JP2000026444A - Oxetane compound and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new oxetane compound excellent in radical polymerization reactivity and cationic polymerization reactivity, and copolymerizability with a poorly compatible fluorovinyl monomer as well, and useful as e.g. a photocurable component. SOLUTION: This new oxetane compound is a compound of formula I (R1 is H, an alkyl, F, a fluoroalkyl, allkyl, an aryl, furyl or thienyl; R2 to R4 are each H or a 1-6C alkyl; (m) and (n) are each 1-10), e.g. 2-(3-methyl-3- oxetanemethoxy)ethyl vinyl ether. The compound of formula I is obtained by reaction between an oxetane alcohol of formula II and a halogenated vinyl ether compound of formula III (X is a halogen) in the presence of a phase- transfer catalyst such as a quaternary ammonium salt.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an oxetane compound and a method for producing the same. More specifically, an oxetane compound having excellent radical polymerization reactivity and cationic polymerization reactivity, and having excellent compatibility and copolymerizability with other unsaturated monomers (such as vinyl monomers) and its oxetane compound can be efficiently obtained. It relates to a manufacturing method.

[0002]

2. Description of the Related Art Epoxy resins are frequently used as photocurable components in photocurable compositions because of their excellent heat resistance, excellent adhesion to various adherends, and excellent cationic polymerization. However, the photocurable composition using the conventional epoxy resin has a problem that in the presence of an acid and an alkali, the reaction is not easy to control and the reaction occurs even at room temperature, resulting in poor storage stability and poor usability. Was seen. For this reason, in a photocurable composition using an epoxy resin, a proposal has been made of physically separating a photocurable component and a photocurable catalyst into a so-called two-pack type. However, the photocurable component and the photocurable catalyst had to be uniformly mixed before use, which was inconvenient to use and poor in photocuring due to insufficient mixing.

Accordingly, oxetane compounds have been proposed as resins capable of cationic polymerization instead of epoxy resins. For example, Japanese Patent Application Laid-Open Nos.
No. 53711, JP-A-7-62082, JP-A-9-31186, JP-A-7-173279 and JP-A-9-143259 disclose an oxetane compound containing no ether bond other than an oxetane group. A photocurable oxetane composition (active energy ray-curable composition) as a main component is disclosed.

Further, JP-A-7-17958 discloses an oxetane compound represented by the following general formula (4), an ultraviolet-curable composition comprising such an oxetane compound and a cationic photopolymerization initiator, and Patissone ( Pattiso
n, J. Am. Chem. Soc., 1958, 79), which discloses a method for producing an oxetane compound.

[0005]

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[In the general formula (4), T ¹ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a fluorine atom,
6 is a fluoroalkyl group, an allyl group, an aryl group, a furyl group or a thienyl group, T ² is an alkyl group having 1 to 6 carbon atoms, and T ³ is a hydrogen atom or 1 to 6 carbon atoms.
6 alkyl groups. ]

However, the above-mentioned oxetane compounds have a problem that they are poor in radical polymerizability and poor in copolymerizability with other vinyl monomers. The oxetane compound represented by the general formula (4) is synthesized using a Patisson synthesis method. In such a synthesis method, an oxetane compound containing a plurality of ether bonds other than an oxetane group in a molecule is used. The compound could not be synthesized.

[0008]

As a result of intensive studies, the inventors of the present invention have found that the above problem can be solved by including a plurality of ether bonds other than oxetane groups in the molecule of the oxetane compound. . That is, by containing a plurality of ether bonds other than the oxetane group in the molecule, the radical polymerizability of the unsaturated group in the oxetane compound was remarkably accelerated, and the cationic polymerizability of the oxetane group in the oxetane compound could be maintained as it was. .

In addition, by including a plurality of ether bonds other than the oxetane group in the molecule, the compatibility with other copolymerizable monomers is improved, and further, since the radical polymerizability is improved, the uniformity is improved. It has been found that a copolymer can be obtained. Therefore, an object of the present invention is to provide an oxetane compound having excellent radical polymerization reactivity and cationic polymerization reactivity, and also having excellent copolymerizability.
Another object of the present invention is to provide a method for efficiently producing an oxetane compound.

[0010]

According to the present invention, there is provided a compound represented by the general formula (1):
Is an oxetane compound containing a plurality of ether bonds other than the oxetane group in the molecule.

[0011]

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[0012] In General Formula (1), the substituent R ¹ is hydrogen atom, an alkyl group, a fluorine atom, a fluoroalkyl group, an allyl group, an aryl group, a furyl group or a thienyl group, a substituted group R ^2, R ³ and R ⁴ are a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, respectively, m and n
Is an integer of 1 to 10, respectively. ]

With such a structure, an oxetane compound having excellent radical polymerization reactivity and cationic polymerization reactivity, and excellent compatibility with other copolymerizable monomers can be obtained.

In constituting the oxetane compound of the present invention, the substituents R ² , R ³ and R ⁴ in the unsaturated group are each preferably a hydrogen atom.

Further, in constituting the oxetane compound of the present invention, the substituent R ¹ is a hydrogen atom or a group having 1 to 4 carbon atoms.
Is preferably an alkyl group.

In forming the oxetane compound of the present invention, the number of repetitions m is preferably an integer of 1 to 4, and the number of repetitions n is preferably an integer of 2 to 5.

Another aspect of the present invention is a method for producing an oxetane compound represented by the above general formula (1), wherein the oxetane alcohol compound represented by the general formula (2) and the oxetane alcohol compound represented by the general formula (3) The present invention relates to a process for producing an oxetane compound, characterized by reacting a halogenated vinyl ether compound represented by the formula (1) in the presence of a phase transfer catalyst.

[0018]

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[In the general formula (2), the substituent R ¹ and the number of repetitions m are the same as those in the general formula (1). ]

[0020]

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[In the general formula (3), the substituents R ² , R ³ , R
⁴ and the number of repetitions n are the same as those in the general formula (1), and X is a halogen atom. ]

By adopting such a production method, it is possible to efficiently produce an oxetane compound having excellent radical polymerization reactivity and cationic polymerization reactivity and also having excellent compatibility with other copolymerizable monomers. it can.

In carrying out the process for producing an oxetane compound of the present invention, the halogenated vinyl ether compound represented by the general formula (3) is used per mole of the oxetane alcohol compound represented by the general formula (2). To
The reaction is preferably carried out within the range of 0.1 to 10 mol.

In carrying out the process for producing an oxetane compound of the present invention, the halogen atom in the halogenated vinyl ether compound represented by the general formula (3) is preferably chloro or bromo.

In carrying out the process for producing an oxetane compound of the present invention, the phase transfer catalyst is preferably a quaternary ammonium salt and / or a quaternary phosphonium salt.

In carrying out the process for producing an oxetane compound of the present invention, the oxetane alcohol compound represented by the general formula (2) and the halogenated vinyl ether compound represented by the general formula (3) are treated under alkaline conditions. It is preferred to react below.

In carrying out the method for producing an oxetane compound of the present invention, the oxetane alcohol compound represented by the general formula (2) and the halogenated vinyl ether compound represented by the general formula (3) are treated with 0 to 10 The reaction is preferably carried out at a temperature in the range of 100 ° C.

[0028]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be specifically described from the viewpoints of the structure of an oxetane compound, a method for producing an oxetane compound, and a use example (photocurable composition) of the oxetane compound.

[First Embodiment] A first embodiment of the present invention is an oxetane compound having a plurality of ether bonds other than an oxetane group in a molecule represented by the general formula (1). .

(1) Example of Structure An example of the structure of the oxetane compound will be described based on the infrared absorption spectrum shown in FIG. 1 and the proton-NMR spectrum shown in FIG.

The infrared absorption spectrum is represented by the following formula (5)
2- (3-methyl-3-oxetanemethoxy) ethyl vinyl ether (Example 1)
It was measured using a Fourier-type infrared spectrometer JIR-5500 (manufactured by JEOL Ltd.). The horizontal axis indicates the wave number (cm ^-1 ) and the vertical axis indicates the infrared absorption ratio (%).

[0032]

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As can be understood from the infrared absorption spectrum shown in FIG. 1, a remarkable peak attributed to the vibration of the oxetane ring appears at a wave number of 977 cm ^-1 . Wave number 16
At 18 cm ⁻¹ , a remarkable peak attributed to the stretching vibration of the vinyl group appears. Further, the wave number 1128cm ^-1, which appeared a peak attributable to an ether bond methoxy moiety, peaks attributable to the ether bond adjacent to the vinyl group at a wave number of 1047cm ^-1 and a wavenumber of 1203cm ^-1 is evident. Therefore, if an infrared absorption peak appears at each of such wave numbers, it can be confirmed that the compound has an oxetane ring, a vinyl group, and a plurality of ether bonds. Therefore, it can be said that there is a high possibility that the compound is the oxetane compound of the first embodiment.

Further, the proton-NMR spectrum shown in FIG. 2 shows that 2- (3-methyl-3-oxetanemethoxy)
For ethyl vinyl ether (Example 1),
The measurement was performed using an NMR measurement apparatus JNM-EX90 (JEOL Ltd.) under the conditions of a solvent CDCl ₃ and a resolution of 90 MHz. The abscissa indicates δ (ppm), and the ordinate indicates hydrogen intensity. Detailed data will be described in Example 1. In the proton-NMR spectrum, the peak attributed to hydrogen of 2- (3-methyl-3-oxetanemethoxy) ethyl vinyl ether has δ = 1.3, 3.5. 3.7, 3.9, 4.0-
4.2, 4.3 to 4.5 and 6.5.

(2) Substituents Next, the substituents in the oxetane compound represented by the general formula (1) will be described. First, the substituent R ¹ in the general formula (1) is a hydrogen atom, an alkyl group, a fluorine atom, a fluoroalkyl group, an allyl group, an aryl group, a furyl group, or a thienyl group, as described above. However, from the viewpoint of more excellent radical reactivity in the unsaturated group and cationic polymerizability of the oxetane ring, the substituent R ¹ is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group and an ethyl group. Group.

The substituents R ² and R ^{3 in the} general formula (1)
And R ⁴ each have a hydrogen atom or a carbon number of 1-6.
And more preferably a hydrogen atom. When the substituents R ² , R ³ and R ⁴ are each a hydrogen atom, the radical reaction rate of the oxetane compound becomes particularly high. The substituents R ² , R ³ and R ⁴ may be the same or different.

The number of repetitions m in the general formula (1) is 1
Is an integer of 10 to 10. However, from the viewpoint that the radical reactivity in the vinyl group is more excellent and the reaction between the raw materials when the oxetane compound is produced easily occurs.
More preferably, the number of repetitions m is an integer in the range of 1 to 4.

The number of repetitions n in the general formula (1) is also an integer of 1 to 10. However, the radical reactivity in the vinyl group is more excellent, and furthermore, the raw materials used in the production of the oxetane compound are not separated from each other. From the viewpoint that the reaction easily occurs, the number of repetitions n is more preferably an integer in the range of 2 to 5.

(3) Copolymer Monomer The oxetane compound according to the first embodiment is characterized by being excellent in compatibility and copolymerizability with other copolymer monomers. Therefore, together with various copolymerized monomers,
A uniform copolymer can be obtained. Here, preferred copolymerizable monomers that can be used in combination include ethylenically unsaturated monomers (other than fluorine-based unsaturated monomers) and fluorine-based unsaturated monomers.

Ethylenically unsaturated monomer An ethylenically unsaturated monomer is a compound having an ethylenically unsaturated bond (C = C) in a molecule, and is a monofunctional compound having one ethylenically unsaturated bond in one molecule. monomer,
And a polyfunctional monomer having two or more ethylenically unsaturated bonds in one molecule. When a copolymer monomer is added, a radical photopolymerization initiator or a pyrolytic radical generator described below is added,
It is preferable to copolymerize with an oxetane compound.

Accordingly, the monofunctional monomer which is an ethylenically unsaturated monomer includes, for example, (meth) acryloylmorpholine, 7-amino-3,7-dimethyloctyl (meth) acrylate, isobutoxymethyl (meth) acrylamide, Bornyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethyldiethylene glycol (meth) acrylate, t-octyl (meth) acrylamide, diacetone (meth) acrylamide, dimethylaminoethyl (meth) Acrylate, diethylaminoethyl (meth) acrylate, lauryl (meth) acrylate, dicyclopentadiene (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, diacrylate Clopentenyl (meth) acrylate, N, N-dimethyl (meth) acrylamide tetrachlorophenyl (meth) acrylate, 2-tetrachlorophenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, tetrabromophenyl (meth) acrylate, 2-tetrabromophenoxyethyl (meth) acrylate, 2-trichlorophenoxyethyl (meth) acrylate, tribromophenyl (meth) acrylate, 2-tribromophenoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2 -Hydroxypropyl (meth) acrylate, vinyl caprolactam, N-vinylpyrrolidone, phenoxyethyl (meth) acrylate,
Butoxyethyl (meth) acrylate, pentachlorophenyl (meth) acrylate, pentabromophenyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, bornyl (meth) acrylate, methyltriethylenediglycol ( (Meth) acrylates.

Further, among the above-mentioned monofunctional monomers,
An acrylate monomer containing no aromatic ring is more preferable for the purpose of securing weather resistance. Such acrylate monomers include, for example, isobornyl (meth) acrylate, lauryl (meth) acrylate, butoxyethyl (meth) acrylate polyethylene glycol mono (meth) acrylate, bornyl (meth) acrylate, methyltriethylenediglycol (meth) Acrylates are mentioned.

Further, among the ethylenically unsaturated monomers,
Examples of the polyfunctional monomer include ethylene glycol di (meth) acrylate, dicyclopentenyl di (meth) acrylate, triethylene glycol diacrylate, tetraethylene glycol di (meth) acrylate, and tricyclodecanediyl dimethylene di (meth) acrylate. Tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, caprolactone-modified tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, trimethylol Propane tri (meth) acrylate, ethylene oxide (hereinafter referred to as “EO”) modified trimethylolpropane tri (meth) acrylate, propylene oxide (hereinafter “PO”) .) Modified trimethylolpropane tri (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, both-terminal (meth) acrylic acid adduct of bisphenol A diglycidyl ether, 1,4
-Butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, polyester di (meth) acrylate, polyethylene glycol di (meth)
Acrylate, dipentaerythritol hexa (meth)
Acrylate, dipentaerythritol penta (meth)
Acrylate, dipentaerythritol tetra (meth)
Acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol penta (meth) acrylate,
Ditrimethylolpropane tetra (meth) acrylate, EO-modified bisphenol A di (meth) acrylate, PO-modified bisphenol A di (meth) acrylate, EO-modified hydrogenated bisphenol A di (meth) acrylate, PO-modified hydrogenated bisphenol A di (meth) A) acrylate, EO-modified bisphenol F di (meth) acrylate, and (meth) acrylate of phenol novolak polyglycidyl ether.

Among these polyfunctional monomers, acrylate monomers containing no aromatic ring are preferred because of their better weather resistance and heat resistance. Thus, for example, ethylene glycol di (meth) acrylate, dicyclopentenyl di (meth) acrylate, triethylene glycol diacrylate, tetraethylene glycol di (meth) acrylate, tricyclodecanediyl dimethylene di (meth) acrylate, trimethylolpropane Tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate, and the like.

The above-mentioned monofunctional monomer and polyfunctional monomer can be used separately, or it is preferable to use a monofunctional monomer and a polyfunctional monomer in combination. The polyfunctional monomer used in such a combination is selected from the above-mentioned tri (meth) acrylate compounds, tetra (meth) acrylate compounds, penta (meth) acrylate compounds, and hexa (meth) acrylate compounds. Is preferred. Among them, trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, ditrimethylolpropanetetra (meth) acrylate Is particularly preferred.

As the fluorine-containing unsaturated monomer (sometimes simply referred to as a fluorinated compound), a compound represented by the following general formula (6) is preferable.

[0047]

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[In the general formula (6), the substituent R ⁵ is a hydrogen atom, a fluorine atom or a chlorine atom, and the substituent R ⁶ is
A group represented by a hydrogen atom, a fluorine atom, a fluoroalkyl group, an alkoxy group, or a fluorinated alkoxy group. ]

The kind of the fluorinated compound represented by the general formula (6) is not particularly limited, but for example, tetrafluoroethylene, hexafluoropropylene,
3,3,3-trifluoropropylene, vinylidene fluoride, or alkyl perfluorovinyl ethers or alkoxyalkyl perfluorovinyl ethers; perfluoro (methyl vinyl ether), perfluoro (ethyl vinyl ether), perfluoro (propyl vinyl ether), Perfluoro (butyl vinyl ether), perfluoro (isobutyl vinyl ether)
Perfluoro (alkyl vinyl ether) s; perfluoro (alkoxyalkyl vinyl ether) s such as perfluoro (propoxypropyl vinyl ether);
And 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 2,2,3,3,3-pentafluoropropyl (meth) acrylate, 2 -(Perfluorobutyl) ethyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, 2- (perfluorooctyl) ethyl (meth) acrylate, and the like.

These fluorinated compounds can be used alone or in a combination of two or more. For example, a combination use of hexafluoropropylene and perfluoroalkyl perfluorovinyl ether, or a combination use of hexafluoropropylene and perfluoroalkoxyalkyl perfluorovinyl ether is preferable.

Next, the amount of the comonomer to be added when radically polymerizing the oxetane compound will be described. That is, the amount of the copolymerized monomer is not particularly limited, but is preferably, for example, a value within the range of 0.1 to 1,000 parts by weight based on 100 parts by weight of the oxetane compound. When the amount of the copolymerized monomer is less than 0.1 part by weight, the effect of addition tends not to be exhibited,
On the other hand, if it exceeds 1000 parts by weight,
Alternatively, the photocurability tends to decrease. Therefore,
The addition amount of the copolymerized monomer is more preferably set to a value within the range of 1.0 to 100 parts by weight, and even more preferably set to a value within the range of 2.0 to 30 parts by weight.

[Second Embodiment] The second embodiment is a method for producing an oxetane compound represented by the general formula (1).

(1) Raw Materials First, raw materials for producing the oxetane compound represented by the general formula (1) will be described. That is, Motoi's method of dehydrohalogenation (Motoi, et. Al., Bull
l. Chem. Soc. Jpn. 61, 1998), any raw material can be used as long as it can produce an oxetane compound. Specifically, the oxetane compound represented by the general formula (1) is subjected to an etherification reaction between the oxetane alcohol compound represented by the general formula (2) and the halogenated vinyl ether compound represented by the general formula (3). Can be manufactured.

More specific oxetane alcohol compounds represented by the general formula (2) include 3-methyl-3-oxetanemethanol, 3-methyl-3-oxetaneethanol, 3-methyl-3-oxetanepropanol,
-Ethyl-3-oxetanemethanol, 3-ethyl-3
Oxetaneethanol, 3-ethyl-3-oxetanepropanol, 3-propyl-3-oxetanemethanol, 3-propyl-3-oxetaneethanol, 3-propyl-3-oxetanepropanol, etc., alone or in combination of two or more. Matching.

Further, more specific halogenated vinyl ether compounds represented by the general formula (3) include 2-chloroethyl vinyl ether, 2-bromoethyl vinyl ether, 3-chloropropyl vinyl ether, 3-bromopropyl vinyl ether, -Chlorobutyl vinyl ether, 4-bromobutyl vinyl ether, etc., alone or in combination of two or more.

The reaction ratio between the oxetane alcohol compound represented by the general formula (2) and the halogenated vinyl ether compound represented by the general formula (3) is not particularly limited. ) Is preferably reacted with the halogenated vinyl ether compound represented by the general formula (3) in a range of 0.1 to 10 mol per mol of the oxetane alcohol compound represented by the formula (3). When the ratio of the halogenated vinyl ether compound is out of such a range, a large amount of unreacted monomer remains, and the radical reactivity of the oxetane compound tends to decrease. Therefore, it is more preferable to react the halogenated vinyl ether compound represented by the general formula (3) in the range of 0.3 to 3.0 mol per 1 mol of the oxetane alcohol compound represented by the general formula (2). .

(2) Reaction Temperature Next, the reaction temperature for producing the oxetane compound represented by the general formula (1) will be described. The reaction temperature is determined in consideration of the yield of the oxetane compound and the like, but is preferably, for example, a temperature in the range of 0 to 100 ° C.
When the reaction temperature is lower than 0 ° C., the reactivity of the reaction raw materials is remarkably reduced, and the yield tends to be extremely lowered. On the other hand, when the reaction temperature is higher than 100 ° C., the types of organic solvents that can be used are limited. Tend to be. Therefore, the reaction temperature at the time of producing the oxetane compound is more preferably set to a value within the range of 10 to 90 ° C, and even more preferably set to a value within the range of 20 to 80 ° C.

(3) Reaction Time Next, the reaction time for producing the oxetane compound represented by the general formula (1) will be described. The reaction time is determined in consideration of the yield of the oxetane compound, the reaction temperature, and the like, and is preferably, for example, a value within a range of 10 minutes to 100 hours at a reaction temperature of 0 to 100 ° C. If the reaction time is less than 10 minutes, a large amount of unreacted raw material tends to remain, while if the reaction time exceeds 100 hours, the productivity tends to decrease. Therefore, the reaction time for producing the oxetane compound is 30 minutes to 5 minutes.
More preferably, the value is within a range of 0 hours, and 1 to 10
More preferably, the value is within the time range.

(4) Reaction atmosphere (pH) Next, the reaction atmosphere (pH) for producing the oxetane compound represented by the general formula (1) will be described. The reaction atmosphere (pH value) is determined in consideration of the yield of the oxetane compound and the like, but is preferably, for example, a value in the range of 5 to 14. When the pH value is less than 5, side reactions tend to occur, and the yield tends to decrease.
When the pH value exceeds 14, the kind of raw material used tends to be excessively limited. Therefore, the pH value at the time of producing the oxetane compound is more preferably set to a value in the range of 6 to 14, and even more preferably to a value in the range of 7 to 14. In order to adjust the pH value to a value within such a range, it is preferable to use an alkali such as sodium hydroxide or potassium hydroxide.

(5) Phase Transfer Catalyst Next, the phase transfer catalyst used for producing the oxetane compound represented by the general formula (1) will be described. Such a phase transfer catalyst is added in order to improve the reactivity between the oxetane alcohol compound and the halogenated vinyl ether compound. For example, when the total amount of the raw materials is 100 parts by weight, the amount of the phase transfer catalyst to be added is 0.1%. It is preferred that the value be in the range of 1 to 30 parts by weight. When the amount of the phase transfer catalyst is less than 0.1 part by weight, the reactivity between the raw materials is significantly reduced, and the yield tends to be extremely reduced. Above this, purification tends to be difficult. Therefore, the addition amount of the phase transfer catalyst used when producing the oxetane compound,
The value is more preferably in the range of 1.0 to 20.0 parts by weight, and even more preferably in the range of 2.0 to 10.0 parts by weight, per 100 parts by weight of the raw material.

The type of the phase transfer catalyst is not particularly limited, either. For example, a quaternary ammonium salt and / or a quaternary phosphonium salt are preferable. More specifically, tetra-n-butyl ammonium bromide, tetramethyl ammonium bromide, benzyl triethyl ammonium bromide, hexadecyl trimethyl ammonium bromide, triethyl hexadecyl ammonium bromide, trioctyl methyl ammonium bromide, methyl triphenyl phosphonium bromide, triethyl hexamide One type alone or a combination of two or more types such as decylphosphonium bromide, tetraphenylphosphonium bromide, tetrabutylphosphonium bromide and the like can be mentioned.

(6) Organic Solvent Next, the organic solvent used for producing the oxetane compound represented by the general formula (1) will be described. Such an organic solvent is a good solvent for the raw material, and has a boiling point of 250 ° C. under atmospheric pressure from the viewpoint of facilitating the production.
The following liquids are preferred. Examples of such organic solvents include hydrocarbons such as hexane, heptane, and octane; halogenated hydrocarbons such as dichloromethane and chloroform; ethers such as diethyl ether, dibutyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, and dioxane. Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, esters such as ethyl acetate, butyl acetate, amyl acetate and γ-butyrolactone, and aromatic hydrocarbons such as benzene, toluene and xylene alone or 2 Combinations of more than one species are included.

Third Embodiment A third embodiment contains an oxetane compound represented by the general formula (1) (hereinafter sometimes referred to as an oxetane compound) and a photoacid generator. It is a photocurable composition. In the third embodiment as well, the oxetane compounds and the like described in the first and second embodiments can be used as they are, and the description thereof is omitted here.

(1) Definition of Photoacid Generator The photoacid generator used in the photocurable composition according to the third embodiment is decomposed by irradiation with energy rays such as light to form an oxetane ring. It is defined as a compound that opens a ring to release a photocurable (crosslinkable) acidic active substance. The third embodiment is characterized in that a photoacid generator that generates an acidic active substance (cation) is used. Further, as a light energy ray to be irradiated to decompose the photoacid generator and generate an acidic active substance, use of visible light, ultraviolet rays, infrared rays, X-rays, α-rays, β-rays, γ-rays or the like is preferable. . However, it has a certain energy level,
It is preferable to use ultraviolet rays from the viewpoints of quick curing, relatively low cost of the irradiation device, and small size.

(2) Types of Photoacid Generator Next, the types of photoacid generator used in the third embodiment will be described. As such a photoacid generator, an onium salt having a structure represented by the general formula (7) (a first group of compounds) or a sulfonic acid derivative represented by the general formula (8) (second compound)
Group of compounds).

[0066] In ^{_{[R 7 a R 8 b R}} 9 c R 10 d W] + m [MZ m + n] m (7) [ Formula (7), the acidic active agent (cationic) is an onium ion, W is S, Se, Te, P, As, S
b, Bi, O, I, Br, Cl or -N≡N;
R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are the same or different organic groups, a, b, c and d are each an integer of 0 to 3, and (a + b + c + d) is equal to the valence of W. M is a metal or metalloid constituting the central atom of the halide complex [MX _{m + n} ], for example, B, P, A
s, Sb, Fe, Sn, Bi, Al, Ca, In, T
i, Zn, Sc, V, Cr, Mn, and Co. Z is
For example, a halogen atom such as F, Cl, or Br, m is the net charge of the halide complex ion, and n is the valence of M. ]

Q _s- [S (= O) ₂ -R ¹¹ ] _t (8) [In the general formula (8), Q represents a monovalent or divalent organic group, R
¹¹ is a monovalent organic group having 1 to 12 carbon atoms, the subscript s is 0 or 1, and the subscript t is 1 or 2. ]

First Group of Compounds First, the first group of compounds, onium salts, are compounds that can release an active substance upon receiving light. Therefore, the anion [M
Z _{m + n} ] as tetrafluoroborate (B
F ^4-), hexafluorophosphate (PF ^6-), hexafluoroantimonate (SbF ^6-), hexafluoroarsenate (AsF ^6-), hexachloroantimonate (SbCl ^6-), and the like.

In the onium salt of the first group of compounds, the anion [MZ _{m + n} ] is replaced by a general formula
It is also preferable to use an onium salt having an anion represented by [MZ ⁿ OH ⁻ ]. Furthermore, perchlorate ion (C
10 ^4- ), trifluoromethanesulfonate ion (C
F ³ SO ³⁻ ), fluorosulfonate ion (FS
It is also preferable to use an onium salt having another anion such as O ³⁻ ), toluenesulfonic acid ion, trinitrobenzenesulfonic acid anion, and trinitrotoluenesulfonic acid anion.

Further, among the above-mentioned compounds of the first group, more preferred are aromatic onium salts, and particularly preferred are diaryliodonium salts represented by the following general formula (9). [R ¹² -Ar ¹ -I ⁺ -Ar ² -R ¹³ ] [Y ⁻ ] (9) [In the general formula (9), R ¹² and R ¹³ are each a monovalent organic group, and are the same or different. And at least one of R ¹² and R ¹³ has an alkyl group having 4 or more carbon atoms, Ar ¹ and Ar ² are each an aromatic group, and may be the same or different; ^- is a monovalent anion, periodic table group 3, group 5 fluoride anions or of, ClO ^4-, CF ₃ -SO ₃ ^- is an anion selected from. ]

Examples of such a diaryliodonium salt include (4-n-decyloxyphenyl) phenyliodonium hexafluoroantimonate,
[4- (2-hydroxy-n-tetradecyloxy) phenyl] phenyliodonium hexafluoroantimonate, [4- (2-hydroxy-n-tetradecyloxy) phenyl] phenyliodonium trifluorosulfonate, [4- (2 -Hydroxy-n-tetradecyloxy) phenyl] phenyliodonium hexafluorophosphate, [4- (2-hydroxy-n-tetradecyloxy) phenyl] phenyliodonium tetrakis (pentafluorophenyl) borate, bis (4
-T-butylphenyl) iodonium hexafluoroantimonate, bis (4-t-butylphenyl) iodonium hexafluorophosphate, bis (4-
t-butylphenyl) iodonium trifluorosulfonate, bis (4-t-butylphenyl) iodonium tetrafluoroborate, bis (dodecylphenyl) iodonium hexafluoroantimonate, bis (dodecylphenyl) iodonium tetrafluoroborate, bis (dodecylphenyl) One or a combination of two or more of iodonium hexafluorophosphate, bis (dodecylphenyl) iodonium trifluoromethylsulfonate and the like can be mentioned.

Second Group of Compounds Next, the sulfonic acid derivatives of the second group of compounds will be described. Preferred types of sulfonic acid derivatives include
Disulfones, disulfonyldiazomethanes, disulfonylmethanes, sulfonylbenzoylmethanes, imidosulfonates, benzoin sulfonates, sulfonates of 1-oxy-2-hydroxy-3-propyl alcohol, pyrogallol trisulfonates, benzyl sulfonates Is mentioned. Further, imidesulfonates are more preferable, and trifluoromethylsulfonate derivatives are more preferable among imidosulfonates.

(3) Amount of Photoacid Generator Added Next, the amount (content) of the photoacid generator used in the third embodiment will be described. The amount of the photoacid generator to be added is not particularly limited, but is preferably in the range of usually 0.1 to 15 parts by weight based on 100 parts by weight of the oxetane compound. If the amount of the photoacid generator is less than 0.1 part by weight, the photocurability tends to decrease and a sufficient curing speed cannot be obtained. On the other hand, if the amount of the photoacid generator exceeds 15 parts by weight, the cured product obtained tends to have reduced weather resistance and heat resistance. Therefore, from the viewpoint of better balance between the photocurability and the weather resistance of the obtained cured product, the addition amount of the photoacid generator is in the range of 1 to 10 parts by weight based on 100 parts by weight of the oxetane compound. It is more preferable to set the value.

(4) Additives The photocurable composition according to the third embodiment may contain a vinyl monomer, as long as the objects and effects of the present invention are not impaired.
It is also preferable to further include additives such as a radical photopolymerization initiator, a photosensitizer, and an organic solvent.

Vinyl monomer and radical photopolymerization initiator In the photocurable composition of the third embodiment, a vinyl monomer such as an acrylic monomer and a radical photopolymerization initiator (radical generator) are added. You may.
The radical generator is a compound that is decomposed by receiving an energy ray such as light to generate a radical, and the radical-reactive group is polymerized by the radical.
Therefore, the vinyl monomer separately added to the photocurable composition can be ring-opened to have a high molecular weight or crosslinked.

Photosensitizer In the photocurable composition of the third embodiment, a photosensitizer may be blended together with a photoacid generator. A photosensitizer is a compound that can effectively absorb energy rays such as light and effectively decompose a photoacid generator. Such photosensitizers include thioxanthone, diethylthioxanthone and thioxanthone derivatives; anthraquinone, bromoanthraquinone and anthraquinone derivatives; anthracene, bromoanthracene and anthracene derivatives; perylene and perylene derivatives; xanthene, thioxanthene and thioxanthene. Derivatives; coumarin and ketocoumarin; Among these photosensitizers, more preferred compounds are diethylthioxanthone and bromoanthracene.

The amount of the photosensitizer to be added is not particularly limited, but is based on 100 parts by weight of the photoacid generator.
The value is preferably in the range of 0.01 to 300 parts by weight. If the amount of the photosensitizer is less than 0.01 part by weight, the effect of addition tends not to be exhibited, while if it exceeds 300 parts by weight, the weather resistance and the like tend to decrease. Therefore, from the viewpoint of better balance between the manifestation of the addition effect and the weather resistance, the amount of the photosensitizer to be added is 0.5 to 100 parts by weight with respect to 100 parts by weight of the photoacid generator. The value is more preferably in the range, and even more preferably in the range of 1.0 to 50 parts by weight.

Organic Solvent In the photocurable composition of the third embodiment, it is preferable to add an organic solvent. By adding the organic solvent, the oxetane compound and the photoacid generator can be more uniformly mixed. In addition, the usability and the coating properties can be improved by adjusting the viscosity of the photocurable resin composition. Therefore, by adding an organic solvent, the viscosity of the photocurable resin composition can be increased to 1 to 10000 cps (25
(° C.). If the viscosity exceeds these ranges, it tends to be difficult to form a uniform coating film.

The organic solvent to be used can be selected within a range that does not impair the objects and effects of the present invention.
Usually, it is an organic compound having a boiling point under atmospheric pressure having a value in the range of 50 to 200 ° C., and is preferably an organic compound that uniformly dissolves each component. Therefore, preferred organic solvents include hydrocarbons such as hexane, heptane and octane; halogenated hydrocarbons such as dichloromethane and chloroform; methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butyl alcohol,
alcohols such as t-butyl alcohol; ethers such as dibutyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, dioxane; acetone;
Ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethyl acetate, butyl acetate,
Esters such as amyl acetate and γ-butyrolactone; and aromatic hydrocarbons such as benzene, toluene and xylene. These can be used alone or in combination of two or more.

Others The photocurable composition according to the third embodiment preferably further contains various additives. Such additives include acrylic resins, epoxy resins, polyamide resins, polyamide imide resins, polyurethane resins, polybutadiene resins, polychloroprene resins, polyether resins, polyester resins, styrene-butadiene block copolymers, petroleum resins, xylene Resin, ketone resin,
Examples include polymers and oligomers such as cellulose resins, fluorine-based polymers, silicone-based resins, and polysulfide-based resins. Other additives include a polymerization inhibitor such as phenothiazine and 2,6-di-t-butyl-4-methylphenol; a polymerization initiation aid; a leveling agent; a thixotropic agent; a wettability improver; Plasticizers; ultraviolet absorbers; antioxidants; silane coupling agents; inorganic fillers; pigments;

(4) Method of Use First, when the photocurable composition of the third embodiment is used, a method of coating a substrate (applied member) is generally employed. Here, the coating method of the photocurable composition includes, for example, a dipping method, a spray method, a bar coating method, a roll coating method, a spin coating method, a curtain coating method, a gravure printing method, a silk screen method, or a method such as an inkjet method. It is preferable to use

The means for photocuring the photocurable composition according to the third embodiment is not particularly limited, and various conventional methods can be employed. For example,
It is preferable to irradiate the entire coating film with light using a light source such as a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, and an excimer lamp. It is also preferable to irradiate the photocurable composition while scanning with laser light or convergent light obtained using a lens, a mirror, or the like. Further, using a photomask having a light transmitting portion of a predetermined pattern, irradiating the composition with non-convergent light through the photomask, or using a light guide member formed by bundling a number of optical fibers, It is also preferable to irradiate the composition with light via an optical fiber corresponding to a predetermined pattern on the optical member.

[Fourth Embodiment] A fourth embodiment is directed to a photocurable composition containing an oxetane compound represented by the general formula (1), a photoacid generator, and a reactive diluent. is there.
By adding (blending) the reactive diluent in this way, it is possible to adjust the physical properties of the obtained photocured product or the photoreactivity of the photocurable composition. In the fourth embodiment, the oxetane compound, the photoacid generator, the method of use, and the like described in the first to third embodiments can be used as they are, and a description thereof will be omitted.

(1) Amount of Reactive Diluent In the fourth embodiment, the amount (addition amount) of the reactive diluent is not particularly limited, but may be, for example, 100 parts by weight of the oxetane compound. Therefore, the value is preferably in the range of 0.1 to 100 parts by weight. When the amount of the reactive diluent is less than 1 part by weight, the effect of addition tends not to be exhibited. On the other hand, when the amount exceeds 100 parts by weight, the heat resistance and weather resistance of the obtained photocured product tend to decrease. is there. Therefore, the amount of the reactive diluent is more preferably set to a value within the range of 1.0 to 50 parts by weight, and even more preferably set to a value within the range of 2.0 to 30 parts by weight.

(2) Type of Reactive Diluent Next, the type of reactive diluent used in the fourth embodiment will be described. As such a reactive diluent, it is preferable to blend a cationically polymerizable monomer and an ethylenically unsaturated monomer or any one of the monomers. Since the type of the ethylenically unsaturated monomer has already been described in the first embodiment, the description is omitted here.

Cationic Polymerizable Monomer The cationic polymerizable monomer, which is a reactive diluent, is defined as an organic compound that undergoes a polymerization reaction or a crosslinking reaction when irradiated with light in the presence of a photoacid initiator. Therefore, for example, epoxy compounds, oxetane compounds, oxolane compounds, cyclic acetal compounds, cyclic lactone compounds, thiirane compounds, thietane compounds, vinyl ether compounds, spiro orthoester compounds which are reaction products of lactones with epoxy compounds, Saturated compounds,
Examples include a cyclic ether compound, a cyclic thioether compound, a vinyl compound, and the like. These cationically polymerizable monomers are also preferably used alone or in combination of two or more.

The epoxy compounds as the above-mentioned cationic polymerizable monomers include, for example, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, and brominated bisphenol F diglycidyl. Ether, brominated bisphenol S diglycidyl ether, epoxy novolak resin,
Hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 2- (3,4- Epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene oxide, 4-vinylepoxycyclohexane, bis (3,4-epoxy -6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3 ', 4'-epoxy-6'-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), Black pentaerythritol diepoxide, ethylene glycol di (3,4-epoxycyclohexylmethyl) ether, ethylenebis (3,4
-Epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, Trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether,
Polypropylene glycol diglycidyl ethers; polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol, and glycerin; long aliphatic chains Diglycidyl esters of dibasic acids; monoglycidyl ethers of higher aliphatic alcohols;
Cresol, butylphenol or monoglycidyl ethers of polyether alcohols obtained by adding alkylene oxide thereto; glycidyl esters of higher fatty acids; epoxidized soybean oil; butyl epoxystearate; octyl epoxystearate; epoxidized linseed oil; Epoxidized polybutadiene is exemplified.

Other cationic polymerizable monomers other than epoxy include trimethylene oxide, 3,3-dimethyloxetane, 3,3-dichloromethyloxetane, 3-ethyl-3-phenoxymethyloxetane, bis (3- Oxetanes such as ethyl-3-methyloxy) butane; oxolanes such as tetrahydrofuran and 2,3-dimethyltetrahydrofuran; trioxane;
Cyclic acetals such as 1,3-dioxolan and 1,3,6-trioxanecyclooctane; cyclic lactones such as β-propiolactone and ε-caprolactone; ethylene sulfide, 1,2-propylene sulfide, thioepichlorochlorode Thiirane such as phosphorus; Thietane such as 3,3-dimethylthiethane; Vinyl ether such as ethylene glycol divinyl ether, triethylene glycol divinyl ether, trimethylolpropane trivinyl ether; Spiro obtained by reacting epoxy compound with lactone Orthoesters; ethylenically unsaturated compounds such as vinylcyclohexane, isobutylene and polybutadiene; and derivatives of the above compounds.

Among the above cationically polymerizable monomers, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, (3,4-epoxycyclohexylmethyl) adipate, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, neopentyl glycol diglycidyl ether, Polyethylene glycol diglycidyl ether and polypropylene glycol diglycidyl ether are preferred.

Particularly preferred cationically polymerizable monomers are 3,4-epoxycyclohexylmethyl-3 ′,
An epoxy compound having two or more alicyclic epoxy groups in one molecule, such as 4'-epoxycyclohexanecarboxylate and bis (3,4-epoxycyclohexylmethyl) adipate. 100 total reactive diluent
When these epoxy compounds are contained at a ratio of 50% by weight or more, the cationic polymerization reaction rate (curing rate) becomes faster, and the curing time can be shortened.

Ethylenically unsaturated monomer As the reactive diluent, the ethylenically unsaturated monomer as a copolymerizable monomer described in the first embodiment can be used as it is. By using the ethylenically unsaturated monomer in this manner, a radical polymerization reaction can be used in photocuring. Therefore, a faster light curing speed can be obtained.

In the case where an ethylenically unsaturated monomer is used in the fourth embodiment, it is preferable to further add a radical photopolymerization initiator (radical generator). The radical generator is a compound that is decomposed by receiving energy rays such as light to generate a radical, and the radical polymerizable group is polymerized by the radical.

Examples of such a radical generator include acetophenone, acetophenone benzyl ketal,
Anthraquinone, 1- (4-isopropylphenyl)-
2-hydroxy-2-methylpropan-1-one, carbazole, xanthone, 4-chlorobenzophenone,
4,4'-diaminobenzophenone, 1,1-dimethoxydeoxybenzoin, 3,3'-dimethyl-4-methoxybenzophenone, thioxanthones, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino -Propan-2-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, triphenylamine, 2,4,6-trimethylbenzoyldiphenylphosphine oxide,
Bis (2,6-dimethoxybenzoyl) -2,4,4-
Tri-methylpentylphosphine oxide, benzyldimethylketal, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, fluorenone, fluorene,
Examples include benzaldehyde, benzoin ethyl ether, benzoin propyl ether, benzophenone, benzophenone derivatives, Michler's ketone, 3-methylacetophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone (BTTB) and the like. In addition, such a radical generator can be used alone or in combination of two or more.

The amount of the radical generator to be added is not particularly limited.
The value is usually in the range of 0.01 to 10 parts by weight, preferably in the range of 0.1 to 5 parts by weight with respect to 0 parts by weight.

[0095]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited to the description of these examples. In the examples, the amounts of the respective components mean parts by weight unless otherwise specified.

[Example 1] (Synthesis of oxetane compound) In a 5-liter separable flask equipped with a stirrer, a thermometer, a cooler and a dropping funnel, 1.2 liters of hexane and 1560 g of 5
After containing a 0% by weight aqueous sodium hydroxide solution, 53 g of tetra-n-butylammonium bromide (0.16 mol, manufactured by Wako Pure Chemical Industries, Ltd.) was used as a phase transfer catalyst.
Was added. Then, 139 g of 3
-Methyl-3-oxetanemethanol (1.36 mol,
Aldrich) and 369 g of 2-chloroethyl vinyl ether (3.46 mol, Nisso Maruzen Chemical Co., Ltd.)
) Was dropped into the separable flask at room temperature (25 ° C).

After completion of the dropping, the separable flask was heated using an oil bath, and the temperature in the separable flask was reduced to 6
7 ° C. At that temperature, 3-methyl-3-oxetanemethanol was reacted with 2-chloroethyl vinyl ether while refluxing for 5 hours to obtain a reaction solution. After cooling the resulting reaction solution to ice temperature, 2.4 liters of ice-cooled water was similarly added to the reaction solution and vigorously shaken. Thereafter, the aqueous layer and the organic layer were separated, and only the organic layer was collected. The obtained organic layer was dehydrated by adding 50 (g) of calcium carbonate. Hexane, which is an organic solvent, was removed from the dried organic layer by vacuum concentration, and further vacuum-distilled at a temperature of 67 ° C. and a pressure of 5 mmHg.
A purified product was obtained.

(Evaluation of oxetane compound) The obtained purified product was measured for infrared absorption spectrum and proton-NM
R and C.I. H. N. Was subjected to elemental analysis. The obtained purified product was evaluated for radical reactivity and copolymerizability with other vinyl monomers.

(1) Measurement of infrared absorption spectrum Fourier transform infrared spectrometer JIR-5500 described above
At room temperature (25 ° C.) with a resolution of 4 using the KBr method.
The measurement was performed under the conditions of cm ⁻¹ , gain of 1, and two scans. FIG. 1 shows the measured infrared absorption spectrum. For reference, 3-methyl-3 represented by the following formula (10) was used as a raw material when synthesizing 2- (3-methyl-3-oxetanemethoxy) ethyl vinyl ether.
FIG. 3 shows an infrared absorption spectrum of -oxetane methanol, and similarly, FIG. 4 shows an infrared absorption spectrum of 2-chloroethyl vinyl ether represented by the following formula (11).

[0100]

Embedded image

[0101]

Embedded image

As understood from the infrared absorption spectrum shown in FIG. 1, a remarkable peak attributed to the vibration of the oxetane ring appears at a wave number of 977 cm ^-1 . Wave number 16
At 18 cm ⁻¹ , a remarkable peak attributed to the stretching vibration of the vinyl group appears. Further, the wave number 1128cm ^-1, which appeared a peak attributable to an ether bond methoxy moiety, peaks attributable to the ether bond adjacent to the vinyl group at a wave number of 1047cm ^-1 and a wavenumber of 1203cm ^-1 is evident. Therefore, the obtained purified product is obtained by taking into account the results of the proton-NMR spectrum and the elemental analysis of CHN described below, and obtaining 2- (3-methyl-3-oxetanemethoxy).
It was confirmed to be ethyl vinyl ether.

(2) Measurement of proton-NMR spectrum The proton-NMR spectrum was measured using a proton-NMR measuring apparatus JNM-EX90 (manufactured by JEOL Ltd.).
It was measured under the conditions of a solvent CDCl ₃ and a resolution of 90 MHz. FIG. 1 shows the measured proton-NMR chart. For reference, 2- (3-methyl-3-
FIG. 5 shows a proton-NMR spectrum of 3-methyl-3-oxetanemethanol used as a raw material when synthesizing (oxetanemethoxy) ethyl vinyl ether.
Similarly, the proton of 2-chloroethyl vinyl ether
The NMR spectrum is shown in FIG.

[0104] As will be understood from the proton -NMR spectrum shown in FIG. 2, δ = 1.3 (peak shape s, 3H, CH ₃ - attributed to CH ₃ hydrogen in the oxetane ring), δ = 3.5 ( Peak shape s, 2H, belonging to CH ₂ hydrogen adjacent to the oxetane ring), δ = 3.7 (peak shape m, 2H, —CH ₂ —CH ₂ —
O-CH = attributable from the left side in CH ₂ in the second CH ₂ hydrogen), δ = 3.9 (peak shape _{m, 2H, -CH 2 -CH 2} -O
Assigned to the left of the CH ₂ hydrogens in _{-CH = CH 2), δ =} 4.0~4.2 ( peak shape quartet, 2H, -CH
= Attributable to the right of the CH ₂ hydrogens in CH _2), [delta] = from 4.3 to 4.5 (peak shape dd, 4H, assigned to CH ₂ hydrogen in oxetane ring), and [delta] = 6.5 (peak shape dd , 1H, assigned to CH hydrogen in -CH = CH ₂₎ data that is obtained.

(3) C.I. H. N. Element analysis CHN coder MT-3 type (Yanaco Co., Ltd.)
Was used to calculate the weight ratio of carbon and hydrogen. As a result, a weight ratio of 60.12% by weight of carbon and 9.34% by weight of hydrogen was obtained. In addition, when the obtained purified product is 2- (3-methyl-3-oxetanemethoxy) ethyl vinyl ether, the theoretical weight (calculated value) is 62.74% by weight of carbon and 9.37% by weight of hydrogen. It was confirmed to show a very good agreement with the value.

(4) Evaluation of Radical Reactivity The stainless steel autoclave with an electromagnetic stirrer having an inner volume of 0.5 liter was sufficiently purged with nitrogen using nitrogen gas. Then, into the autoclave, 20 g of the obtained purified product (2- (3-methyl-3-oxetanemethoxy) ethyl vinyl ether), 0.2 g of benzoyl peroxide as a radical generator, and 2 g of ethyl acetate as an organic solvent.
00g. Then, after sufficiently stirring the inside of the autoclave, the temperature in the autoclave was cooled to −50 ° C. using dry ice and methanol, and oxygen in the system was removed again using nitrogen gas.

Next, the temperature in the autoclave was set to 70 ° C.
, And with stirring, for 20 hours, 2- (3-
Radical polymerization of methyl-3-oxetanemethoxy) ethyl vinyl ether was performed. Thereafter, the autoclave was cooled with water to stop the reaction, and an oxetane polymer solution (polymer solution) was obtained. The obtained oxetane polymer solution was poured into a large amount of methanol to precipitate an oxetane polymer. Thereafter, the oxetane polymer was washed with a large amount of methanol, and further dried under vacuum at a temperature of 50 ° C. to obtain a purified oxetane polymer. Therefore, it was confirmed that the obtained purified product, 2- (3-methyl-3-oxetanemethoxy) ethyl vinyl ether, had excellent radical polymerizability.

(5) Evaluation of copolymerizability (Preparation of oxetane copolymer) A stainless steel autoclave with an inner volume of 0.5 liter and equipped with an electromagnetic stirrer was sufficiently purged with nitrogen using nitrogen gas. Next, the obtained purified product (2- (3-methyl-3-) was placed in the autoclave.
Oxetane methoxy) ethyl vinyl ether) 19.0
g of ethyl vinyl ether and 31.8 g of ethyl vinyl ether.
Further, 10 g of a nonionic reactive emulsifier (NE-30, manufactured by Asahi Denka Co., Ltd.) as a radical generator, and azo group-containing polydimethylsiloxane (VP, manufactured by Wako Pure Chemical Industries, Ltd., VP
S-1001) 1.0 g and lauroyl peroxide 0.5 g
And finally 300 g of ethyl acetate as an organic solvent
Was accommodated. After sufficiently stirring the copolymerization components and the like, the temperature in the autoclave was cooled to -50 ° C using dry ice and methanol, and oxygen in the system was removed again using nitrogen gas.

Next, after 99.3 g of hexafluoropropylene (gas) was introduced into the autoclave, the temperature in the autoclave was raised to 70 ° C. Note that 70
The pressure in the autoclave at the time when the temperature was raised to 5 ° C was 5.
It was 8 kgf / cm ² . While stirring the copolymer components and the like in the autoclave, while maintaining the temperature at 70 ° C,
Radical polymerization was performed for 20 hours. When the pressure in the autoclave dropped to 2.5 kgf / cm ² , the autoclave was cooled with water to stop the reaction.
After confirming that the temperature in the autoclave had dropped to room temperature, the autoclave was opened to release unreacted monomers out of the system, and an oxetane copolymer solution (polymer solution) was taken out.

The obtained oxetane copolymer solution was poured into a large amount of methanol to precipitate the oxetane copolymer. Thereafter, the oxetane copolymer was washed with a large amount of methanol, and further dried under vacuum at a temperature of 50 ° C. to obtain a purified oxetane copolymer. Therefore,
It was confirmed that the obtained purified product, 2- (3-methyl-3-oxetanemethoxy) ethyl vinyl ether, had excellent compatibility with other copolymerizable monomers. In addition, the obtained oxetane copolymer was measured five times for each of the following evaluation items, and it was confirmed that the oxetane copolymer exhibited uniform characteristics (value).

(Evaluation of Oxetane Copolymer) (1) Measurement of Number Average Molecular Weight The obtained oxetane copolymer was dissolved in THF (tetrahydrofuran) to a concentration of 0.5% by weight.
Next, the GPC device HLC-8020 (Tosoh Corporation)
The elution time from the GPC column was detected by a refractometer (RI), and the number average molecular weight was calculated from the obtained elution time as a polystyrene equivalent molecular weight. As a result, the number average molecular weight of the obtained oxetane copolymer was 40.
000.

(2) Fluorine content The fluorine content of the obtained oxetane copolymer was measured according to the alizarin complexon method. As a result, the fluorine content of the obtained oxetane copolymer was 48.0% by weight.

(3) Measurement of glass transition temperature The glass transition temperature of the obtained oxetane copolymer was determined by using DS
Using a C apparatus 910 (manufactured by DuPont),
0 ° C./min, using a nitrogen stream). As a result, the glass transition temperature of the obtained oxetane copolymer was 2
8.0 ° C.

(4) Measurement of Contact Angle The contact angle of the obtained oxetane copolymer was determined by FASE
Using a CA-X type contact angle meter manufactured by Co., Ltd., the measurement was carried out at a temperature of 23 ° C. and a humidity of 50% RH. As a result, the contact angle of the oxetane copolymer with pure water was 97 °. In addition, when the contact angle is 90 ° or more, it can be generally said that there is excellent water repellency.

(6) Evaluation of Cationic Polymerizability 1 100 parts by weight of the obtained purified product, 2- (3-methyl-3-oxetanemethoxy) ethyl vinyl ether, was mixed with a thermal acid generator, Sun-Aid SI-80L ( Sanshin Chemical Co., Ltd.) was added in an amount of 3 parts by weight and uniformly mixed. The obtained liquid mixture was applied on a quartz plate using a bar coater (No. 10) to form a coating film having a uniform thickness. When this coating film was heated at 100 ° C. for 1 hour using an oven, a colorless and transparent cured film was obtained. Therefore, it was confirmed that the obtained purified product, 2- (3-methyl-3-oxetanemethoxy) ethyl vinyl ether, had excellent thermocationic polymerizability.

(7) Evaluation of cationic polymerizability 2 100 parts by weight of the obtained purified product, 2- (3-methyl-3-oxetanemethoxy) ethyl vinyl ether, was added to a photoacid generator, Sun-Aid SI-100L ( 3 parts by weight (Sanshin Chemical Co., Ltd.) was added and mixed uniformly. The obtained mixed solution was coated on a quartz plate with a bar coater (No. 10).
To form a coating film having a uniform thickness. When this coating film was irradiated with ultraviolet light using a high-pressure mercury lamp (Oak Seisakusho Co., Ltd.) under the condition that the exposure amount was 200 mJ / cm ² , a colorless and transparent cured film was obtained. Therefore, it was confirmed that the obtained purified product, 2- (3-methyl-3-oxetanemethoxy) ethyl vinyl ether, had excellent photocationic polymerizability.

[Comparative Example 1] Radical polymerizability of propenyl ether propylene carbonate (manufactured by ISP) as a compound having one ether bond in the molecule other than the oxetane group was evaluated. First, a stainless steel autoclave with an internal volume of 0.5 liter and equipped with an electromagnetic stirrer was sufficiently purged with nitrogen using nitrogen gas. Next, 20.0 g of propenyl ether propylene carbonate, 0.2 g of benzoyl peroxide as a radical generator, and 200 g of ethyl acetate as an organic solvent were accommodated in the autoclave. Then, after sufficiently stirring the inside of the autoclave, the temperature in the autoclave was cooled to −50 ° C. using dry ice and methanol, and oxygen in the system was removed again using nitrogen gas.

Next, the temperature in the autoclave was set to 70 ° C.
Then, radical polymerization of propenyl ether propylene carbonate was carried out for 20 hours while stirring. Then, the solution after the radical reaction was poured into a large amount of methanol as in Example 1, and reprecipitation purification was performed. However, a high molecular weight product could not be obtained as a solid content. Therefore, it was confirmed that propenyl ether propylene carbonate had poor radical polymerizability.

Further, as in Example 1, hexafluoropropylene (gas) was introduced into the autoclave, and then a copolymerization reaction was carried out. However, a copolymer as a solid content could be obtained. Did not. Therefore, it was confirmed that propenyl ether propylene carbonate was poor in radical polymerizability and poor in compatibility with the fluorine-containing unsaturated monomer.

[0120]

EFFECTS OF THE INVENTION The oxetane compound of the present invention is excellent in radical polymerization reactivity and cationic polymerization reactivity, and is copolymerized with other unsaturated monomers (vinyl monomers and the like), especially fluorine-based vinyl monomers generally having poor compatibility. An oxetane compound having excellent properties can be provided.

The oxetane compound can be efficiently obtained by reacting the oxetane alcohol compound with the halogenated vinyl ether compound in the presence of a phase transfer catalyst in accordance with the oxetane compound production method of the present invention. It became so.

[Brief description of the drawings]

FIG. 1: 2- (3-methyl-3-oxetanemethoxy)
It is an infrared absorption spectrum of ethyl vinyl ether.

FIG. 2. 2- (3-methyl-3-oxetanemethoxy)
It is a proton-NMR spectrum of ethyl vinyl ether.

FIG. 3 is an infrared absorption spectrum of 3-methyl-3-oxetanemethanol.

FIG. 4 is an infrared absorption spectrum of 2-chloroethyl vinyl ether.

FIG. 5 is a proton-NMR spectrum of 3-methyl-3-oxetanemethanol.

FIG. 6 shows protons of 2-chloroethyl vinyl ether.
It is an NMR spectrum.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) // C07B 61/00 300 C07B 61/00 300 (72) Inventor Hozumi Sato 2-chome Tsukiji 2-chome, Chuo-ku, Tokyo No. 24 JSR Co., Ltd. F term (reference) 4C048 TT02 UU03 UU05 XX02 XX05 4C063 AA01 BB01 CC75 CC92 DD72 EE05 EE10 4H039 CA61 CD10 CD20

Claims (10)

[Claims] An oxetane compound represented by the following general formula (1). Embedded image [In the general formula (1), the substituent R ¹ is a hydrogen atom, an alkyl group, a fluorine atom, a fluoroalkyl group, an allyl group, an aryl group, a furyl group or a thienyl group;
² , R ³ and R ⁴ are each a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and m and n are each an integer of 1 to 10. ] 2. The oxetane compound according to claim 1, wherein said substituents R ² , R ³ and R ⁴ are each a hydrogen atom. 3. The oxetane compound according to claim 1, wherein the substituent R ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. 4. The oxetane compound according to claim 1, wherein the number of repetitions m is an integer of 1 to 4, and the number of repetitions n is an integer of 2 to 5. 5. A method for producing an oxetane compound represented by the following general formula (1), wherein the oxetane alcohol compound represented by the following general formula (2) and a halogenated vinyl ether represented by the following general formula (3) A method for producing an oxetane compound, comprising reacting a compound with a compound in the presence of a phase transfer catalyst. Embedded image [In the general formula (1), the substituent R ¹ is a hydrogen atom, an alkyl group, a fluorine atom, a fluoroalkyl group, an allyl group, an aryl group, a furyl group or a thienyl group;
² , R ³ and R ⁴ are each a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and m and n are each an integer of 1 to 10. ] [In the general formula (2), the substituent R ¹ and the number of repetitions m are
It is the same as the content of the general formula (1). ] [In the general formula (3), the substituents R ² , R ³ , R ⁴ and the number of repetitions n are the same as those in the general formula (1), and X is a halogen atom. ] 6. The halogenated vinyl ether compound represented by the general formula (3) is used in an amount of 0.1 to 1 mol per 1 mol of the oxetane alcohol compound represented by the general formula (2).
The method for producing an oxetane compound according to claim 5, wherein the reaction is carried out within a range of 10 mol. 7. The halogenated vinyl ether compound represented by the general formula (3), wherein the halogen atom is chloro or bromo.
3. The method for producing an oxetane compound according to item 1. 8. The process for producing an oxetane compound according to claim 5, wherein the phase transfer catalyst is a quaternary ammonium salt and / or a quaternary phosphonium salt. 9. An oxetane alcohol compound represented by the general formula (2) and a halogenated vinyl ether compound represented by the general formula (3) are reacted under alkaline conditions. The method for producing an oxetane compound according to any one of the above. 10. An oxetane alcohol compound represented by the general formula (2) and a halogenated vinyl ether compound represented by the general formula (3) are reacted at a temperature within a range of 0 to 100 ° C. A method for producing an oxetane compound according to any one of claims 5 to 9.