JPH1025316A - Polyfunctional vinyl ether compound, polymerizable composition and cured product therefrom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound useful as e.g. a coating agent as a polymerizable compound of low skin irritancy by vinyl etherification of the phenolic OH group of a specific polymer. SOLUTION: This new compound is obtained by vinyl etherification of the phenolic OH group of (A) a phenol-modified butadiene oligomer prepared by addition reaction of (ii) a phenolic compound to (i) a butadiene oligomer with (B) a vinyl ether group-bearing compound of the formula (R is a 1-10C alkylene; (q) is 0-10) (e.g. chloroethyl vinyl either). It is preferable that the vinyl etherification is carried out, for example, in the presence of a basic compound such as sodium hydroxide by combined use of a phase-transfer catalyst such as tetrabutylammonium bromide in a solvent such as dimethyl sulfoxide at 60-110 deg.C for about 7-10h.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel polyfunctional vinyl ether compound used for a polymerizable composition, a polymerizable composition containing the polyfunctional vinyl ether compound, 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: Butadiene Low (co) polymer in phenol added phenol butadiene low is obtained (co) polymer phenolic OH group a general formula of _{- {R-O-} q -CH} = CH 2 ( wherein R Is a linear or branched alkylene group having 1 to 10 carbon atoms, q is an integer of 0 to 10), and a polyfunctional vinyl ether compound obtained by vinyl etherification with a compound having a vinyl ether group represented by the formula: A polymerization initiator; 2. A polymerizable composition containing the polyfunctional vinyl ether compound according to the above. The above 2. It is intended to provide a cured product obtained by curing the polymerizable composition described above.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION As a general method for synthesizing the polyfunctional vinyl ether compound of the present invention, a low-butadiene (co) polymer and a phenolated low-butadiene (co) polymer obtained by adding phenols are provided. Acetylene, or general formula (A) Z- {RO} _r -CH = CH ₂ (A) (wherein Z is a halogen atom, R is a linear or branched alkylene group having 1 to 10 carbon atoms, r Are each an integer of 0 to 10.) in the presence of a basic compound.

Specific examples of the compound of the formula (A) that can be used include chloroethyl vinyl ether, chlorobutyl vinyl ether and bromoethyl vinyl ether. The amount of the compound of the formula (A) to be used is usually 0.1 mol or more, preferably 0.3 mol or more, particularly preferably 1 mol equivalent to 1 mol equivalent of the phenolic OH group of the phenolated butadiene low (co) polymer. 1 to 3 mol.

[0007] Examples of a method for synthesizing a phenolated low-butadiene (co) polymer include a method of adding phenols to a low-butadiene (co) polymer. The butadiene (co) polymer preferably has a number average molecular weight of 300 to 3000, more preferably 500 to 200.
0 butadiene low polymer, or a low copolymer of butadiene and a conjugated diolefin and / or an aromatic vinyl monomer.

The low polymer of butadiene can be produced by a known method. For example, it can be produced by a method in which butadiene is anionically polymerized at a temperature of 0 to 100 ° C. using an alkali metal or organic alkali metal compound as a catalyst. In this case, in order to control the molecular weight and obtain a low polymer having a small gel content, an organic alkali metal compound such as benzyl sodium is used as a catalyst, and a compound having an alkylaryl group, for example, toluene is used as a chain transfer agent. Chain transfer polymerization method, living polymerization method using a polycyclic aromatic compound such as naphthalene as an activator in a tetrahydrofuran solvent and an alkali metal catalyst such as sodium as a catalyst, aromatic hydrocarbons such as toluene and xylene as a solvent, sodium, etc. A polymerization method in which a molecular weight is controlled by adding an ether such as dioxane using an alkali metal as a catalyst, or a coordination using a acetylacenate compound of a Group VIII metal such as cobalt or nickel and an alkylaluminum halide as a catalyst A method such as an anionic polymerization method is preferred.

The low-butadiene copolymer is preferably, for example, 3 to 40 mol%, more preferably 5 to 30 mol% of isoprene, 2,
It can be produced by copolymerizing a conjugated olefin such as 3-dimethylbutadiene and piperylene or an aromatic vinyl monomer such as styrene, α-methylstyrene, vinyltoluene and vinylbenzene.

The method for adding phenols to the butadiene low (co) polymer is not particularly limited, and for example, a method described in JP-A-61-126162 can be used.

That is, a method of reacting a butadiene low (co) polymer with a phenol or the like in the presence of a Lewis acid catalyst can be used. Specific examples of phenols that can be used at this time include phenol, o-cresol, m
-Cresol, p-cresol, 2,4-dimethylphenol, 2,6-dimethylphenol, 2-tertbutyl-5-methylphenol, brominated phenol, hydroquinone, 2-methylhydroquinone, resorcinol,
Catechol, 1 naphthol, 2 naphthol, 2, 7
Examples include, but are not limited to, dihydroxynaphthalene and 1,6-dihydroxynaphthalene.

The amount of the phenols to be used must be larger than the number of moles of the double bond present in the low butadiene (co) polymer, preferably 1.2 times or more, more preferably 1.2 times or more. Is 1.2 to 2 moles. Also,
The addition amount of phenols is preferably from 0.25 to 0.5 mol, and more preferably from 0.27 to 0.45 mol, per 1 mol of the double bond present in the butadiene low (co) polymer. Is particularly preferred.

Specific examples of the usable Lewis acid catalyst include boron trifluoride complexes such as boron trifluoride / ether complex and boron trifluoride / phenol complex. The amount of the Lewis acid catalyst used is not particularly limited,
It can be appropriately selected according to the type of the catalyst to be used. For example, when boron trifluoride is used, the amount is preferably 5 to 50 mmol, more preferably 10 to 20 mmol, per 100 g of the butadiene low (co) polymer.

The reaction of adding a phenol to the butadiene low (co) polymer can be carried out usually at 50 to 120 ° C., preferably at 70 to 100 ° C.

In the above reaction, a cyclization reaction of the double bond present in the butadiene (co) polymer is caused simultaneously with the addition reaction of the phenols, and heat is generated. , And / or a method of sequentially adding a low-butadiene (co) polymer, and the like, are particularly preferable.

In the above reaction, a small amount of an inert solvent such as toluene is used for the purpose of lowering the viscosity of the reaction mixture.
Xylene or the like can also be used. Further, the amount of water in the reaction mixture is usually 100 ppm by weight or less, preferably 60 ppm by weight or less.

The phenolated butadiene low (co) polymer obtained by the above reaction has a softening point of 90 to 200 ° C, preferably 100 to 160 ° C, and a hydroxyl equivalent of usually 250 to 200 ° C.
It is preferably 700 g / equivalent, preferably 280-600 g / equivalent.

The polyfunctional vinyl ether compound of the present invention comprises
It can be obtained by adding acetylene to the phenolic OH group of the phenolated butadiene low (co) polymer obtained as described above, or by reacting the OH group with the compound of the formula (A). The reaction for adding acetylene is carried out by a known method using potassium hydroxide, potassium alcoholate, sodium hydroxide, sodium alcoholate or the like as a catalyst. The reaction pressure is from normal pressure to 100 kg /
cm ² , preferably normal pressure to 50 kg / cm ² , the reaction temperature is 30 to 250 ° C., preferably 60 to 200 ° C., and the reaction time is 4 to 15 hours, preferably 6 to 12 hours, but is not limited thereto. Not something. The target compound can be obtained by purifying the reaction product by distillation or the like.

When the phenolated butadiene (low) copolymer is reacted with the haloalkyleneoxyvinyl compound of the formula (A) in the presence of a basic substance, a specific example of a basic compound that can be used is water. Alkali metal compounds such as sodium oxide, potassium hydroxide and sodium hydride; alkali metal alcoholates such as sodium methylate; and alkali metals such as sodium metal are used in low (co) weight phenolated butadiene. It is usually 0.5 to 10 mol, preferably 1.0 to 3.0 mol, per 1.0 mol equivalent of the combined phenolic OH group. At this time, tetrabutylammonium bromide, benzyltriethylammonium chloride, trioctylmethylammonium chloride, tetrabutylammonium hydrogen sulfate, dicyclohexyl-18
-Crown-6, dibenzo-18-crown-6,18
If a phase transfer catalyst such as Crown-6 and polyethylene glycol 400 is used in combination, the reaction is further promoted. The amount used is 0.1 to 20 with respect to 1.0 molar equivalent of the phenolic OH group of the phenolated butadiene low (co) polymer.
Mol%, preferably 0.5 to 10 mol%.

The reaction is carried out in an inert solvent such as dimethylsulfoxide, dimethylsulfone, dimethylformamide,
The reaction may be performed in a solvent such as an aprotic polar solvent such as N-methylpyrrolidone or N, N-dimethylimidazolidone. The reaction temperature is usually 30 to 150 ° C, preferably 60 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, and the organic layer is extracted with methyl ethyl ketone, methyl isobutyl ketone, etc., and washed several times with water, so that unreacted phenolated butadiene low (co) polymer, by-product inorganic salt Is removed, and the organic layer is dried with a desiccant such as anhydrous sodium sulfate, and then the solvent is removed under reduced pressure to obtain the desired product.

The polyfunctional vinyl ether compound of the present invention comprises
The polymerizable composition of the present invention can be obtained by mixing a polymerization initiator and, if necessary, various polymerizable compounds, dyes, pigments, plasticizers, inorganic fillers, solvents and the like. 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-52-1.
4277, JP-B-52-14278, JP-B-52-14279, JP-B-52-25686, JP-B-61
-34752, JP-A-54-53181, JP-A-5-53181
4-95686, JP-B-61-36530, JP-B-59-19581, JP-B-63-65688, JP-A-55-164204, JP-B-60-30690,
JP-B-63-36332, JP-B1-39423,
Japanese Patent Publication No. 2-10171, Japanese Patent Publication 5-15721, Japanese Patent Publication No. 4-621310, Japanese Patent Publication No. 62-57653, Japanese Patent Publication No. 3-12081, Japanese Patent Publication No. 3-12082, Japanese Patent Publication No. 3-16361, Japanese Patent Publication No. JP-B-63-12092, JP-B-63-12093, JP-B-63-12095, JP-B-63-12094, JP-B-2-37924, JP-B-2-35764, JP-B-4-13374, JP-B 4-75908, JP-B-4-73428, JP-B-53-32831, JP-A-2-150848, JP-A-2-296514, U.S. Pat. No. 4,069,055.
No. 4,069,056, U.S. Pat.
No. 703,296, etc., sulfonium salts, diazonium salts, ammonium salts, phosphonium salts, iodonium salts, arsonium salts, iron / arene complexes and the like. These polymerization initiators are usually used in an amount of 0.01 to 50 based on the polyfunctional vinyl ether compound of the present invention.
% By weight, preferably 0.1 to 20% by weight, and may be mixed with the polyfunctional vinyl ether compound of the present invention when obtaining the cured product of the present invention, or may be mixed in the polymerizable composition. .

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

[0023]

The polyfunctional vinyl ether compound obtained by the present invention is used as a polymerizable compound having low skin irritation in various fields such as coating agents, inks, 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.

[0024]

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 In a reactor equipped with a thermometer, a reflux condenser, a dropping funnel, a nitrogen introducing device, and a stirring device, phenolated butadiene low (co) was added.
Polymer (Nippon Petrochemical Co., Ltd., hydroxyl equivalent 317 g /
eq, trade name "Nisseki special phenolic resin PP-700-
300 "), 32 g of dimethyl sulfoxide and 40 ml of dimethyl sulfoxide were charged and dissolved, and then 12 g of powdered potassium hydroxide was added, followed by stirring at 60 ° C. for 30 minutes. Then, 42 g of 2-chloroethyl vinyl ether is added dropwise over 60 to 90 minutes while maintaining the temperature in the reactor at 70 ° C. 75-80
Stirring is continued at 5 ° C. for 5 hours to complete the reaction. The reaction solution was cooled to room temperature, and methyl ethyl ketone 200 g, water 300 g
, The target compound is extracted into the organic layer, the inorganic salt is added to the aqueous layer,
Dissolve unreacted raw materials. Next, the aqueous layer is separated with a separating funnel, and the organic layer is washed with water five times. Anhydrous sodium sulfate is added to the organic layer and the mixture is left overnight. After filtration, methyl ethyl ketone and excess chloroethyl vinyl ether were distilled off under reduced pressure to obtain 33 g of the desired compound. 1610 cm ^-1 in the infrared absorption spectrum of the product, absorption by a vinyl group in 975cm ^-1, observed absorption by ether bond 1200 cm ^-1, the absorption due to hydroxyl group near 3400 cm ^-1 disappeared completely It was confirmed that it was a more desired polyfunctional vinyl ether compound of the present invention.
(Compound A)

Example 2 In an autoclave reactor equipped with a thermometer and a gas inlet tube, 32 g of Nisseki special phenol resin PP-700-300 was added.
After charging and dissolving 50 ml of dimethyl sulfoxide,
8 g of powdered potassium hydroxide was added and heated to 110 ° C. Nitrogen gas is added to this to make the pressure 10 kg / cm ² , and acetylene is added to make it 15 kg / cm ² . When the introduction of acetylene is completed, the introduction of acetylene is stopped, the mixture is cooled, a gas is released, and the reaction product is taken out at normal pressure. Add methyl ethyl ketone 20 to the reaction mixture.
0 g and 300 g of water are added, the target compound is extracted into the organic layer, and the unreacted raw material is dissolved in the aqueous layer. Next, the aqueous layer is separated with a separating funnel, and the organic layer is washed with water five times. Anhydrous sodium sulfate is added to the organic layer and the mixture is left overnight. After filtration,
Methyl ethyl ketone was distilled off under reduced pressure to obtain 21 g of the desired product. The infrared absorption spectrum of this product shows 1610c
m ^-1 , absorption at 975 cm ^-1 by vinyl group, 1250c
m- ¹ showed absorption by an ether bond, and 3400 c
Since the absorption by the hydroxyl group near m ^-1 was completely eliminated, it was confirmed that the compound was the intended polyfunctional vinyl ether compound of the present invention. (Compound B)

Test Example Each of the polyfunctional vinyl ether compounds of the present invention obtained in Examples 1 and 2 was used as a polymerizable composition having the following composition and subjected to a curing test. Composition of polymerizable composition Compounds A to B 10 parts Polymerization initiator (types are 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 each of the following curing judgment tests. 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.

[0028]

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 A SP-170 13 36 Compound B SP-170 1 25 Mixture of compound A and maleimide DETX-S247 (mixing weight ratio 5/5) Comparative example A SP-17036-Comparative example B SP-17058-

In Table 1, SP-170; Adeka optomer (photocationic polymerization initiator, manufactured by Asahi Denka Co., Ltd.) DETX-S; Kayacure (photopolymerization initiator, manufactured by Nippon Kayaku Co., Ltd.) Comparative Example A; Celloxide 2021 (alicyclic epoxy resin, manufactured by Daicel Corporation) Comparative Example B; Epicoat 828 (aromatic epoxy resin,
Yuka Shell Epoxy Co., Ltd.)

As is evident from Table 1, the polymerizable composition containing the polyfunctional vinyl ether compound of the present invention has an excellent curing rate, and therefore has a small number of irradiations.

Claims (3)

[Claims] A phenolic OH group of a phenolated butadiene low (co) polymer obtained by adding a phenol to a butadiene low (co) polymer is represented by the general formula-{RO-} _q -CH = CH ₂ (wherein R represents a linear or branched alkylene group having 1 to 10 carbon atoms, and q represents an integer of 0 to 10), and is a polyfunctional compound obtained by vinyl etherification with a compound having a vinyl ether group. Vinyl ether compounds. 2. A polymerizable composition comprising a polymerization initiator and the polyfunctional vinyl ether compound according to claim 1. 3. A cured product obtained by curing the polymerizable composition according to claim 2.