JP2001081131A - Fluorooligomer containing functional groups at both terminals of main chain, its production and curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition which can produce a cured product having excellent toughness, excellent elasticity, excellent elasticity, and the like at a high curing rate by allowing a curable composition to contain a fluorooligorrter containing functional groups at both the terminals of the main chain. SOLUTION: The fluorooligomer containing ester groups at both the terminals of the main chain, the fluorooligomer containing, unsaturated groups at both the terminals of the main chain, or the fluorooligomer containing alcoholic hydroxyl groups at both the terminals of the main chain is a fluorooligomer which has a number-average mol.wt. of 1,000 to 10,000 and has ester groups, unsaturated groups or alcoholic hydroxyl groups at both the terminals of the main chain of the fluorooligomer. The method for producing the fluorooligomer having the unsaturated groups or the alcoholic hydroxyl groups at both the terminals of the main chain comprises reacting the fluorooligomer having the ester groups at both the ends of the main chain with an unsaturated group-containing amine or an alcoholic hydroxyl group- containing amine at <=60 deg.C. The curable composition comprises the fluorooligomer containing the unsaturated groups at both the terminals of the main chain, (meth)acrylic monomer, and a photopolymerization initiator or a radical-generating agent. The curable composition further comprises the fluorooligomer containing the alcoholic hydroxyl groups at both the terminals of the main chain and a polyisocyanate compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a fluorine oligomer having ester groups at both ends of the main chain, a fluorine oligomer having unsaturated groups at both ends of the main chain, and a fluorine oligomer having an alcoholic hydroxyl group at both ends of the main chain. For oligomers. The invention also relates to a method for producing these fluorine oligomers. Further, a curable composition comprising a fluorine oligomer having an unsaturated group at both ends of the main chain, a (meth) acrylic monomer and a photopolymerization initiator or a radical generator, and a fluorine having an alcoholic hydroxyl group at both ends of the main chain The present invention relates to a curable composition comprising an oligomer and a polyisocyanate compound.

[0002]

2. Description of the Related Art Fluorine oligomers having carboxyl groups at both ends of the main chain are expected to be useful compounds as raw materials for chain extenders such as epoxy resins and isocyanate resins or solvent-resistant sealants, adhesives and paints. Compound. Conventionally, fluorine-containing oligomers having a carboxyl group at both ends, for example, U.S. Pat.
No. 761 discloses a method of dehydrofluorinating a vinylidene fluoride-hexafluoropropene copolymer and oxidatively decomposing a double bond formed therewith with KMnO ₄ to obtain a COO group-containing fluorine copolymer. However, this method has a problem that a fluorine oligomer having carboxyl groups completely at both ends of the main chain cannot be obtained, and a step such as removal of heavy metal Mn is required.

Further, “functional fluorine-containing polymer” (No. 11)
Pp. 12, 1982, published by Nikkan Kogyo Shimbun), it is reported that CF ₂ ＣＦCFO (CF ₂ ) ₄ COOCH _{3 is} added to tetrafluoroethylene.
Can be produced to produce a fluorine oligomer having an ester group in a side chain. Also, a method is described in which a side chain ester group is hydrolyzed to produce a fluorine oligomer having a carboxyl group in the side chain of the oligomer. However, in such a method, a fluorine oligomer having carboxyl groups at both ends of the main chain cannot be obtained, and an ester group-containing monomer used in this copolymerization reaction is extremely expensive, and is not suitable for industrial use. Is not suitable. Furthermore, since the hydrolysis reaction of the ester group does not proceed sufficiently under alkaline conditions, there is a problem that it is difficult to apply the reaction to a vinylidene fluoride-based copolymer.

By the way, vulcanized rubber waste typified by burrs generated at the time of vulcanization molding of rubber has little merit in terms of cost even in the case of regenerating and using general rubber. For expensive fluororubbers, the use of vulcanized rubber waste is an important issue from the viewpoint of cost reduction. Therefore, it has been desired to develop a method for producing a fluorine oligomer having carboxyl groups at both ends of the main chain by reusing such vulcanized fluororubber waste.

In the conventional method of regenerating a crosslinked vulcanized fluororubber, burrs and debris are mechanically pulverized,
A plasticizing method or a method of further treating the same with nitric acid, potassium permanganate, various amines or the like has been used [JP-A-59-217734 and JP-A-59-217].
735, U.S. Pat.No. 3,291,761, German Patent Application Publication Nos. 2 360 927, 2420 993, Kautschuk +
Gummel ・ Kunststoffe23. Jahrgang, Heft 3/1976, 218
45, Jahrgang, Nr. 9/92, p. 742, Proizvo Shin,
Rezinotekhn; Asbestotekhn. Izdlii (Moskva) 1979,
6 pages, 7 pages], the resulting recycled product is virgin rubber (new rubber)
And is used as a kind of filler.

However, in order to obtain a reclaimed fluororubber from a crosslinked vulcanized fluororubber, the crosslinked structure must be decomposed, and a vinylidene fluoride copolymer generally used as a fluororubber is used. From the vinylidene fluoride structure, the decomposition method under basic conditions is difficult to apply,
In addition, the crosslinked structure by the polyhydroxy compound (polyol) has a problem that decomposition does not proceed to such an extent that the rubber component can be regenerated and isolated even when a strong acid such as nitric acid is used.

Further, in the crosslinked vulcanized fluoro rubber,
In most cases, a filler is contained, and it has been desired to obtain a reclaimed fluororubber in which such a filler is completely separated. Further, there is also a problem that the above-mentioned regenerating method may not be applicable depending on a crosslinking system at the time of forming the vulcanized fluoro rubber. In response to such a problem, the present applicant has filed Japanese Patent Application Nos. 10-150743 and 10-0.
No. 90856, a novel fluorine oligomer containing carboxyl groups at both ends of the main chain (hereinafter sometimes referred to as a “carbon oligomer containing carboxyl groups at both ends of the main chain”) and vulcanized fluoro rubber Using waste as a raw material, a method for safely and inexpensively producing a fluorocopolymer containing carboxyl groups at both ends of the main chain from the waste was proposed.

That is, a method for producing a carboxyl group-containing vinylidene fluoride copolymer by treating the vinylidene fluoride copolymer with a base and a peroxide has been proposed. Also,
An oligomer obtained by decomposing a cross-linked fluororubber, which can be easily separated from fillers and the like due to solvent solubility, and is effectively used as a chain extender for epoxy resins, isocyanate resins, oxazoline resins, etc. The resulting fluorine oligomer containing a carboxyl group at both ends of the main chain was proposed.

However, the above-mentioned fluorine oligomer containing a carboxyl group at both ends of the main chain has a problem that the curing rate of a curable composition containing the fluorine oligomer cannot be said to be high at all, and the application or the curing process is limited. was there. For this reason, the curing speed is fast, useful as a raw material such as a chain extender such as an epoxy resin and an isocyanate resin or a solvent-resistant sealant, an adhesive and a paint.
The emergence of a fluorine oligomer having a functional group such as an ester group at both ends of the main chain and a method for producing the same are desired.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to solve the problems associated with the prior art as described above, and it is an object of the present invention to provide a fluorine oligomer having a functional group such as an ester group at both terminals of a main chain having an excellent curing rate; It is an object of the present invention to provide a method for producing the composition and a curable composition comprising the fluorine oligomer and the like and having an excellent curing rate.

[0011]

SUMMARY OF THE INVENTION The fluorine oligomer having ester groups at both ends of the main chain according to the present invention has a number average molecular weight of 1,000 to 100.
00 is a fluorine oligomer having ester groups at both ends of the main chain of the fluorine oligomer. Further, the fluorine oligomer containing unsaturated groups at both ends of the main chain according to the present invention has a number average molecular weight of 1,000 to 100.
A fluorine oligomer which is 00, having an unsaturated group at both terminals of the main chain of the fluorine oligomer. Further, the fluorine oligomer having an alcoholic hydroxyl group at both ends of the main chain according to the present invention has a number average molecular weight of 100.
A fluorine oligomer having a molecular weight of 0 to 10000, wherein the fluorine oligomer has an alcoholic hydroxyl group at both ends of the main chain. Such a fluorine oligomer is preferably a copolymer containing a repeating unit derived from vinylidene fluoride.

The process for producing a fluorine oligomer having an unsaturated group at both ends of the main chain according to the present invention comprises the step of:
The reaction is characterized below. In addition, the method for producing a fluorine oligomer having an alcoholic hydroxyl group at both ends of the main chain according to the present invention comprises:
It is characterized in that the reaction is performed at a temperature of not more than ℃.

The curable composition according to the present invention is characterized by comprising the above-mentioned fluorine oligomer having an unsaturated group at both ends of the main chain, a (meth) acrylic monomer and a photopolymerization initiator. Further, the curable composition according to the present invention is characterized by comprising the above-mentioned fluorine oligomer having an unsaturated group at both ends of the main chain, a (meth) acrylic monomer and a radical generator. Furthermore, the curable composition according to the present invention is characterized by comprising the above-mentioned fluorine oligomer having an alcoholic hydroxyl group at both ends of the main chain and a polyisocyanate compound.

[0014]

DETAILED DESCRIPTION OF THE INVENTION The fluorine oligomer having a functional group at both ends of the main chain, the method for producing the same, and the curable composition according to the present invention will be specifically described below. Fluorine Oligomer Containing Both Main-Terminal Functional Groups The oligomer having a main- terminal both terminal functional group in the present invention includes a fluorine oligomer containing both main-terminal ester groups, a fluorine oligomer containing both main-chain unsaturated terminals, and an alcoholic compound having both main-chain terminals. A hydroxyl group-containing fluorine oligomer is exemplified. Since such a fluorine oligomer having a functional group at both ends of the main chain is obtained from a fluorine oligomer having a carboxyl group at both ends of the main chain, the fluorine oligomer having a carboxyl group at both ends of the main chain will be described first.

A carboxyl group-containing fluorine atom at both ends of the main chain
Gomer A fluorine oligomer having carboxyl groups at both ends of the main chain, which is a starting material of the present invention, is described in, for example, Japanese Patent Application No. 10-1980.
It can be obtained by subjecting a crosslinked fluoro rubber to a decomposition treatment according to the method described in Japanese Patent No. 50743. Fluororubber used as such a raw material is a burr when vulcanized and molded with polyol, amine or peroxide, etc.
It is waste such as waste and defective molded products. Further, a fluorine oligomer having carboxyl groups at both ends of the main chain may be newly synthesized from fluororubber.

The vulcanized and cross-linked fluororubber is not particularly limited as long as it is a fluororubber containing fluorine, and examples thereof include a copolymer of vinylidene fluoride and another fluorinated olefin or olefin. .
As a copolymer containing vinylidene fluoride, specifically,
Vinylidene fluoride and perfluoro (alkyl vinyl ether) such as tetrafluoroethylene, hexafluoropropene, chlorotrifluoroethylene, pentafluoropropene and perfluoro (methyl vinyl ether);
Copolymer with at least one of propylene, vinylidene fluoride-hexafluoropropene-tetrafluoroethylene terpolymer, vinylidene fluoride-tetrafluoroethylene-propylene terpolymer, vinylidene fluoride-tetrafluoroethylene -Perfluoro (methyl vinyl ether) terpolymer and the like.

Further, the crosslinked fluororubber formed by vulcanization includes tetrafluoroethylene-propylene copolymer, tetrafluoroethylene-perfluoro (methyl vinyl ether) copolymer, and tetrafluoroethylene-perfluoro (methyl vinyl ether). And tetrafluoroethylene copolymers such as an ethylene terpolymer. As these various copolymers, in the copolymer, bromine and / or iodine-containing compound, nitrile group, glycidyl group, hydroxyalkyl group, cross-linkable group-containing monomers such as perfluorophenyl group is copolymerized. Can also be used.

These crosslinked fluororubbers are immersed in an organic solvent for one day or more to sufficiently swell the organic solvent in the crosslinked fluororubber and then subjected to a decomposition treatment. As such an organic solvent, any one can be used as long as it can swell the crosslinked fluororubber, for example, ketones, dimethylformamide, amides such as dimethylacetamide, dimethylsulfoxide, sulfolane and the like Sulfur-containing compounds, alcohols, lower fatty acids, esters, halogen-containing compounds such as trichlorotrifluoroethane, hexafluoroisopropanol, trifluoroethanol, and trichloroacetic acid are used.

The decomposition treatment of the crosslinked fluororubber after swelling is as follows:
The reaction is performed in the presence of a base and a peroxide. As the base, specifically, hydroxides, carbonates, organic acid salts, tertiary amines, tertiary phosphines and the like of alkali metals are used. Specific examples of the peroxide include hydrogen peroxide, persulfate, peracetic acid, organic peroxides, and organic hydroperoxides. Of these, hydrogen peroxide is particularly preferred in terms of cost. The addition of base and peroxide
In the order of peroxide and base, it can be carried out once or several times.

When the crosslinked fluororubber dispersed in the latex state is decomposed, the catalyst is usually used as a catalyst when the crosslinked fluororubber dispersed in the latex state is swollen with an organic solvent in order to increase the decomposition treatment speed. , 4
It is preferable to use a quaternary phosphonium salt such as a quaternary ammonium salt or a quaternary onium salt. The decomposition treatment is usually performed at a temperature of about 0 to 100 ° C, and is not particularly limited, but is preferably performed at about 10 to 30 ° C from the viewpoint of suppressing heat generation. The molecular weight and the acid value of the decomposition product can be arbitrarily adjusted by introducing a double bond with a base.

The decomposed fluororubber crosslinked product is subjected to phase separation with strong hydrochloric acid, a coarse filler material portion is first separated using a filter, the washing solution and the filtrate are combined, and the mixture is added to a large amount of water to be decomposed. The processed product precipitates and is vigorously stirred for a long time. After such an operation is repeated 3 to 5 times to precipitate again, the obtained product is dried at about 65 ° C. for about 3 days to obtain a fluorine oligomer having a carboxyl group at both ends of the main chain. be able to. Due to the structure of the decomposition, the probability of producing a fluorine oligomer having three or more terminals is low. In addition to the fluorine oligomer having a carboxyl group at both ends of the main chain, only one end of the main chain has a carboxyl group. Can be produced.

Fluorinated oligo containing ester group at both ends of main chain
In the present invention, the main chain terminal carboxyl group-containing fluorine oligomer obtained as described above is dissolved in an organic solvent,
Esterify. Esterification of the fluorine oligomer having a carboxyl group at both ends of the main chain is carried out, for example, by esterifying the fluorine oligomer having a carboxyl group at both ends of the main chain and an alcohol in a solvent in the presence of an acid catalyst.

Examples of the alcohol include aliphatic alcohols having 1 to 5 carbon atoms and aromatic alcohols having 6 to 12 carbon atoms. Specific examples include aliphatic alcohols such as methanol, ethanol, n-propyl alcohol, and isopropyl alcohol, and aromatic alcohols such as benzyl alcohol. Specific examples of the solvent include ketones, alcohols, lower fatty acids, esters, and halogen-containing compounds.

Further, specific examples of the acid catalyst include concentrated sulfuric acid, hydrochloric acid, p-toluenesulfonic acid, acetic anhydride, trifluoroacetic anhydride and the like. Such an acid catalyst is used in an amount of 1 to 10% by weight, preferably 3 to 5% by weight, based on 100% by weight of the fluorine oligomer having a carboxyl group at both ends of the main chain. The reaction temperature of the esterification of such a fluorine oligomer containing a carboxyl group at both ends of the main chain,
It is generally 0 ° C to 150 ° C, preferably 70 ° C to 12 ° C.
0 ° C. Such a reaction is usually performed for 1 to 5 hours, preferably for 2 to 3 hours.

After completion of the reaction, the solvent is distilled off. At this time,
If the amount to be distilled off is small, the purity of the reaction product becomes low, and if it is too large, the reaction product becomes high in viscosity. Therefore, the amount of the solvent to be distilled off is preferably 50 to 90%, particularly 70 to 80%. Preferably, there is. After distilling off the solvent, the resulting solution containing the reaction product is introduced into a large amount of water, and the reaction product is precipitated and vigorously stirred. In this case, water is preferably about 5 to 50 times the reaction product.
After stirring, the reaction product is recovered by filtration, and the precipitate is again added to a large amount of water and stirred vigorously. Such an operation is usually performed about 3 to 10 times to precipitate a reaction product. When the precipitate thus obtained is dried at about 40 to 80 ° C., a fluorine oligomer having ester groups at both ends of the main chain (hereinafter, sometimes referred to as “a fluorine oligomer having ester groups at both ends of the main chain”) Is obtained.

Specific examples of the ester group of the obtained fluorinated oligomer having ester groups at both ends of the main chain include methyl ester, ethyl ester, n-propyl ester, isopropyl ester, benzyl ester and the like. Such a fluorinated oligomer having ester groups at both ends of the main chain is a fluorine oligomer having a number average molecular weight in the range of 1,000 to 10,000.

In the case where the crosslinked fluororubber used as a raw material is a copolymer containing a repeating unit derived from vinylidene fluoride, the resulting fluorine oligomer containing both ester groups at both ends of the main chain is derived from vinylidene fluoride. It is a fluorine oligomer containing a repeating unit. In the case where the starting material is a fluorine oligomer having a carboxyl group at one end of the main chain, the same method as that for esterifying a fluorine oligomer having a carboxyl group at both ends of the main chain is used. The fluorine oligomer having a terminal carboxyl group can be esterified to obtain a fluorine oligomer having an ester group at one end of the main chain.

Fluorinated oligomer containing unsaturated groups at both ends of main chain
-And main chain both ends alcoholic hydroxyl group-containing fluorinated
Rigomer The fluorinated oligomer having an ester group at both ends of the main chain obtained as described above is reacted with an amine having an unsaturated group such as an allyl group or an amine having an alcoholic hydroxyl group to amidate, and an amidation occurs at both ends of the main chain. Fluorinated oligomers containing a saturated group (hereinafter sometimes referred to as “fluorine oligomers containing unsaturated groups at both ends of the main chain”) or fluorinated oligomers containing alcoholic hydroxyl groups at both ends of the main chain (hereinafter “both ends of the main chain”) Alcoholic hydroxyl group-containing fluorine oligomer ").

Specifically, a fluorine oligomer having ester groups at both ends of the main chain is dissolved in a solvent, and an amine having an unsaturated group or an alcoholic hydroxyl group is added to the solution to amidate the solution. A fluorinated oligomer containing an unsaturated group or a fluorinated oligomer containing an alcoholic hydroxyl group at both ends of the main chain can be obtained. Such solvents include acetone, tetrahydrofuran,
Examples include methyl ethyl ketone, methanol, ethanol, n-propyl alcohol and the like.

The amine containing an unsaturated group is represented by the following general formula [I]

[0031]

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[Wherein R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 2 carbon atoms or a phenyl group, and n is an integer of 1 or 2 Or the following general formula [II]

[0033]

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Wherein R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom or an alkyl group having 1 to 2 carbon atoms. Specific examples of the amine [I] include allylamine, diallylamine, 3-amino-1-methyl-1-propene, 3-amino-1-ethyl-1-propene, and 3-amino-1-npropyl-1. -Propene, 3-amino-1-
Phenyl-1-propene, 3-amino-2-methyl-1
-Propene, 3-amino-2-ethyl-1-propene,
3-amino-2-npropyl-1-propene, 3-amino-2-phenyl-1-propene, 3-amino-3-methyl-1-propene, 3-amino-3-ethyl-1-propene, 3 -Amino-3-npropyl-1-propene,
3-amino-3-phenyl-1-propene, N-methyl-3-amino-1-propene, N-ethyl-3-amino-1-propene, N-phenyl-3-amino-1-propene, N- Examples of the amine of the general formula [II] include n-propyl-3-amino-1-propene, and specific examples thereof include p-amino-stilbenzene and N-methyl-pamino-stilbenzene.

The amine containing an alcoholic hydroxyl group is
The following general formula [III]

[0036]

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Wherein R ⁸ is an aliphatic alkyl group having 2 to 5 carbon atoms, and R ⁹ is an aliphatic alkyl group having 1 to 3 carbon atoms or a phenyl group. An amine having an alcoholic hydroxyl group, specifically, ethanolamine, N-methyl-ethanolamine, N-phenyl-ethanolamine, N-phenyl-n-propanolamine, N-phenyl-n-butanolamine, etc. No.

It is desirable that such an amine is used in an amount of 2 to 5 mol, particularly preferably 2 to 3 mol, per 1 mol of the fluorine oligomer having ester groups at both ends of the main chain.
The reaction temperature of the fluorine oligomer having an ester group at both ends of the main chain with the amine having an unsaturated group or the amine having an alcoholic hydroxyl group is usually from -10 to 60C, preferably from 0C to 40C.

After completion of the reaction, the solvent was removed,
After drying for about 10 to 30 hours, a fluorine oligomer containing an unsaturated group or an alcoholic hydroxyl group at both ends of the main chain is obtained. The functional groups at both ends of the fluorine oligomer having an unsaturated group at both ends of the main chain are represented by the following general formula [IV]
Or [V]

[0040]

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[0041]

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[Wherein R ¹ , R ² , R ³ , R ⁴ , n, R ⁵ ,
R ⁶ and R ⁷ are each represented by the general formulas [I] and [I
I] has the same meanings as R ¹ , R ² , R ³ , R ⁴ , n, R ⁵ , R ⁶ and R ⁷ ]. Such a fluorinated oligomer having unsaturated groups at both ends of the main chain has a number average molecular weight of 1,000 to 1,000.
An oligomer having a value of 10,000.

The functional groups at both ends of the fluorine oligomer having an alcoholic hydroxyl group at both ends of the main chain are represented by the following general formula [VI]

[0044]

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[0045] [wherein, R ⁸ and R ⁹ are each the same meaning as R ⁸ and R ⁹ in the general formula [III]] represented by. Such a fluorinated oligomer having an alcoholic hydroxyl group at both ends of the main chain has a number average molecular weight of 1,000 to 1,000.
An oligomer having a value of 0.

Such a fluorinated oligomer having an unsaturated group at both ends of the main chain and a fluorinated oligomer having an alcoholic hydroxyl group at both ends of the main chain are obtained by cross-linking a raw rubber as a raw material,
In the case of a copolymer containing vinylidene fluoride, it is a fluorine oligomer containing a repeating unit derived from vinylidene fluoride. In the case where the above-mentioned fluorine oligomer containing one end ester group at the main chain is used as a starting material, the fluorine oligomer containing ester group at both ends of the main chain is subjected to an amidation reaction with an amine containing an unsaturated group or an amine containing an alcoholic hydroxyl group, and both ends of the main chain are mixed. In the same manner as in the method for obtaining a terminal oligomer having a terminal unsaturated group or a fluorine oligomer having an alcoholic hydroxyl group at both ends of the main chain, the main chain one-terminal ester group-containing fluorine oligomer is amidated to obtain a main chain having one terminal unsaturated group-containing fluorine. Oligomers or fluorine oligomers having an alcoholic hydroxyl group at one terminal of the main chain can be obtained. Curable composition (i) Main-chain terminal unsaturated terminal group-containing fluorine oligomer (hereinafter sometimes referred to as “fluorine oligomer (A)”) obtained as described above, and (meth) as a reactive diluent A curable composition can be obtained from the acrylic monomer (C) and the photopolymerization initiator (D) or the radical generator (E).

The fluorine oligomer (A) is used in an amount of 20 to 80% by weight, preferably 50 to 70% by weight, based on 100% by weight of the curable composition. (ii) a curable composition comprising a fluorine oligomer having an alcoholic hydroxyl group at both ends of the main chain obtained as described above (hereinafter sometimes referred to as “fluorine oligomer (B)”) and a polyisocyanate compound (I) You can get things.

The fluorine oligomer (B) is used in an amount of 20 to 80% by weight, more preferably 50 to 70% by weight, based on 100% by weight of the curable composition. In the present invention, in obtaining such a curable composition, other reactive diluents, other curing agents (F), inorganic / organic pigments (G), and other additives (H) are appropriately used. Is done.

Reactive Diluent In the present invention, it is preferable to add a diluent when preparing the curable composition comprising the fluorine oligomer (A). Since fluorine oligomers having functional groups at both ends of the main chain have high viscosity, processing operations such as mixing of the fluorinated oligomer (A) with a pigment or filler, application of a curable composition, and injection are easy as they are. It is not.
As such a diluting solvent, a reactive diluent is preferably used. The reactive diluent is a fluorine oligomer (A)
It is particularly preferably used when preparing a cured composition by using a photopolymerization initiator and / or a radical generator.

As such a reactive diluent, a (meth) acrylic monomer (C) is preferred from the viewpoint of curing speed. Any such (meth) acrylic monomer can be used as long as it dissolves the fluorine oligomer (A). Further, either a monofunctional or polyfunctional (meth) acrylic monomer can be used. Specific examples of such (meth) acrylic monomers include (meth) acrylates of alkoxyalkylene glycols, mono- or di (meth) acrylates of alkylene glycols, and mono- or poly (meth) acrylates of alkylene oxide adducts of polyols. And the like.

Examples of the (meth) acrylate of alkoxyalkylene glycol include mono (meth) acrylate of methoxyethylene glycol and mono (meth) acrylate of ethoxyethylene glycol. Examples of the alkylene glycol mono- or di (meth) acrylate include ethylene glycol mono- or di (meth) acrylate and propylene glycol mono- or di (meth) acrylate.

In the mono- or poly (meth) acrylates of the alkylene oxide adducts of polyols, polyols include alkylene glycols such as ethylene glycol and propylene glycol, triols such as trimethylolethane, trimethylolpropane and glycerin, pentaerythritol and diol. Examples include polyols having four or more hydroxyl groups, such as pentaerythritol. Examples of the alkylene oxide include ethylene oxide, propylene oxide and butylene oxide. The addition mole number of the alkylene oxide is preferably 1 to 10 moles.
Specific examples of the (meth) acrylate include diethylene glycol mono or di (meth) acrylate, tetraethylene glycol mono or di (meth) acrylate, dipropylene glycol mono or di (meth) acrylate, and tripropylene glycol mono or di ( Mono or di (meth) acrylates of polyalkylene glycols, such as meth) acrylates, and trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate and dipentaerythritol hexaacrylate Examples include modified ethylene oxide and propylene oxide.

Further, two or more kinds of such reactive diluents can be used in combination. Further, methyl (meth) may be used within a range that does not adversely affect the finally obtained reactive resin.
Alkyl (meth) acrylates such as acrylate, ethyl (meth) acrylate, and propyl (meth) acrylate; trimethylolpropane tri (meth) acrylate; pentaerythritol tri (meth) acrylate;
Reactive diluents such as pentaerythritol tetra (meth) acrylate and dipentaerythritol hexaacrylate can also be mixed.

As reactive diluents, monofunctional and polyfunctional (meth) acrylic monomers can also be used. Specific examples of the monofunctional monomer include acrylamide, 7-amino-3,7-dimethyloctyl (meth) acrylate, isobutoxymethyl (meth) acrylamide, isobornyloxyethyl (meth) acrylate,
Isobornyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethyldiethylene glycol (meth) acrylate, t-octyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone (meth) acrylamide, N, N-dimethylaminoethyl ( (Meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, lauryl (meth) acrylate, dicyclopentadiene (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, N, N -Dimethyl (meth) acrylamidotetrachlorophenyl (meth) acrylate, 2-tetrachlorophenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, tetrabromophenyl ( Data) acrylate, 2-
Tetrabromophenoxyethyl (meth) acrylate,
2-trichlorophenoxyethyl (meth) acrylate,
Tribromophenyl (meth) acrylate, 2-tribromophenoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 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) acrylate, and General formulas [VII] to [IX]

[0055]

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[In the formula, R ⁶ represents a hydrogen atom or a methyl group, R ⁷ is an alkylene group having 2 to 6, preferably 2 to 4 carbon atoms, and R ⁸ is a hydrogen atom or 1 to 1 carbon atom.
2, preferably an alkyl group of 1 to 9, Ar ¹ is a divalent aromatic group such as a phenylene group, a biphenylene group, a naphthylene group, and s is a number of 0 to 12, preferably 1 to 8 ]

[0057]

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Wherein R ⁹ is a hydrogen atom or a methyl group, R ¹⁰ is an alkylene group having 2 to 8, preferably 2 to 5 carbon atoms, and t is 1 to 8, preferably 1 to 4 Is the number of

[0059]

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Wherein R ¹¹ represents a hydrogen atom or a methyl group; R ¹² represents an alkylene group having 2 to 8, preferably 2 to 5 carbon atoms; R ¹³ represents a hydrogen atom or a methyl group; t is a number of 1 to 8, preferably 1 to 4, and a plurality of R ¹³ may be the same or different.] (meth) acryloyl group-containing monomer; -Vinyl-containing monomers such as vinylpyrrolidone and N-vinylcaprolactam.

These monofunctional monomers include, for example, Aronix M-111, M-113, and M-117 (all of which are manufactured by Toagosei Co., Ltd.)
KAYARAD TC110S, R-629, R-644 (Nippon Kayaku Co., Ltd.), Viscort 3700 (Osaka Organic Chemical Industry Co., Ltd.)
) Can also be used.
When using a monofunctional monomer,
N-vinylpyrrolidone, N-vinylcaprolactam and acryloylmorpholine are preferred.

Examples of the polyfunctional monomer include, 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 di (meth) acrylate, trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate, tripropylene glycol di (meth) ) Acrylate, neopentyl glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, pentaery Ritorutori (meth)
Acrylate, polyester di (meth) acrylate,
Polyethylene glycol di (meth) acrylate, tris [(meth) acryloxyethyl] isocyanurate and the following general formula [X]

[0063]

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In the formula, R ¹⁴ represents a hydrogen atom or a methyl group, and X is a divalent group such as an alkylene group having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms, a phenylene group, a biphenylene group and a naphthylene group. And p and q are each independently 1 to
(Preferably from 1 to 5)] and (meth) acryloyl group-containing monomers such as compounds represented by the formula (I).

When a polyfunctional monomer is used, among these, in particular, tris ((meth) acryloxyethyl) isocyanurate, trimethylolpropane triacrylate, EO-modified trimethylolpropane triacrylate, tricyclodecanediyl dimethylene dimethyl ( (Meth) acrylate, tetraethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate,
The (meth) acryloyl group-containing monomer represented by the formula [IIX] is preferable.

As the polyfunctional monomer, specifically, Iupima UV, SA1002 (above, Mitsubishi Chemical Corporation)
Manufactured), VISCOAT 700 (Osaka Organic Chemical Industry Co., Ltd.)
KAYARAD R-604, D-310, D-330 (all manufactured by Nippon Kayaku Co., Ltd.), ARONIX M-210, M-315 (all manufactured by Toagosei Co., Ltd.), epoxy ester 40EM, 70PA, 200PA, 1
600A, 80MFA, 3002M, 3002A, 3000M, 3000A, 200EA, 40
Commercially available monomers such as 0EA (all manufactured by Kyoeisha Chemical Co., Ltd.) can also be used.

The above monofunctional and polyfunctional monomers are:
One type may be used alone, or two or more types may be used in combination. In addition, (meth) acrylate monomers having a polyester in the side chain are also preferably used. For example,
ω-carboxypolycaprolactone monoacrylate (M
-5300, manufactured by Toagosei Co., Ltd.), acrylic acid dimer (M-5
600, manufactured by Toagosei Co., Ltd.), polyester acrylate (M-6100, M-6200, M-6250, M-6500, M-7100, M-8030,
M-8060, M-8100, M-8530, M-8560, M-9050, manufactured by Toagosei Co., Ltd.), etc., such as Plaxel F, FD, FMA, DC
Daicel Chemical Industries, Ltd.).

In particular, when the mechanical properties of the curable composition are to be improved, acrylates collectively referred to as urethane acrylates can be used. Specifically, the following general formula [XI], [XII] CH 2 = CHCOOR'OCONH- (R-NHCOO- [ _{Polyol] -OCONH) n - R-NHCOOR'OCOCH} = CH 2 ··· [XI] or _{CH 2 = CHCOOR'OCONH- (R-NHCOO-} [ polyol] -OCONH) _n - [polyol] -OH ··· [XII] [wherein, R, R 'are each independently alkyl of 1 to 5 carbon atoms Acrylate (M-1100, 120
0, 1210, 1310, 1600 (manufactured by Toagosei Co., Ltd.)).

In the general formulas [XI] and [XII], examples of the alkyl group having 1 to 5 carbon atoms include a methyl group,
Ethyl group, n-propyl group, i-propyl group, n-butyl group,
Examples thereof include a t-butyl group, an n-pentyl group, and an i-pentyl group. Among them, an alkyl group having 1 to 3 carbon atoms is preferable. These reactive diluents can be used alone or in combination of two or more.

In the present invention, such a reactive diluent is
20 to 75% by weight based on 100% by weight of the curable composition,
In particular, it is preferable to mix in an amount of 30 to 50% by weight. 7
If the content exceeds 5% by weight, the curable composition tends to have reduced dent resistance, and the durability of repeated printing tends to be reduced. When the amount is less than 20% by weight, the viscosity of the curable composition increases, and it becomes difficult to perform processing operations such as application and injection of the curable composition.

Photopolymerization Initiator (D) In the present invention, a photopolymerization initiator can be added to the curable composition comprising the fluorinated oligomer (A). As the photopolymerization initiator, any may be used as long as it is decomposed by light irradiation to generate radicals and initiate polymerization,
If necessary, a sensitizer can be further used. Here, “light” refers to ultraviolet light, visible light, or the like. When curing by electron beam, it is not necessary to mix a photopolymerization initiator.

Specific examples of such a photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone,
2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1
-One, 1,1-dimethoxydeoxybenzoin, 3,3'-dimethyl-4-methoxybenzophenone, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-methyl-1 -[4- (Methylthio) phenyl] -2-morpholino
-Propan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl-2,4,6-trimethylbenzoylphenylphosphinate, bis- (2,6-dimethoxybenzoyl) -2,4,4- Trimethylpentylphosphine oxide, bisacylphosphine oxide, methylbenzoyl formate, 4-benzoyl-4'-methyldiphenylsulfide, benzyldimethylketal, fluorenone, fluorene, benzaldehyde, benzoin ethyl ether, benzoin propyl ether, Michler's ketone, 2- Benzyl-2-dimethylamino-1-
(4-morpholinophenyl) -butan-1-one, acetophenone, 3-methylacetophenone, benzophenone, 4,
4′-dimethoxybenzophenone, 4,4′-diaminobenzophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone (BTTB), acetophenone benzyl ketal, triphenylamine, carbazole,
4-chlorobenzophenone, anthraquinone, xanthone, diethylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2-chlorothioxanthone, 1-chloro-4-propoxythioxanthone,
And BTTB and a dye sensitizer; for example, a combination of xanthene, thioxanthene, coumarin, ketocoumarin and the like. In addition, the following general formula (XIII)

[0073]

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Wherein R ⁴ and R ⁵ are each independently an alkyl group having 1 to 5 carbon atoms, Ar is a divalent aromatic group such as a phenylene group, a biphenylene group, a naphthylene group, and r is 2 to 50, preferably 2 to 20]. The general formula [XI
II], the alkyl group having 1 to 5 carbon atoms includes, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group, n-pentyl group, i-pentyl And the like. Among them, an alkyl group having 1 to 3 carbon atoms is preferable.

Of these, benzyldimethyl ketal, benzophenone, 1-hydroxycyclohexylphenyl ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl-2,4,6-trimethylbenzoylphenylphosphinate, bis- ( 2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2 -
Dimethylamino-1- (4-morpholinophenyl) -butane
1-one and the like are preferred. These commercial products include Irg
acure 184, 651, 500, 907, 369, 784, 2959 (or more, manufactured by Ciba-Geigy), Lucirin TPO, LR8893 (or more, BASF
Darocur 1116, 1173 (Merck), Juvecryl P36 (UCB), ESCACURE KIP150, ESC
ACURE KIP100F (all manufactured by LAMBERTI) can be mentioned.

In the present invention, a photopolymerization initiator can be added to the aqueous dispersion, particularly when the composition is cured by irradiation with ultraviolet rays. As the photopolymerization initiator, a water-soluble or hydrophilic photopolymerization initiator is preferable, and specifically, Darocure 2959, 1173, 116, Irgacure 184, 261, 500,
651, 907, 369, 819, 1700, 2959, 1173 (all manufactured by Ciba Specialty Chemicals), Kanta Cure AB
Q, BTC and QTX (all manufactured by Shell Chemical). In addition, benzoin, benzoin methyl ether, which is usually used in a solvent system or a non-solvent system,
Benzophenone, benzyldimethyl ketal and 2,4-
Dimethylthioxanthone and the like can also be used.

Such photopolymerization initiators can be used alone or, if necessary, in combination of two or more. When two types are used in combination, a combination of 1-hydroxycyclohexylphenyl ketone and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one or 2,4,6-trimethylbenzoyl It is preferable to use a combination of diphenylphosphine oxide and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one.

The photopolymerization initiator is preferably used in an amount of 0.01 to 100 parts by weight based on the total weight of the curable composition.
It is 10 parts by weight, more preferably 0.02 to 8 parts by weight, particularly preferably 0.03 to 6 parts by weight. If the amount exceeds 10 parts by weight, the curing properties of the resin liquid, the physical properties of the cured product, and handling may be adversely affected. If the amount is less than 0.01 parts by weight, the curing speed decreases and the productivity tends to decrease. I do.

The photopolymerization initiator may be added before or after dispersion in water. In the case of using a photopolymerization initiator which is solid and has particularly low solubility in water, it is preferable to add the photopolymerization initiator before dispersing in water because the photopolymerization initiator is easily dissolved in water. Prior to curing, it is preferable that water as a dispersion medium and ammonia or an organic amine as a preferable neutralizing agent be evaporated and scattered by heating. If moisture remains in the cured coating film, the film strength may be insufficient or the transparency of the film may be impaired.

Radical Generator (E) In the present invention, when curing the curable composition containing the fluorine oligomer (A), a two-component main agent type acrylic adhesive may be used as a radical generator for curing. it can. Such a two-pack main agent type acrylic adhesive comprises a first liquid mainly composed of a polymerizable (meth) acrylic monomer and an organic peroxide generating radicals, and a polymerizable (meth) acrylic adhesive.
It comprises an acrylic monomer and an organic peroxide in the first liquid and a second liquid mainly composed of a reducing agent forming a redox catalyst system. Specifically, the first liquid contains phosphorous acid or / And the following general formulas [XIV], [XV] and [XV
I]

[0081]

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Wherein R ₁ is an aryl group, having 1 to 5 carbon atoms
An alkyl group, a halogenated alkyl group or R ₃ OR ₄ —
(R ₃ and R ₄ are the same or different alkyl groups having 1 to 5 carbon atoms), and R ₂ is hydrogen or R ₁ ]

[0083]

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[Wherein, R ₅ is an aryl group and R ₆ is a hydroxyl group or an aryl group]

[0085]

Embedded image

Wherein R ₇ is an aryl group, and R ₈ is a hydroxyl group or an aryl group, which contains one or more acidic phosphorus compounds selected from the group consisting of: A two-pack main agent type acrylic adhesive characterized by being a soluble vanadium compound is exemplified. Examples of the organic peroxide contained in the first liquid include hydroperoxides such as t-butyl hydroperoxide, p-methane hydroperoxide, cumene hydroperoxide, and diisopropylbenzene hydroperoxide;
Peroxyesters such as t-butylperoxylaurate, t-butylperoxybenzoate, and t-butylperoxide decanoate are suitable, and hydroperoxide is particularly preferable.

The content of the organic peroxide in the first liquid is 1 to 20% by weight, preferably 7 to 20% by weight in the first liquid.
Preferably, it is used in an amount of from 10 to 10% by weight. Examples of the phosphorous acid or the acidic phosphorus compound represented by the general formula [XIV], [XV] or [XVI] contained in the first liquid include monomethyl phosphate, dimethyl phosphate, monoethyl phosphate, diethyl phosphate, and monophosphate. Isopropyl phosphate, diisopropyl phosphate,
Monobutyl phosphate, dibutyl phosphate,
Mono-β-chloroethyl phosphate, di-β-chloroethyl phosphate, mono-β-bromoethyl phosphate, di-β-bromoethyl phosphate, monoethoxyethyl phosphate, diethoxyethyl phosphate, monobutoxy Ethyl phosphate, dibutoxyethyl phosphate, phenyl phosphate, diphenyl phosphate, phenyl phosphonic acid, diphenyl phosphonic acid, phenyl phosphinous acid, diphenyl phosphinous acid, and the like.
Species or mixtures of two or more are used.

The content of the acidic phosphorus compound in the first liquid is 0.01 to 10% by weight, preferably 0.1 to 10% by weight.
5 to 7% by weight is suitable. Specific examples of the soluble vanadium compound contained in the second liquid include vanadyl acetylacetonate, vanadyl stearate, vanadium naphthenate, vanadium acetylacetonate, vanadium benzoylacetonate, vanadyl oxalate, and the like. These soluble vanadium compounds are:
The content in the second liquid is 0.01 to 1% by weight, preferably 0.1 to 0.5% by weight.

Other curing agent (F) In the present invention, m-phenylenebismaleimide is used as a curing agent in order to increase the curing speed of the curable composition containing the fluorine oligomer (A) and the fluorine oligomer (B). , 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, N, N '-(4,4'-diphenylmethane)
Bismaleimides such as bismaleimide, 1,3-cyclohexylene-bis-maleimide, and hexamethylene bismaleimide can also be blended.

As an additive for increasing the curing rate of the curable composition containing the fluorine oligomer (A) and the fluorine oligomer (B), a curing accelerator such as ethylenethiourea, acetylthiourea or benzoylthiourea is used. It can also be blended with these curable compositions. When such a curing agent is blended, the amount used is preferably from 0.01 to 1 per 100 parts by weight of the total weight of the curable composition.
0 parts by weight, more preferably 0.1 to 5 parts by weight.

Pigment (G) In the present invention, the curable composition containing the fluorine oligomer (A) or the fluorine oligomer (B) may optionally contain an inorganic or organic pigment. Specific examples of the pigment include white pigments such as titanium oxide, zinc white, lead white, lithobon and antimony oxide, black pigments such as aniline black, iron black and carbon black, graphite, yellow iron oxide, titanium yellow, and Hansa yellow. (10G, 5G, 3G, etc.), yellow pigments such as benzine yellow and permanent yellow, orange pigments such as chrome vermillion, permanent orange, Vulcan fast orange and indanthrene brilliant orange, iron oxide, permanent brown and para brown, etc. Brown pigment, red bengala, cadmium red, antimony vermilion, permanent red, rhodamine lake, alizarin lake, thioindigo red, PV carmine, monolite forst red and quinacdrine red pigment Red pigment, cobalt purple,
Purple pigments such as manganese purple, fourth violet, methyl violet lake, indanthren brilliant violet and dioxazine violet, ultramarine, navy blue, cobalt blue, alkali blue lake, peacock blue lake, Victoria blue lake, metal-free phthalocyanine blue, copper phthalocyanine Besides blue pigments such as blue, indaslen blue and indigo, chrome green, chromium oxide, emerald green, naphthol green, green gold, acid green lake, malachite green lake, green pigments such as phthalocyanine green and polychlorobrom copper phthalocyanine, Examples include various fluorescent pigments, metal powder pigments, extender pigments, and the like.

These pigments are preferably blended in an amount of 1 to 50 parts by weight, more preferably 5 to 30 parts by weight, based on the composition excluding the photopolymerization initiator. Other Additives (H) In the present invention, other additives as long as the function of the cured composition such as the curing speed or the strength of the curable composition containing the fluorine oligomer (A) and the fluorine oligomer (B) is not hindered. Additives can be included in the curable composition. For example, liquid rubber such as liquid acrylonitrile-butadiene copolymer, fine powdered polyethylene for the purpose of imparting thixotropic properties, dibenzylidene-D-sorbitol, cellulose triacetate, stearic amide, bentonite, fine powdered silica, etc. Thixotropic agent,
To enhance long-term storage stability at room temperature, 2,6-di-t
-Butyl-4-methylphenol, 2,2-methylenebis (4-methyl-6-t-butylphenol), benzoquinone, hydroquinone, tetrasodium ethylenediaminetetraacetate, oxalic acid, N-methyl-N-nitrosoaniline, N-nitroso If desired, a radical polymerization inhibitor such as diphenylamine may be added.

In the present invention, the curable composition may be used after being diluted with an organic solvent, if necessary. The organic solvent is not particularly limited as long as it is an organic solvent that dissolves the fluorine oligomer (A), the fluorine oligomer (B), the photopolymerization initiator (D), and the radical generator (E).
Preferably the boiling point is 50 ° C to 200 ° C, more preferably 6 ° C.
A solvent having a temperature of 0 ° C to 160 ° C. A solvent having a boiling point of less than 50 ° C. has a high risk of ignition when the organic solvent is dried and removed after application of the composition of the present invention, and it is difficult to control the thickness of the coating layer because it is easily volatilized. . Boiling point is 200
If the solvent exceeds ℃, it is difficult to volatilize, and thus it is difficult to dry and remove the organic solvent. Specific examples of such an organic solvent include alcohols such as methanol, ethanol, isopropyl alcohol, butanol, and cyclohexanol; ethyl acetate, butyl acetate, isoamyl acetate, and esters such as 3-methoxymethyl propionate; Examples include ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, and aromatic hydrocarbons such as benzene, toluene and xylene. These solvents can be used alone or in combination of two or more.

Among these, preferred organic solvents are ethanol, isopropyl alcohol, butanol, and these alcohol solvents and acetate solvents such as ethyl acetate and butyl acetate, 3-methoxymethyl propionate, and toluene and xylene. And a mixed solvent comprising an aromatic hydrocarbon. Various other additives can be further added to the curable composition of the present invention as needed. These additives include, for example, sensitizers, antioxidants, light stabilizers, silane coupling agents,
Anti-aging agent, thermal polymerization inhibitor, leveling agent, surfactant, antistatic agent, storage stabilizer, coloring agent, ultraviolet absorber,
Examples thereof include a plasticizer, a lubricant, an inorganic filler other than the pigment (G) component of the present invention, an organic filler, a wettability improver, and a coating surface improver.

Examples of sensitizers include triethylamine, diethylamine, N-methyldiethanolamine, ethanolamine, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate,
There are isoamyl dimethylaminobenzoate and the like, and as commercial products, Ubecryl P102, 103, 104, 105 (above, UCB
KAYACURE DMBI, EPA (Nippon Kayaku Co., Ltd.)
Manufactured).

As antioxidants, Irganox 1010, 103
5, 1076 and 1222 (all manufactured by Ciba Geigy). As UV absorbers, Tinuvin P, 234, 32
0, 326, 327, 328, 213 (all manufactured by Ciba Geigy), S
umisorb 110, 130, 140, 220, 250, 300, 320, 340, 35
0, 400 (all manufactured by Sumitomo Chemical Co., Ltd.).

As light stabilizers, Tinuvin 292, 144, 62
2LD (all manufactured by Ciba-Geigy), Sanol LS-770, 76
5, 292, 2626, 1114, 744 (Mitsui Chemicals, Inc.)
Manufactured). As a silane coupling agent, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, and as a commercial product, SH60
62, SZ6030 (all manufactured by Dow Corning Toray Silicone Co., Ltd.), KBE903 and KBM803 (all manufactured by Shin-Etsu Silicone Co., Ltd.).

As anti-aging agents, Antigene W, S, P,
3C, 6C, RD-G, FR, AW (all manufactured by Sumitomo Chemical Co., Ltd.)
And the like. Non-static antistatic agents such as polyoxyethylene amines, polyoxyethylene alkyl amides, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, glycerin fatty acid esters, sorbitan fatty acid esters, etc. Agents, anionic antistatic agents such as alkylsulfonates, alkylbenzenesulfonates, alkyl sulfates and alkyl phosphates, quaternary ammonium salts, alkyl betaines and the like.

Further, the curable composition of the present invention contains epoxy resin, acrylic resin, acrylic group-containing monomer and N-
Polymer with vinylpyrrolidone, urethane acrylate,
Polymerizable compounds such as vinyl ether, propenyl ether, maleic acid derivative, polyamide, polyimide, polyamide imide, polyurethane, polybutadiene, chloroprene, polyether, polyester, pentadiene derivative, styrene / butadiene / styrene block copolymer, styrene / ethylene / butene / Styrene block copolymer, styrene / isoprene / styrene / block copolymer, acrylic resin containing styrene as main chain component, petroleum resin, xylene resin, ketone resin, fluorine oligomer, silicone oligomer, polysulfide oligomer Such polymers or oligomers can be appropriately blended.

Polyisocyanate Compound (I) In the present invention, a curable composition can also be obtained by blending a fluorine oligomer (B) and a polyisocyanate compound. Examples of such polyisocyanate compounds include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, (o, m or p) -xylene diisocyanate, and methylene bis (cyclohexyl isocyanate). , Trimethylhexamethylene diisocyanate,
Cyclohexane-1,3-dimethylene diisocyanate, cyclohexane-1,4-dimethylene diisocyanate and
At least one selected from 1,5-naphthalenediisocyanate is included.

The curable composition comprising the fluorinated oligomer (B) and the polyisocyanate compound may be used in combination with a polymer polyol or a dihydroxy compound used in the production of ordinary polyurethane. As the polymer polyol, specifically, at least one kind of polyether diol selected from polyethylene glycol, polypropylene glycol and polytetramethylene glycol, and at least one kind of polyester based diol selected from esters of polyhydric alcohol and polybasic acid Examples include at least one kind of polycarbonate diol selected from diol, hexamethylene carbonate and pentamethylene carbonate, and at least one kind of polylactone diol selected from polycaprolactone diol and polybutyrolactone diol. One or more of these polyether diols, polyester diols, polycarbonate diols and polylactone diols may be used in combination.

The number average molecular weight of such a polymer polyol is from 200 to 2,000, preferably from 600 to 1500. In particular, in the case of polytetramethylene glycol, a polymer obtained by curing a urethane / unsaturated organo oligomer using a material having a molecular weight of 850 is an elongation of 269%, a strength of 382 kg / cm ² , and a polycaprolactone diol having a molecular weight of 1,000 is used. Similarly, an elongation of 314% and strength of 293 kg / cm ² , and polycaprolactone diol having a molecular weight of 1250 provides excellent properties of an elongation of 383% and strength of 417 kg / cm ² .

The dihydroxyl compound is preferably at least one kind selected from glycols having a hydrocarbon skeleton having 2 to 10 carbon atoms.
More preferably, it is desirable to use a glycol having 2 to 6 carbon atoms. As such glycols, specifically, ethylene glycol, 1,3-propanediol, 1,
4-butanediol, neopentyl glycol, 3-methyl
-1,5-pentanediol and the like.

The amount of such a polymer polyol or dihydroxyl compound is preferably 10 to 60% by weight, more preferably 30 to 50% by weight, based on 100% by weight of the curable composition. The polyisocyanate compound is preferably 10 to 50% by weight, more preferably 15 to 30% by weight, based on 100% by weight of the curable composition.
The amount by weight is used.

Curing composition comprising fluorine oligomer (A)
Preparation of Products In the preparation of the curable composition of the present invention, the order of mixing the components is not essential, but it is usually easy to work and easy to disperse the inorganic particles as the pigment (G) component. In view of the above, a reactive diluent such as a fluorine oligomer (A) or a (meth) acrylic monomer (C), a polymerization initiator (D) or a radical generator (E), and an organic solvent as another additive (H) It is preferable that the pigment (G) is blended with the mixture to which the curing agent (F) and the like are added, if necessary, and the mixture is stirred until the inorganic particles are uniformly dispersed. The viscosity of the obtained cured composition at 25 ° C. is usually 1 to 100,000 mPa · s, preferably 5 to 50,000 mPa · s.

Further, the curable composition of the present invention can be coated on a substrate by various commonly used methods. Examples of such a coating method include methods such as dip coating, spray coating, flow coating, roll coating, and screen printing. The thickness of the coating film in these coatings is usually 0.1 to 50 μm, preferably 1 to 10 μm.

For curing the curable composition having the fluorinated oligomer (A) of the present invention, electron beam, ultraviolet ray, active energy ray and heat can be used. this house,
When curing with light, it is preferable to use ultraviolet light. The ultraviolet light used has a wavelength of 400 nm or less, and as a light source, for example, a metal halide lamp or a mercury lamp (high, medium, or low pressure may be used) can be used. The irradiation light amount is usually 0.01 to 10 J / cm ² , more preferably 0.1 to 10 J / cm ^2.
３3 J / cm ² .

When the composition of the present invention contains a solvent, after coating the composition, the composition is applied within the range of 1 second to 24 hours, preferably 10 seconds to 1 hour, at 0 to 200 ° C., preferably 20 seconds. ~ 150 ° C, more preferably 40 ~ 10
After the volatile components are dried as necessary at a temperature of 0 ° C., they can be cured by irradiation with radiation. Preparation of Cured Composition Containing Fluorine Oligomer (B) The curable composition comprising the main chain both-terminal alcoholic hydroxyl group-containing fluorinated oligomer (B) and the polyisocyanate compound (I) is subjected to a condensation reaction by a usual method. Can be cured. Further, a polymer polyol or a dihydroxyl compound, another curing agent (F), a pigment (G), and other additives (H) can be appropriately added to the curable composition as needed.

Use and method of use of the curable composition The curable composition according to the present invention has an excellent curing rate,
Paints, sealants, liquid casting gaskets, printing inks,
It can be used for an adhesive or the like. When the curable composition is directly applied as a coating, a spray coating or a roll coating method is preferably used. When the curable composition according to the present invention is used for a printing ink, an offset, a gravure offset, or a flexographic method is preferably used. When using a liquid dispenser, fill with sealant, In P
A lace gasket (IPG) can be used to form a sealing material between the objects to be sealed or on the sealing surface. In this case, a high viscosity and high thixotropy are required, so a thickness of 50 μ to 10 mm is required. .

[0110]

According to the present invention, the curable composition contains a fluorine oligomer having a functional group at both ends of the main chain in the curable composition, whereby the curing speed is high and the curing is excellent in toughness, stretchability, elasticity and the like. The composition can be provided.

[0111]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

[0112]

Example 1 [Fluorine Oligomer Containing Methyl Ester Groups at Both Main Chain Terminals] A carboxyl group at both main chain terminals obtained by the method described in Japanese Patent Application No. 10-150743 was placed in a separable flask having an internal volume of 3 liters. 156 g of the contained fluorine oligomer and 1017 g of methanol were introduced. After the fluorine oligomer was completely dissolved, 6.2 g of H ₂ SO ₄ was added dropwise, the external temperature of the flask was raised to 100 ° C., and the flask was refluxed for 3 hours. After the reflux, 75 to 80% of methanol was distilled off, and the solution containing the reaction product was allowed to reach room temperature.
Slowly introduce water into 0 volume of water while stirring,
A precipitate was obtained by decanter. The precipitate was washed with water about 5 times, and dried in a vacuum oven at 50 ° C. for 2 days to obtain 149 g of a yellow viscous compound. The yield was 95.5%. The obtained yellow viscous compound was identified by IR and NMR, and it was confirmed that this compound was a vinylidene fluoride-based fluorine oligomer having methyl esters at both ends of the main chain.

IR spectrum: 1781 cm ^-1 (-COO
CH ₃₎ [- COOH is ^{1771cm - 1] 1 H-NMR} ( acetone, TMS): 3.909ppm (-
COOCH ₃ )

[0114]

Example 2 [Fluorine Oligomer Containing Unsaturated Groups at Both Main Chain Terminals] 131 g of the fluorine oligomer having methyl ester groups at both main chain terminals obtained in Example 1 and 586 g of THF were introduced into a separable flask having an internal volume of 1 liter. did. After the fluorine oligomer was completely dissolved, the flask was cooled in a water bath containing ice, and the external temperature of the flask was reduced to 0%.
〜5 ° C. was maintained. Subsequently, 7.8 g of allylamine was dropped into the flask, and reacted for 1 hour. After the completion of the reaction, the product is transferred to an eggplant flask and T
HF was distilled off. The obtained reaction product is kept at 40 ° C.
In a vacuum oven overnight to give 128.6 g of a clear red-brown viscous compound. The yield was 98.2%. The obtained compound was identified by IR, and this compound was found to have an allyl group [-(CONHCH) at both ends of the main chain.
₂ CH = CH ₂ ) ₂ ] was confirmed to be a vinylidene fluoride-based fluorine oligomer. IR spectrum: 3462 cm ^-1 , 1543 cm ^-1 (CO
NH) 1717 cm ^-1 (N.H) 1654 cm ^-1 (CH = CH ₂ )

[0115]

[Example 3] [Fluorine oligomer having alcoholic hydroxyl groups at both ends of main chain] A methyl ester group at both ends of main chain was prepared in the same manner as in Example 2 except that 130 g of methanolamine was used instead of allylamine. Amidation of the contained fluorine oligomer yielded 126.9 g of a clear red-brown viscous compound. The yield is 97.
6%. IR and N
Identification by MR confirmed that this compound was a vinylidene fluoride-based fluorine oligomer having an alcoholic hydroxyl group [-(CONHCH ₂ CH ₂ OH) ₂ ] at both ends of the main chain. IR spectrum: 1711 cm ^-1 (-CONH-) ¹ H-NMR (acetone, TMS): 3.6 to 3.8 ppm
(-CH ₂ OH)

[0116]

Example 4 [Curing composition comprising fluorine oligomer containing unsaturated groups at both ends of main chain] To 50 phr of the product of Example 2,
ω-carboxypolycaprolactone monoacrylate (A
25 phr of RONIX M-5300 (manufactured by Toagosei Co., Ltd.) and 25 phr of light ester CH (manufactured by Kyoeisha Chemical Co., Ltd.) were added and stirred to obtain a transparent yellow mixture. To this mixture was added a photopolymerization initiator (IRGACURE 819 (manufactured by Ciba Chemical Co., Ltd.)) at 0.0
The composition obtained by adding 3 phr was irradiated with 500 W UV for 13 minutes to obtain a light-transparent brown cured product having excellent elongation.

[0117]

Example 5 [Curing composition comprising fluorine oligomer containing unsaturated groups at both ends of main chain] To 50 phr of the product of Example 2,
Methoxytriethylene glycol acrylate 25ph
r, 25 phr of ARONIX M-5300 (manufactured by Toagosei Co., Ltd.) was added and stirred to obtain a transparent yellow mixture. To this mixture was added a photopolymerization initiator (IRGACURE 819 (manufactured by Ciba Chemical Co., Ltd.)) in an amount of 0.1 g.
The composition obtained by adding 03 phr was irradiated with UV for 15 minutes to obtain a cured product excellent in flesh-colored elongation.

[0118]

Example 6 [Curing composition comprising fluorine oligomer containing unsaturated groups at both ends of main chain] To 50 phr of the product of Example 2,
50 phr of light ester CH (manufactured by Kyoeisha Chemical Co., Ltd.)
Was added and stirred to obtain a clear yellow mixture. A photopolymerization initiator (IRGACURE 819 (manufactured by Ciba Chemical Co., Ltd.)) is added to this mixture.
Was irradiated with UV for 15 minutes to obtain a flesh-colored and tough cured product.

[0119]

Example 7 [Curing composition comprising fluorine oligomer containing unsaturated groups at both ends of main chain]
25 phr of TG-A (manufactured by Kyoeisha Chemical Co., Ltd.) and 25 phr of light ester CH (manufactured by Kyoeisha Chemical Co., Ltd.) are added and stirred.
A clear yellow mixture was obtained. Add this mixture to IRGACURE 819
A composition obtained by adding 0.1 phr of a photopolymerization initiator mixed with IRGACURE 1700 (manufactured by Ciba Chemical Co., Ltd.) at a ratio of 1: 1 was irradiated with UV for 15 minutes, and became translucent yellow and elastic. An excellent cured product was obtained.

[0120]

Example 8 [Curing composition comprising fluorine oligomer containing unsaturated groups at both ends of main chain] To 50 phr of the product of Example 2,
Light ester CH (manufactured by Kyoeisha Chemical Co., Ltd.) 50 phr
Was added and stirred to obtain a clear yellow mixture. Add this mixture to IRGACURE 819 and IRGACURE 1700 (Ciba Chemical Co., Ltd.)
0.11 ph of a photopolymerization initiator obtained by mixing
When the composition obtained by adding r was irradiated with UV for 20 minutes, a glossy and tough cured product having good surface curing was obtained.

[0121]

Example 9 [Curing composition comprising fluorine oligomer containing unsaturated groups at both ends of main chain] To 30 phr of the product of Example 2, M
To a composition obtained by adding and stirring 70 phr of TG-A (manufactured by Kyoeisha Chemical Co., Ltd.), 0.3 phr of vanadium (III) acetylacetonate (V (III) -AAc), trimethyl phosphate (TMP) 3 .6 phr, 1,4-benzoquinone (PBQ)
0.25 phr was added and stirred to give a brown mixture. 4.6 phr of a polymerization initiator cumene hydroperoxide (CHPO, manufactured by NOF CORPORATION) was added to the mixture, and the mixture was cured at room temperature. As a result, a translucent yellow cured product having excellent elasticity was obtained.

[0122]

Example 10 [Curing composition comprising fluorine oligomer containing unsaturated groups at both ends of main chain] The product of Example 2 (50 phr)
To the composition obtained by adding 50 phr of ARONIX M-5300 (manufactured by Toagosei Co., Ltd.) and stirring, was added V (III) -AAc 0.3
2 phr and TMP 3.1 phr were added and stirred well to obtain a clear yellow mixture. This mixture is added to the polymerization initiator CHPO
(Nippon Oil & Fats Co., Ltd.) 4.7 phr was added and the mixture was cured at room temperature to obtain a beige cured product excellent in elongation.

[0123]

Example 11 [Curing composition comprising fluorine oligomer containing unsaturated group at both ends of main chain] The product of Example 2 (50 phr)
MTG-A (manufactured by Kyoeisha Chemical Co., Ltd.) 33 phr, ARONIXM-53
To the composition obtained by adding 17 phr and stirring, was added V (III)
-AAc 0.3 phr, TMP 3.33 phr, PBQ
0.17 phr was added and stirred well to obtain a brown mixture. To this mixture was added 4.57 phr of a polymerization initiator CHPO (manufactured by NOF CORPORATION), and the mixture was cured at room temperature. As a result, a glossy cured product having good surface curing was obtained.

[0124]

Example 12 [Curing composition comprising fluorine oligomer containing unsaturated groups at both ends of main chain] The product of Example 2 (50 phr)
To the composition obtained by adding 25 phr of MTG-A and 25 phr of ARONIX M-5300 to 0.28 ph of V (III) -AAc
r, 2.9 phr of TMP and 0.3 phr of PBQ were added, and the mixture was stirred well to obtain a brown mixture. 4.26 ph of a polymerization initiator CHPO (manufactured by NOF CORPORATION) was added to this mixture.
When r was added and the mixture was cured at room temperature, a brown cured product having good elasticity and elongation was obtained.

[0125]

Example 13 [Curing composition composed of a fluorine oligomer containing an alcoholic hydroxyl group at both ends of the main chain] Acetone was added to 4.3 g of the product of Example 3, and 50% of the fluorine oligomer was added.
A composition was prepared, and 0.91 g of 3,3′-dimethyl-4,4′-biphenylenediisocyanate was added thereto and stirred to obtain a brown viscous mixture. The obtained mixture was heated in an oven at 40 ° C. for 10 minutes and further in an oven at 120 ° C. for 15 minutes to obtain a hardened ocher-colored cured product.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08F 290/04 C08F 290/04 C08G 18/62 C08G 18/62 F term (Reference) 4J011 QA12 QA13 QA17 QA22 QA23 QA24 QB01 SA01 SA21 SA31 SA51 SA63 SA64 UA01 4J027 AA08 BA07 BA08 BA14 BA19 BA20 BA21 BA24 BA25 BA26 CB10 CC03 CC04 CC05 4J034 DA01 DB03 DB04 DD07 DP15 GA50 HA01 HA07 HC12 HC17 HC22 HC46 HC52 HC61 HC71 HC73 4J100 AC22 BA CA04 CA05 HA61 HA62 HC09 HC47 HC48

Claims (9)

[Claims] 1. A fluorine oligomer having a number average molecular weight of 1,000 to 10,000 and having an ester group at both ends of the main chain of the fluorine oligomer, which has ester groups at both ends of the main chain of the fluorine oligomer. 2. A fluorine oligomer having a number average molecular weight of 1,000 to 10,000 and having unsaturated groups at both terminals of the main chain of the fluorine oligomer, wherein the fluorine oligomer has an unsaturated group at both terminals of the main chain of the fluorine oligomer. 3. A fluorine oligomer having a number average molecular weight of 1,000 to 10,000 and having an alcoholic hydroxyl group at both ends of the fluorine oligomer main chain. 4. The fluorine oligomer according to claim 1, wherein the fluorine oligomer is a copolymer containing a repeating unit derived from vinylidene fluoride. 5. A method according to claim 1, wherein the fluorine oligomer having an ester group at both ends of the main chain and the amine having an unsaturated group are reacted at 60 ° C.
The method for producing a fluorine oligomer having an unsaturated group at both ends of the main chain according to claim 2, wherein the reaction is carried out as follows. 6. The method according to claim 1, wherein the fluorine oligomer having both ester groups at both ends of the main chain and the amine having an alcoholic hydroxyl group are reacted at 60 ° C. or lower.
2. The method for producing a fluorine oligomer having an alcoholic hydroxyl group at both ends of the main chain according to the above. 7. A curable composition comprising the fluorine oligomer having an unsaturated group at both ends of the main chain according to claim 2, a (meth) acrylic monomer and a photopolymerization initiator. 8. A curable composition comprising the fluorine oligomer having an unsaturated group at both ends of the main chain according to claim 2, a (meth) acrylic monomer and a radical generator. 9. A curable composition comprising the fluorine-containing oligomer having an alcoholic hydroxyl group at both ends of the main chain according to claim 3 and a polyisocyanate compound.