JPH107790A - Prolyfunctional vinyl ether, polymerizable composition, and cured material obtained therefrom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyfunctional vinyl ether which is useful in the fields of coating materials, inks, paints, adhesives, resists, plate making materials, etc., as a polymerizable compound lowly irritant to the skin by selecting a specified polyfunctional vinyl ether. SOLUTION: This vinyl ether is represented by formula I wherein A is O or S; V is a vinyl ether group represented by -(R4 -O-)q -CH=CH2 (wherein R4 is a 1-10C alkylene; and q is 1 to 10); R1 and R2 are each H, alkyl, phenyl, or an α-amino acid side chain; and X is a group of formula II [wherein n=0 or 1; n+m=1 or 2; and R3 is H or methyl]}. It is obtained by reacting a compound represented by formula III with a haloalkylenoxyvinyl compound represented by Z-(R4 -O-)r -CH=CH2 (wherein Z is halogeno; and or is 1 to 10) in the presence of a basic compound. It is mixed with a polymerization initiator, etc., for use as a polymerizable composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel polyfunctional vinyl ether, a polymerizable composition containing the polyfunctional vinyl ether, and a cured product thereof.

[0002]

2. Description of the Related Art At present, polymerizable compositions such as ultraviolet curable resins and electron beam curable resins are used in many fields such as inks, paints, adhesives, resists and plate-making materials. An acrylic monomer or a polyfunctional acrylic compound is used as the main agent.

[0003]

However, acrylic monomers have strong skin irritation and odor, and have problems in workability. Therefore, recently, vinyl ether compounds having low odor and little skin irritation have attracted attention. Further, since the vinyl ether compound is cationically polymerizable and has a high curing rate, the disadvantage of the acrylic compound can be improved. However, in the market, the types thereof are smaller than those of acrylic compounds, and the price is expensive, so that it is not possible to sufficiently meet the needs.

[0004]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems and completed the present invention. That is, the present invention provides (1) the following general formula (1)

[0005]

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(In the formula (1), A represents an oxygen atom or a sulfur atom. V represents a general formula-｛R ₄ -O-｝ _q -CH ＝ CH _{2, wherein} R ₄ is a linear or R ₁ and R ₂ each represent a hydrogen atom or an alkyl group, a phenyl group, or a side chain of an α-amino acid. X represents the general formula (2)

[0007]

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(Where n = 0 or 1 in the formula (2) and n +
m = 1 or 2. R ₃ represents a hydrogen atom or a methyl group. )) A polyfunctional vinyl ether represented by
(2) A polymerizable composition containing a polymerization initiator and the polyfunctional vinyl ether described in (1) above, and (3) a cured product obtained by curing the polymerizable composition described in (2) above. .

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION As a general method for synthesizing a compound represented by the general formula (1) described in the above (1), general formula (3)

[0010]

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(In the formula (3), A, R ₁ , R ₂ and X each have the same meaning as in the formula (1)) and a compound of the general formula (4) Z- ｛R ₄ − _{O-} r -CH = CH 2 (} 4) ( wherein Z represents a halogen atom, R ₄ is from 1 to 10 linear or branched alkylene group having a carbon number, r is represented an integer of 1 to 10, respectively. )) In the presence of a basic compound.

Specific examples of the compound of the formula (4) that can be used include chloroethyl vinyl ether, chlorobutyl vinyl ether and bromoethyl vinyl ether. The amount of the compound of the formula (4) to be used is generally 2 mol or more, preferably 3 mol or more, per 1 mol of the compound of the formula (3).

In the compound represented by the general formula (3), R
_As the alkyl group of ₁ , R ₂ , an alkyl group having 1 to 4 carbon atoms is preferable, and as a side chain of the α-amino acid,
In addition to alkyl groups such as methyl group, isopropyl group, isobutyl group and secondary butyl group, carboxymethyl group, carbamoylmethyl group, β-carboxyethyl group, β-carbamoylethyl group, mercaptomethyl group,
Preferred specific examples include a β-methylthioethyl group, an ω-aminobutyl group, an N-amidino γ-aminopropyl group, and a benzyl group.

Specific examples of the compounds of the formula (3) which can be used include 2,4-imidazolidione, 5-methyl-2--4-imidazolidione, 5,5'-dimethyl-2-4-imidazolidione and 2-thioxo. 4-imidazolidinone,
2-imidazolididone, 2-thioxoimidazolidone,
4-methyl-2-imidazolidone, 4,4'-dimethyl-2-imidazolidone, 4,5-dimethyl-2-imidazolidone, 5-methylthioethyl-2--4-imidazolidione, 5-phenyl-2-4-imidazolidione, tetrahydro-2-pyrimidinone, 5,6 Examples include dihydrouracil, 5,6 dihydrothymine and the like, but are not limited thereto as long as the compound is represented by the formula (3).

Specific examples of the basic compound which can be used in the reaction of the compound of the formula (3) with the haloalkyleneoxyvinyl compound of the formula (4) include sodium hydroxide, potassium hydroxide and sodium hydride. Alkali metal compounds,
Examples thereof include an alkali metal alcoholate such as sodium methylate and an alkali metal such as sodium metal, and the amount thereof is usually 0.5 to 10 mol, preferably 2 to 10 mol, per 1.0 mol of the compound of the formula (3). 0.0 to 4.0 mol. At this time, tetrabutylammonium bromide, benzyltriethylammonium chloride, trioctylmethylammonium chloride, tetrabutylammonium hydrogen sulfate, dicyclohexyl-18-crown-6, dibenzo-18-crown-6, 18-crown-6, polyethylene glycol 40
If a phase transfer catalyst such as 0 is used in combination, the reaction is further promoted. The amount of the phase transfer catalyst used is the compound of formula (3) 1.0
Usually 0.1 to 20 mol%, preferably 0.1 to 20 mol%, is used.
5 to 10 mol%.

The reaction is carried out in an inert solvent such as dimethylsulfoxide, dimethylsulfone, dimethylformamide,
It may be carried out in a solvent such as an aprotic polar solvent such as N-methylpyrrolidone and N, N-dimethylimidazolidone. The reaction temperature is usually 30 to 150 ° C., preferably 6
The reaction time is usually 0 to 110 ° C and the reaction time is usually 5 to 12 hours, preferably 7 to 10 hours. Further, the reaction can be allowed to proceed while removing the water generated by the reaction outside the reaction system. After completion of the reaction, the reaction mixture is cooled to room temperature, the by-produced inorganic salt is filtered off, and the reaction solvent is distilled off under reduced pressure. Next, the product represented by the general formula (1) is extracted from the reaction mixture with an aliphatic hydrocarbon such as hexane or heptane, and the extraction solvent is evaporated under reduced pressure to obtain the desired product.

The polymerizable composition of the present invention is obtained by mixing the polyfunctional vinyl ether of the present invention, a polymerization initiator, and other various polymerizable compounds, dyes, pigments, plasticizers, inorganic fillers, and solvents as required. Can be obtained. The polymerization initiator is not particularly limited as long as it can cause radical polymerization or ionic (cation) polymerization, such as a thermal polymerization initiator, a photoradical or a cationic photopolymerization initiator. Specific examples of the thermal polymerization initiator that can be used include benzoyl peroxide, acetyl peroxide, lauroyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, azobisisobutyronitrile, azobis-2-4-dimethylvalero. Examples thereof include nitrile and azobiscyclohexanecarbonitrile. Specific examples of the photoradical polymerization initiator that can be used include 2,4-diethylthioxanthone, benzophenone, 4-dimethylaminoisoamylbenzoate, and 4-dimethylaminoethylbenzoate. Specific examples of the cationic photopolymerization initiator that can be used include JP-B-53-32831 and JP-B-52-1427.
7, No. 52-14278, No. 52-142
79, JP-B-52-25686, JP-B-61-34
No. 752, JP-A-54-53181, JP-A-54-9
No. 5686, JP-B-61-36530, JP-B-59-19581, JP-B-63-65688, JP-A-55
-164204, JP-B-60-30690, JP-B63-36332, JP-B1-39423, JP-B2-10171, JP-B5-15721, and JP-B-4
-62310, JP-B 62-57653, JP-B-3
No. 12081, No. 3-12082, No. 3-16361, No. 63-12092, No. 63
No. 12093, No. 63-12095, No. 6
3-12094, Tokuhei 2-37924, Tokuhei 2
JP-A-35764, JP-B-4-13374, JP-B4-75908, JP-B4-73428, JP-B-53-32831, JP-A-2-150848, JP-A-2-296514, U.S. Pat. U.S. Pat. No. 4,069,056; U.S. Pat.
No. 3,296, for example, arylsulfonium salts, aryldiazonium salts, ammonium salts, phosphonium salts, aryliodonium salts, arsonium salts, arylselenonium salts, and iron / arene complexes. These polymerization initiators are usually used in an amount of 0.01 to 50% by weight, preferably 0.1% by weight, based on the compound of the formula (1).
When used to obtain the cured product of the present invention, it may be mixed with the compound of the formula (1) or may be mixed in the polymerizable composition of the present invention.

The cured product of the present invention can be obtained by irradiating or heating the polyfunctional vinyl ether of the present invention as it is, preferably as the polymerizable composition of the present invention, with an electron beam or radiation.

[0019]

Industrial Applicability The polyfunctional vinyl ether of the present invention is a polymerizable compound having low skin irritation as a coating agent, an ink,
It is extremely useful in various fields such as paints, adhesives, resists, and plate-making materials. Particularly, a polymerizable composition with a cationic photopolymerization initiator has a feature that the curing speed is high and the polymerization is hardly inhibited by oxygen. Further, since most of the polyfunctional vinyl ethers obtained in the present invention are also water-soluble, water can be used as a diluent, or when used as an image forming resin, development with water is possible. .

[0020]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Example 1 2-4-imidazolidione 40 was added to a reactor equipped with a thermometer, a reflux condenser, a dropping funnel, a nitrogen introducing device and a stirring device.
g, 160 ml of dimethyl sulfoxide and dissolved therein, 23 g of powdered potassium hydroxide was added, and the mixture was heated to 70 ° C. Then, 2-chloroethyl vinyl ether 84.
8 g is added dropwise with stirring over a period of 60 to 90 minutes while maintaining the temperature in the reactor at 70 ° C. Further, stirring is continued at 75 to 80 ° C. for 5 hours to complete the reaction. The reaction solution is cooled to room temperature, and the by-product inorganic salt is filtered off. Then, dimethyl sulfoxide was distilled off from the reaction solution under reduced pressure, and 500 m
Add 1 hexane and extract the product at 60 ° C. Then, hexane was evaporated from the extract under reduced pressure to obtain 81 g of a product. The infrared absorption spectrum of the product shows 161
0 cm ^-1, absorption by a vinyl group in 975cm ^-1, 120
At 0 cm ^-1 , absorption due to an ether bond was recognized, and 320
The disappearance of the absorption by the amino group at around 0 cm ^-1 confirmed that the target polyfunctional vinyl ether of the present invention was obtained. (Compound 1)

Example 2 43.1 g of 2-imidazolidone was placed in a reactor equipped with a thermometer, a reflux condenser, a dropping funnel, a nitrogen introducing device, and a stirring device.
After 160 ml of dimethyl sulfoxide is charged and dissolved, 40 g of powdery sodium hydroxide is added, and the mixture is heated to 70 ° C. Next, 2-chloroethyl vinyl ether 159
g is added dropwise with stirring over a period of 60 to 90 minutes while maintaining the temperature inside the reactor at 70 ° C. Further, stirring is continued at 75 to 80 ° C. for 5 hours to complete the reaction. The reaction solution is cooled to room temperature, and the by-product inorganic salt is filtered off. Then, dimethyl sulfoxide and excess 2-chloroethyl vinyl ether are distilled off from the reaction solution under reduced pressure, and 500 ml of hexane is added to the residue to extract the product at 60 ° C. Then, hexane was evaporated from the extract under reduced pressure to obtain 90 g of a product. 1610c in infrared absorption spectrum of product
m ^-1 , absorption at 975 cm ^-1 by vinyl group, 1200 c
m- ¹ , absorption by an ether bond was observed, and 3200 c
The disappearance of the absorption by the amino group near m ^-1 confirmed that the target polyfunctional vinyl ether of the present invention was obtained. (Compound 2)

Example 3 A reactor equipped with a thermometer, a reflux condenser, a dropping funnel, a nitrogen introducing device and a stirring device was charged with 51.2 g of 5,5'-dimethyl-2-4-imidazolidione and 10% of dimethyl sulfoxide.
After 0 ml was charged and dissolved, 40 g of powdered sodium hydroxide was added, and the mixture was heated to 70 ° C. Then, 159 g of 2-chloroethyl vinyl ether is added dropwise with stirring over a period of 60 to 90 minutes while maintaining the temperature in the reactor at 70 ° C. Further, stirring is continued at 75 to 80 ° C. for 5 hours to complete the reaction. The reaction solution is cooled to room temperature, and the by-product inorganic salt is filtered off. Then, dimethyl sulfoxide and excess 2-chloroethyl vinyl ether are distilled off from the reaction solution under reduced pressure, and 500 ml of hexane is added to the residue to extract the product at 60 ° C. Then, hexane was evaporated from the extract under reduced pressure to obtain 110 g of a product. Product 1610 cm ^-1 in the infrared absorption spectrum of the absorption by the vinyl group 975Cm ^-1, observed absorption by ether bond 1200 cm ^-1, object than to absorption by amino group near 3200 cm ^-1 had disappeared It was confirmed to be a polyfunctional vinyl ether of the present invention. (Compound 3)

EXAMPLE 4 57.6 g of 5,5'-dimethyl-2-thioxo-4-imidazolidinone, 57.6 g of dimethyl sulfoxide were placed in a reactor equipped with a thermometer, a reflux condenser, a dropping funnel, a nitrogen introducing device and a stirring device. After charging and dissolving 100 ml, 40 g of powdered sodium hydroxide is added and heated to 70 ° C. Then 2
159 g of chloroethyl vinyl ether is added dropwise with stirring over a period of 60 to 90 minutes while maintaining the temperature in the reactor at 70 ° C. Further, stirring is continued at 75 to 80 ° C. for 5 hours to complete the reaction. The reaction solution is cooled to room temperature, and the by-product inorganic salt is filtered off. Then, dimethyl sulfoxide and excess 2-chloroethyl vinyl ether are distilled off from the reaction solution under reduced pressure, and 500 ml of hexane is added to the residue to extract the product at 60 ° C. Then, hexane was evaporated from the extract under reduced pressure to obtain 95 g of a product. Product 1610 cm ^-1 in the infrared absorption spectrum of the absorption by the vinyl group 975Cm ^-1, observed absorption by ether bond 1200 cm ^-1, object than to absorption by amino group near 3200 cm ^-1 had disappeared It was confirmed to be a polyfunctional vinyl ether of the present invention. (Compound 4)

Example 5 5,6-Dihydrouracil was placed in a reactor equipped with a thermometer, a reflux condenser, a dropping funnel, a nitrogen introducing device, and a stirring device.
After 6 g and 160 ml of dimethyl sulfoxide are charged and dissolved, 23 g of powdered potassium hydroxide is added, and the mixture is heated to 70 ° C. Then 2-chloroethyl vinyl ether 8
4.8 g was added to 60 to 9 while maintaining the temperature in the reactor at 70 ° C.
Add dropwise over 0 minutes with stirring. Further, stirring is continued at 75 to 80 ° C. for 5 hours to complete the reaction. The reaction solution is cooled to room temperature, and the by-product inorganic salt is filtered off. Then, dimethyl sulfoxide was distilled off from the reaction solution under reduced pressure, and 50
Add 0 ml of hexane and extract the product at 60 ° C.
Then, hexane was evaporated from the extract under reduced pressure to give 76 g.
Was obtained. The product has an infrared absorption spectrum of 1
610 cm ^-1, absorption by a vinyl group in 975cm ^-1, 1
Absorption due to an ether bond was observed at 200 cm ^-1 and 3
The disappearance of the absorption by the amino group at around 200 cm ^-1 confirmed that the target polyfunctional vinyl ether of the present invention was obtained. (Compound 5)

Test Example Each of the polyfunctional vinyl ethers of the present invention obtained in Examples 1 to 5 was used as the following polymerizable composition, and a curing test was performed. Composition of polymerizable composition Compounds 1 to 5 10 parts Polymerization initiator (type is shown in Table 1) 0.1 part Solvent (methyl ethyl ketone) 3 parts Curing method Photocuring; Apply polymerizable composition to PET film with RI tester (Film thickness 10 μm), and after drying, a high-pressure mercury lamp 80 W /
cm 1 light, under lamp 10cm, conveyor speed 1
0, 20, 50 m / min. Irradiation was repeated several times for the following curing judgment test. Determination of curing: The number of passes (the number of repetitions of irradiation) in which the resin film was not peeled off in 50 MEK (methyl ethyl ketone) rubbing tests was determined to be curing. Table 1 shows the results.

[0027]

Table 1 Table 1 Number of passes before curing Conveyor speed (m / min.) 10 20 50 Composition of polymerizable composition Vinyl ether Polymerization initiator Compound 1 PCI-020 1 24 Compound 2 PCI-020 1 25 Mixture of compound 1 and maleimide DETX-S236 (mixing weight ratio 5/5) Compound 3 PCI-020113 Compound 4 PCI-020124 Compound 5 PCI-020125 Comparative Example 1 SP-170 36-Comparative Example 2 SP-170 58-

In Table 1, PCI-020; Photopolymerization initiator (Nippon Kayaku Co., Ltd.) DETX-S; Kayakua (Photopolymerization initiator, Nippon Kayaku Co., Ltd.) SP-170; Adeka Optomer ( Photocationic polymerization initiator, manufactured by Asahi Denka Co., Ltd.) Comparative Example 1; Celloxide 2021 (alicyclic epoxy resin, manufactured by Daicel Co., Ltd.) Comparative Example 2: Epicoat 828 (aromatic epoxy resin,
Yuka Shell Epoxy (manufactured by Corporation)

As is clear from Table 1, the polymerizable composition containing the vinyl ether of the present invention has a low curing frequency because of its excellent curing rate.

Claims (3)

[Claims] (1) The following general formula (1): (Equation (1) Medium A is .V general formula represents an oxygen atom or a sulfur atom _{- {R 4 -O-} q -CH} = CH 2 (R 4 is a straight-chain also branched in 1 to 10 carbon atoms R ₁ and R ₂ each represent a hydrogen atom or an alkyl group, a phenyl group, or a side chain of an α-amino acid. Is the general formula (2) (Where n = 0 or 1 and n + m = 1 or 2 in the formula (2), and R ₃ represents a hydrogen atom or a methyl group.). 2. A polymerizable composition comprising a polymerization initiator and the polyfunctional vinyl ether according to claim 1. 3. A cured product obtained by curing the polymerizable composition according to claim 2.