitizers for active energy radiation curable resin compositions.

This is achieved by using an acid sensitizer.

Formula [wherein R1 is H or an alkyl group having 1 to 4 carbon atoms, R
2 is H or a methyl group] acryloyloxyprobiophenone derivative.

Formula [wherein R3 is ■ (or an alkyl group having 1 to 4 carbon atoms,
A sensitizer for active energy ray-curable compositions comprising an acryloyloxyprobiophenone derivative represented by R2 is H or a methyl group.

[Embodiments of the invention]

The compound represented by the formula (1) used in the present invention can be produced, for example, by an esterification reaction between a keto alcohol represented by the following formula (2) and acrylic acid, acrylic acid chloride, methacrylic acid, or methacrylic acid chloride. can.

(J 1-1 [wherein R1 has the same meaning as in formula (1)]
Examples of compounds represented by formula (2) include 2-hydroquine-2-methyl-1-phenyl-propane-1-
2-hydroquine-2-one, 2-hydroquine-2-one, 1-paramethylphenyl-propan-1-one, 2-hydroquine-2-methyl-1-paraethylphenyl-propan-1-one,
Examples include 2-hydroquine-2-methyl-1-paraisopropylphenyl-propan-1-one, 2-hydroxy-2-methyl-1-parabutylphenyl-propan-1-one, and the like.

Examples of the acryloyloxyprobiophenone derivative represented by formula (1) produced as described above include the following compounds.

2-(meth)acryloyloxy-2-methyl-1-phenyl-propan-1-one, 2-(meth)acryloyloxy-2-methyl-1-paramethylphenyl-propan-1-one, 2-(meth) Acryloyloxy-2-methyl-1-valisopropylphenyl-propane-1-
on, 2-(meth)acryloyloxy-2-methyl-1
-parabutylphenyl-propan-1-one. The expression "(meth)acryloyloxy" mentioned above in the present invention + two terms means both acryloyloxy and methacryloyloxy.

The compound represented by the above formula (1) can be exposed to ultraviolet rays, electron beams,
It is used as a sensitizer (curing agent) for resin compositions that are curable with active radiation such as beta rays and gamma rays, and Lugie rays. That is, the compound of the above formula (1) can be cured by irradiating the composition with an active A-Lugie ray in the form of a composition with a radically polymerizable compound.

As a radically polymerizable compound, a (meth)acrylate compound is typical. Here, (meth)acrylate means both acrylate and methacrylate. A (meth)acrylate compound is a compound having one or more acryloyloxy groups (CH2C/> or methacryloyloxy groups\C0O- (CH2=Cζ:')-) in the molecule,
Specifically, the following are exemplified.

1) Monool (meth)acrylates Acrylic esters or methacrylic esters of monools such as 2-ethylhexanol and tetrahydrofurfuryl alcohol. Specific examples of monools include butyl alcohol, hexyl alcohol, and 2-ethylhexanol. , lauryl alcohol, benzyl alcohol, nclohexanol, furfuryl alcohol, tetrahydrofurfuryl alcohol, etc., and compounds obtained by adding ethylene oxide, propylene oxide, r-butyrolactone, ε-caprolactone, etc. to these monools, phenol, cresol, nonylphenol, etc.

2) Poly(meth)acrylate of polyol Acrylic ester or methacrylic ester of polyol. Specific examples of polyols include ethylene glycol, diethylene glycol, fluoropylene gellicol, dipropylene glycol, butanediol, hequinanediol, neopentyl glycol, chlorohexanedimethanol, water, bisphenol A, limethylolpropane, glycerin, and pentaerythritol. , dipentaerinurritol, and the like.

3) Poly(meth)acrylate of polyether polyol Acrylic acid ester or methacrylic acid ester of polyether polyol. Specific examples of polyether polyols include triethylene glycol, tetraethylene glycol, polyethylene glycol, tripropylene glycol, tetrapropylene glycol, polypropylene glycol, polyquine tetramethylene glycol,
Examples include polyoxypropylene triol, polyokinetetramethylene triol, and polyols obtained by adding one or more moles of ethylene oxide or propylene oxide to the above-mentioned polyols, polyether polyols, bisphenol Δ, bisphenol F, and the like.

4) Poly(meth)acrylate of polyester polyol Acrylic ester or methacrylic ester of polyester polyol. Specific examples of polyester polyols include the aforementioned polyols, polyether polyols, cohelic acid, adipic acid, sepatenoic acid, dodecanedicarboxylic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, phthalic anhydride, Examples include polyesters having two or more hydroxyl groups in the molecule, polybutyrolactone polyols, polycaprolactone polyols, etc. made from polybasic acids such as isophthalic acid, terephthalic acid, trimellitic anhydride, maleic anhydride, and fumaric acid. .

5) Epoxy (meth)acrylate A resin obtained by adding methacrylic acid or acrylic acid to Evoquin resin. Specific examples of epoxy resins include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, novolac polygrindyl ether, ethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane triglycidyl ether, and tetrahydrophthalic acid. Digrindyl ester, Union Carbide products ERL-4206, ERL-4221, E n L -
4299, butyl glycidyl ether, and phenyl glycidyl ether.

6) Urethane (meth)acrylate The above-mentioned polyols, polyether polyols and polyester polyols together with tolylene diisonanate, diphenylmethane-4,4'-diisocyanate, hexamethylene diisonanate, isophorone diisocyanate, xylylene/diisocyanate Reaction with diisocyanate compounds such as diisocyanate, naphthalene diisocyanate, and (meth)acrylates having hydroxyl groups such as hydroxyethyl acrylate, hydroquine ethyl methacrylate, hydroquine propyl acrylate, and hydroquine propyl methacrylate. (meth)acrylate compound.

7) Other (meth)acrylates such as silicone (meth)acrylate, melamine acrylate, modified products of the above-mentioned (meth)acrylate compounds, acrylic acid, methacrylic acid, hydroquine ethyl (
meth)acrylate, hydroquinepropyl(meth)acrylate, dimethylaminoethyl(meth)acrylate, diethylaminoethyl(meth)acrylate, t-butylaminoethyl(meth)acrylate, glinosyl(
(meth)acrylate, etc.

In addition to the above-mentioned (meth)acrylate compounds, aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, p-methylstyrene, vinyl acetate,
Vinyl esters such as vinyl propionate, acrylamide, methacrylamide, hydroxymethyl acrylamide, butquin methyl acrylamide, dimethyl acrylamide, octylacrylamide, and allyl compounds can also be mentioned as examples of the radically polymerizable compound of the present invention.

The compound represented by the above formula (1) and the radically polymerizable compound are used as a composition. The proportion of both in the composition is preferably 15 to 0.2 parts of the compound represented by formula (1) per 100 parts of both in total;
The amount is preferably 7 to 0.4 parts.

If the amount of the compound represented by the above formula (1) is less than 0.2 parts, the curing speed of the composition will be extremely slow, and unreacted compounds will remain, resulting in a decrease in gel fraction, resulting in a cured product. Oral changes in sexual IQ. On the other hand, exceeding 15 parts has no further effect on curability and is only economically disadvantageous.

Is the above composition an active energy ray? Cures by irradiation. Examples of active energy rays include ultraviolet rays, rays, beta rays, and gamma rays. The above compositions are particularly well cured by UV radiation. Examples of sources of ultraviolet light include mercury lamps, metal halide lamps, carbon arc lamps, xenon lamps, microwave discharge lamps, and sunlight.

The above composition can be cured without using a so-called ordinary sensitizer, but examples include benzoin, benzoin alkyl ether, benzyl, benzophenone, anthraquinone and its derivatives, benzyl dimethyl ketal, 2-hydroquine-2- Addition of ordinary sensitizers and sensitization aids such as methylpropiophenone, diphenyl sulfide, Schedkin acetophenone, thioxanthone and its 1-transparent conductor, Michler's ketone, morpholine, diethylamine, etc. to the extent that the effects of the present invention are not impaired. You can. In addition, various additives such as ordinary solvents, plasticizers, leveling agents, seed modification agents, anti-cissing agents, anti-blocking agents, slick agents, coupling agents, thickeners, and polymerization inhibitors, as well as talc, calcium carbonate, Fillers such as alumina, mica, phosphoric acid, barium sulfate, magnesium carbonate, glass powder, various polymer powders, titanium oxide, zinc white,
carbon black, red iron, phthalocyanine blue,
It is also possible to add pigments and dyes such as phthalonanine green, as well as resins such as polyester resins, acrylic resins, vinyl chloride resins, polyvinyl butyral, Epoquin resins, urethane resins, and waxes.

The composition of the present invention can be used for purposes such as casting, embedding, sealing, impregnation, molding, coating, insulation, and adhesion.

The present invention will now be illustrated in more detail with reference to Synthesis Examples and Examples. In the present invention, parts and percentages are based on weight unless otherwise specified.

Synthesis Example 1 1611 parts (1 mol) of 2-hydroquine-2-methylpropiophenone and 121 parts (1 mol) of triethylamine were placed in a flask equipped with a cooling condenser, a stirrer, and a dropping funnel.
, 2 mol), 800 parts of chloroform f-1 included, /7
109 parts (1.2 moles) of Lorado acrylate were added dropwise to the mixture while cooling the mixture to 20° C. or lower. After 7 drops 2
The reaction was completed by stirring for 30 minutes at 0° C. or lower and for an additional 30 minutes at room temperature. Pour the reaction solution into a separating container and add 50 ml of water.
After adding 0 ml and shaking, the aqueous layer and chloroform layer were separated. Add chloride to the chloroform layer, dry it, and then filter it.
2-acryloyloxypropiophenone (hereinafter referred to as A-1
Synthesis Example 2 Synthesis example 2 except that 206 parts (1 mole) of 4'-isopropyl-2-hydroquine-2-methylpropiophenone was used instead of 2-hydroxy-2-methylglopiophenone in Synthesis Example 1. synthesized 4'-isopropyl-2-methyl-b-acryloyloxypropiophenone (hereinafter referred to as A-2) in the same manner as in Synthesis Example 1.

Example 1 From 40 parts of urethane acrylate synthesized from 1 mole of polypropylene glycol having a molecular ffi of 700, 2 moles of tolylene diisocyanate and 2 moles of hydroquine ethyl acrylate, 55 parts of phenoxyethyl acrylate, and 15 parts of A-1 synthesized in Synthesis Example 1. A curable composition was coated onto a glass plate to a film thickness of approximately 150 μm. Next, this coating film was cured by irradiating ultraviolet rays of 500 mj/7 using a high-pressure mercury lamp, and then the cured coating film was removed from the glass plate.
jIshita. The obtained cured coating film was extracted for 15 hours using a Soxhlet extractor using A7T as a solvent, and the residue was dried and weighed to obtain a gel fraction. The gel content was 98.4%.

Furthermore, when the cured coating 114γ was left in a constant temperature tank at 100° C. for 5 days, the weight decreased by 068”.

Comparative Example 1 Ultraviolet rays were irradiated in the same manner as in Example 1 except that part A-15 was not used, but no curing occurred.

Example 2 Evaluation was carried out in the same manner as in Example 1 using a resin having the composition shown in Table 1. The results are summarized in Table 1.

Example 3 A cured coating film was prepared in the same manner as in Example 1 using a resin having the composition shown in Table 2 (=). After this hardened coating film and this coating film were left at 100°C for 5 days, The tensile strength and roughness of the coating film were measured according to JISK-6301.The results are summarized in Table 2.

〔Effect of the invention〕

As is clear from the examples, the curable composition containing the sensitizer of the present invention cures without using a conventional so-called sensitizer. Even when the curable composition is cured, there is little weight loss and little change in physical properties. It can be used in fields where it could not be used due to the migration of uncured components from the cured product during use or large changes in physical properties.

Claims (1)

[Claims] 1. Formula ▲ Numerical formula, chemical formula, table, etc. ▼ (1) [In the formula, R_1 is H or an alkyl group having 1 to 4 carbon atoms,
An acryloyloxypropiophenone derivative represented by R_2 is H or a methyl group. 2. Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (1) [In the formula, R_1 is H or an alkyl group having 1 to 4 carbon atoms,
A sensitizer for active energy ray-curable compositions comprising an acryloyloxypropiophenone derivative represented by R_2 is H or a methyl group.