JPH03106915A - curable composition - Google Patents

Abstract

PURPOSE:To obtain a curable composition having good quality and excellent compatibility with another component such as a crosslinking agent by mixing a polymerizable fluorine compound containing a diisocyanate residue, a diol residue and a polymerizable unsaturated bond with a curing agent. CONSTITUTION:A curable composition comprising a fluorine compound having a structural unit of formula I (wherein R is an alkylene) and a structural unit of formula II (wherein Rf is a fluoroalkylene) and a polymerizable unsaturated bond and a curing agent. Examples of the diisocyanate residue of the structural unit of formula I include tolylene diisocyanate and tetramethylxylene diisocyanate. Examples of the diol residue of the structural unit of formula II include 4,4,4-trifluorobutane-1,2-diol and 2,2,3,3,-tetrafluorobutane-1,4-diol. To introduce the polymerizable unsaturated bond, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate or the like is used.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a curable composition comprising a polymerizable fluorine compound and a curing agent, which can be used as adhesives, sealants, paints, etc.

(Prior Art and Problems to be Solved by the Invention) Acrylic curable compositions are widely used as adhesives, sealants, and paints. Further, organic fluorine compounds, particularly compounds having a perfluoroalkyl group, have a low critical interfacial tension and exhibit remarkable water and oil repellency. Therefore, by incorporating a polymerizable compound having a fluoroalkyl group into an acrylic curable composition, adhesives, sealants, and paints can be coated with fluorine's unique properties such as chemical resistance, water repellency, oil repellency, and low refractive index. It is possible to give characteristics such as:

When attempting to introduce such properties unique to fluorine into an acrylate-based cured composition, conventionally a method using a fluorinated alkyl acrylate as a polymerizable compound having a fluoroalkyl group has been generally carried out. However, acrylates having fluoroalkyl groups with high fluorine content, such as 1,1,2,2-tetrahydrohebbutadecafluorodecyl acrylate, may be combined with other components such as trimethylolbroban triacrylate as a crosslinking agent. are incompatible. Therefore, it has been difficult to obtain high-quality hardenable kumikaimono.

(Means for Solving the Problems) Therefore, as a result of various studies on fluorine-containing curable compositions free from the above-mentioned drawbacks, the present inventors found that when a specific polymerizable fluorine compound described below is used, the compound The present invention was completed based on the discovery that a high-quality curable composition can be obtained that has good compatibility with other components such as a crosslinking agent.

That is, the present invention provides the following structural unit (in the formula, R represents an alkylene group) and the following structural unit -[0-Rf-0 code
(II) (in the formula, Rf represents a fluoroalkylene group), and is a curable composition containing a polymerizable fluorine compound having a polymerizable unsaturated bond and a curing agent.

The present invention will be explained in detail.

First, the polymerizable fluorine compound used in the present invention will be explained. Examples of the residual diisocyanate of the structural unit (1), which is one of the structural units of this polymerizable fluorine compound, include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, and tolydine diisocyanate. , 1.6
-Hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, 4,4'-
Cyclohexylmethane diisocyanate, lysine diisocyanate, p-phenyl diisocyanate, transcyclohexane-1,4-diisocyanate, tetramethylxylene diisocyanate, etc. are used.

Further, examples of the diol residue of the structural unit (II), which is one of the structural units of the polymerizable fluorine compound used in the present invention, include 4,4,4-trifluorobutane-1.
2-diol, 4,4,5.5-tetrafluorobentane-1,2-diol, 4,4,5,5,5-pentafluoropentane-1,2-diol, 4,4,5,5,
6,6-hexafluorohexane-1,2-diol,
4,4,5,5,6,6,6-hebutafluorohexane-1,2-diol, 4,4,5,5, 6, 6,
7, 7-octafluorohebutane-1,2-diol, 4,4,5,5,6,6,7,7,8,8,9,9,
9-tridecafluorononane-1,2-diol, 4
,4,5,5,6,6,7,7,8,8,9,9,10
, 10,11,11,11-hebutadecafluorotridecane-1,2-diol, 2,2,3.3-tetrafluorobutane-1,4-diol, 2,2,3,3,4,
4-hexafluoropentane-1,5-diol, 2,
2,3,3,4,4,5,5-octafluorohexane-1,6-diol, 2,2,3,3,4,4,5,
5, 6, 6-decafluorohebutane-1,7-diol, 2,2, 3, 3, 4, 4, 5, 5,
6, 6, 7, 7-dodecafluorooctane-1
,8-diol, 2,2,3,3,4,4,5,5,6
,6,7,7,8,8-tetradecafluorononane-1
．． 9-diol, 2, 2, 3, 3, 4, 4,
5, 5, 6, 6, 7, 7, 8, 8, 9
, 9-hexadecafluorodecane-L,10-diol, etc. are used.

Furthermore, the polymerizable fluorine compound used in the present invention has a polymerizable unsaturated bond, but the number of these unsaturated bonds is 1 or 2 or more, and the introduction thereof requires a group that reacts with the diisocyanate or diol described above. and a compound containing one or more polymerizable unsaturated bonds is used. For example, 2-hydroxyethyl acrylate, 2-hydroxybrobyl acrylate, 2-hydroxyethyl methacrylate, 2
-Hydroxybutylene methacrylate, allyl alcohol, 2-hydroxybutane-1,3-diol diacrylate, 2-hydroxypropane-1,3-diol diacrylate, etc. are used.

The polymerizable fluorine compound used in the present invention is produced by reacting the diisocyanate, diol, and polymerizable unsaturated bond-containing compound. For example, it is produced by first reacting a diisocyanate and a diol, and then reacting the reaction product with a polymerizable unsaturated bond-containing compound. It is effective to use a catalyst in these reactions. Examples of catalysts include triethylene diamine, N, N, N', N
',N'-tetramethylhexamethylenediamine, N,
N'-dimethylcyclohexylamine, methylenebis(
Dimethylcyclohexyl)amine, N,N-dimethylcetylamine, N,N-dimethylbenzylamine, morpholine, phenothiazine, etc. are used.

In addition to the above polymerizable fluorine compound, the curable composition of the present invention may contain other polymerizable monomers as necessary. In that case, the amount of the polymerizable fluorine compound used is 5% by weight or more of the total polymerizable monomers in the composition. This polymerizable monomer is as follows.

Examples of monofunctional monomers include acrylic acid, methacrylic acid, acrylic esters, methacrylic esters, and fluoroalkyl acrylates and fluoroalkyl methacrylates having a fluoroalkyl group in the ester moiety.

Further, as a polyfunctional crosslinking monomer, for example, 1.3-
Butanediol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, diethylene glycol diacrylate, neopentyl glycol diacrylate, polyethylene glycol diacrylate, tripropylene glycol diacrylate, hydroxy bivalic acid ester neo Pentyl glycol diacrylate, hydroxy bivalic acid ester neobel glycol derivative diacrylate, neopentyl glycol-modified trimethylolpropane diacrylate, trifunctional monomers such as trimethylolpropane triacrylate, pentaerythritol triacrylate, pentafunctional monomers such as Examples include dipentaerythritol monohydroxybentaacrylate, hexafunctional monomers such as diventaerythritol hexaacrylate, and the like.

As the curing agent used in the present invention, a radical polymerization initiator is preferable, and various polymerization initiators can be selected as described below depending on the purpose.

(1) Polymerization initiators for sensitized photopolymerization include carbonyl compounds such as benzoin and polynuclear quinones, azo compounds such as azobisisobutyronitrile and diazonium compounds, organic sulfur compounds such as mercaptans, alkyl disulfides, etc. Examples include redox systems such as iron (U)/hydrogen peroxide, amines such as aliphatic amines, aromatic amines, and nitrogen-containing heterocyclic compounds such as biperidine.

Note that as the storage stabilizer, quaternary ammonium chloride, diethylhydroxyamine, cyclic amide, nitrile compound, hydroquinone, etc. are used. Further, examples of the polymerization accelerator include dimethylaminoethanol. The amount of photopolymerization initiator added is preferably about 2.5% by weight, and is determined in consideration of efficiency, cost, compatibility, etc. The amount of the storage stabilizer added is preferably 200 to 2000 ppm, and the amount of the polymerization accelerator added is preferably about 2.5% by weight.

(2) As the polymerization initiator for anaerobic polymerization, for example, diasilver oxide, peroxy ester, dialkyl peroxide, hydroperoxide, ketone peroxide, etc. are used. Examples of the polymerization accelerator include primary amines, tertiary amines, hydrazine and its derivatives, urea or thiourea and its derivatives, O-penzsulfonimide, ascorbic acid, and the like.

In this case, storage stabilizers include penzoquinone,
Hydroquinone phenol derivatives, metal chelating agents such as ethylenediaminetetraacetic acid or its disodium salt,
Examples include acetylacetone.

(3) Examples of the polymerization initiator for the two-component modified acrylic adhesive include organic hydroperoxides such as tert-butyl peroxide and organic peresters. As the polymerization accelerator, tertiary amines such as N,N-dimethylaniline,
Examples include triethylamine, polyamines such as diethylenetriamine, triethylenetetramine, thiourea and its derivatives.

The curable composition of the present invention includes a polymerizable monomer containing 5% by weight or more of a polymerizable fluorine compound, a curing agent such as a polymerization initiator,
It can be prepared by adding storage stabilizers, polymerization accelerators, etc. and mixing well.

Example (1) Synthesis method 1 of polymerizable fluorine compound used in the present invention
An example is shown below.

The reactor equipped with a cooling tube was purged with nitrogen, and 48.4 parts by weight of isophorone diisocyanate and 0.0 parts by weight of phenothiazine were added as a catalyst. O
Add I part by weight and maintain at 40°C. There, 4, 4, 5, 5
, 6,6,7,7,8,8,9,9,9-tridecafluorononane-1,2-diol, 40.8 parts by weight are added, and after the addition, the temperature is raised to 75°C. After stirring for 2 hours, it was cooled to 40°C, and 30.8 parts by weight of 2-hydroxyethyl acrylate and 0.8 parts by weight of phenothiazine were added. A solution of parts by weight of Ol is added dropwise.

After the dropwise addition is completed, the temperature is raised to 65° C. and stirred for 6 hours to obtain a polymerizable fluorine compound as a viscous and transparent liquid.

(2) As shown in Table 1, four types of composition samples were prepared and irradiated with light using a high-pressure mercury lamp with an irradiation energy of 80 W/cm at an irradiation distance of 15 cm to create cured product samples. All of the obtained cured products had good transparency.

Table 1 shows trimethylolbroban triacrylate, component 4 shows hexanediol diacrylate, and component 5 shows l-hydroxycyclohexyl phenyl ketone (Irgacure 184 manufactured by Ciba Geigy: photopolymerization initiator).

(Effects of the Invention) The curable composition of the present invention is homogeneous, has a low viscosity, and has a low curing speed because it uses the above-mentioned specific polymerizable fluorine compound that has good compatibility with other components such as a crosslinking agent. It is quick, and the cured resin obtained is transparent and has excellent chemical resistance, water repellency, and oil repellency. Therefore, the curable composition of the present invention can be used as a paint,
Useful for sealants, optical materials, etc.

Claims (1)

[Claims] 1. The following structural unit ▲ Numerical formula, chemical formula, table, etc. ▼ (I) (in the formula, R represents an alkylene group) and the following structural unit -[O-Rf-O]-(II ) (wherein Rf represents a fluoroalkylene group), and a curable composition containing a polymerizable fluorine compound having a polymerizable unsaturated bond and a curing agent.