JP3352516B2 - Fluorine-containing phenolic resin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention is not only excellent in mechanical strength (in particular, toughness) and heat resistance in comparison with conventional general phenolic resins, but also has water repellency that phenolic resins do not have. The present invention relates to a multifunctional fluorine-containing phenol resin having properties such as oil repellency, antifouling property and sliding property.

[0002]

2. Description of the Related Art Phenol resin has mechanical strength, heat resistance,
It is a relatively inexpensive resin with excellent electrical insulation, chemical resistance, dimensional stability, workability, etc.It is widely used in various fields, but especially in the field of industrial materials (for example, parts for electrical and electronic products) , Automotive parts, mechanical parts, etc.) are required to have improved mechanical strength (particularly, toughness) and heat resistance. In order to respond to such a request, an N-hydroxyphenylmaleimide polymer-modified phenol resin composition has been proposed [for example, JP-A-4-59855 and "thermosetting resin", Vol. 13, No. 4, See pages 20-27 (1992)], and relatively good results have been obtained. However, in the phenolic resin industry in recent years, in order to further expand the applications, properties that phenolic resins lack, such as water and oil repellency,
Development of a multifunctional phenolic resin having properties such as antifouling property and slidability has been demanded.

[0003]

SUMMARY OF THE INVENTION The present invention responds to such a demand and, compared to a conventional general phenol resin,
Providing multifunctional phenolic resins that are not only excellent in mechanical strength (particularly toughness) and heat resistance, but also have properties such as water repellency, oil repellency, and stain resistance that phenolic resins lack. It was done to do so.

[0004]

That is, the present invention provides a compound represented by the following general formula (I):

Embedded image (Wherein, R represents a hydrogen atom or a methyl group, Rf represents a monovalent residue having a perfluoroalkyl group or a perfluoroalkenyl group having 1 to 10 carbon atoms, and p represents 1
And n is an integer of from 1 to 100
Of the fluorinated phenolic resin represented by
Concerning the construction method .

In the general formula (I), R represents a hydrogen atom or a methyl group, and Rf represents a monovalent residue having a perfluoroalkyl group or a perfluoroalkenyl group having 1 to 10 carbon atoms. Such monovalent residues include-
_{CH 2 CF 3, -CH 2 C} 2 F 5, -CH 2 CH 2 C 6 F 13, -
_{CH 2 CH 2 C 8 F 17} , -CH 2 CH 2 OC 9 F 17, -CH 2
_{CH (OH) CH 2 C 6} F 13, -CH 2 CH 2 OCO · C 6 H 4
· OC ₉ F _17, and _{-CH 2 CH 2 (C 3 H} 7) NO 2 SC 8
F ₁₆ and the like.

In the general formula (I), p represents a number of 1 to 3, and n and m each independently represent a number of 1 to 100. The preferred molecular weight of the fluorine-containing phenolic resin represented by the general formula (I) is 1,000 to 200,000.

A preferred method for producing the compound represented by the general formula (I) is the general formula (II):

Embedded image (Wherein p is as defined above) and a general formula (III):

Embedded image (Wherein R and Rf are as defined above) in a fluorine-containing solvent or a mixed solvent of a fluorine-containing solvent and a polar organic solvent in the presence of a radical initiator. In the reaction.

The N-hydroxyphenylmaleimide represented by the general formula (II) includes N-2-hydroxyphenylmaleimide, N-3-hydroxyphenylmaleimide, N-4-hydroxyphenylmaleimide, N-2,
3-dihydroxyphenylmaleimide, N-2,4-dihydroxyphenylmaleimide, N-2,5-dihydroxyphenylmaleimide, N-2,6-dihydroxyphenylmaleimide, N-3,4-dihydroxyphenylmaleimide, N-3, Examples thereof include 5-dihydroxyphenylmaleimide and N-2,4,6-trihydroxyphenylmaleimide, and two or more of them may be used in combination as needed.

Examples of the polymerizable acrylate monomer represented by the general formula (III) include the above-mentioned polymerizable acrylates and methacrylates having a fluorine-containing monovalent residue. May be.

The reaction ratio between the N-hydroxyphenylmaleimide and the polymerizable acrylate monomer is not particularly limited, but is usually 99: 1 to 1:99, preferably
90:10 to 10:90, and in general, when the former reaction ratio is high, a fluorine-containing phenol resin having particularly excellent heat resistance is obtained, and conversely, when the reaction ratio of the polymerizable acrylate monomer is high, Can obtain a fluorinated phenol resin which is particularly excellent in toughness, water / oil repellency, stain resistance and the like. Therefore, by appropriately selecting the reaction ratio between N-hydroxyphenylmaleimide and the polymerizable acrylate monomer, the characteristics of the fluorinated phenol resin can be adjusted according to the application.

As the reaction solvent, a fluorinated solvent or a fluorinated solvent and a polar organic solvent are used. Examples of the fluorinated solvent include 2,2,2-trifluoroethanol, hexafluoroisopropanol, 2,2,3,3,3-pentafluoropropanol, 1,3-bis (trifluoromethyl) benzene and 1,4-bis (Trifluoromethyl) benzene and the like are exemplified, and as the polar organic solvent used in combination with these fluorine-based solvents, nitrile-based solvents (e.g., acetonitrile, propionitrile, butyl nitrile and the like),
Amide solvents (e.g., N, N-dimethylformamide,
N, N-dimethylacetamide, N, N-dimethylimidazolidinone, N-methylpyrrolidone, etc.) and sulfur solvents (eg, dimethylsulfoxide, sulfolane, etc.).

Mixing ratio of fluorinated solvent to polar organic solvent
The (volume ratio) may be appropriately selected according to the type of the N-hydroxyphenylmaleimide and the polymerizable acrylate monomer and the reaction ratio thereof, and is not particularly limited. 1: 0.9, preferably
0.9: 0.1 to 0.2: 0.8. Generally, when the reaction ratio of N-hydroxyphenylmaleimide is high, the latter is frequently used, and when the reaction ratio of the polymerizable acrylate monomer is high, the former is frequently used.

As the radical initiator, organic peroxides known per se (for example, ketone peroxide, diacyl peroxide, hydroperoxide, dialkyl peroxide, peroxyketal, peroxyester, peroxycarbonate, etc.) and azo compounds (Eg, azobisformamide, azobisisobutyronitrile, etc.) and the like may be used as appropriate. The amount of the radical initiator to be used is usually 0.1 to 10 parts by weight based on 100 parts by weight of all the above-mentioned reaction components. Generally, when the use amount of the radical initiator is relatively small, the molecular weight of the fluorine-containing phenol resin represented by the general formula (I) becomes relatively large, but when the use amount becomes relatively large, Thus, a fluorine-containing phenol resin having a relatively small molecular weight can be obtained.

The reaction temperature and the reaction time may be appropriately selected according to the type and the reaction ratio of the above-mentioned reaction components, the type of the reaction solvent and the radical initiator, etc. 1 to 20 hours.

[0015]

The present invention will be described below with reference to examples. Example 1 50 m of N, N'-dimethylformamide was placed in a reaction vessel equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen gas inlet pipe.
l, 1,3-bis (trifluoromethyl) benzene 50 ml,
11.36 g of N-4-hydroxyphenylmaleimide
(0.06 mol), 25.08 g (0.06 mol) of 2-perfluorohexylethyl acrylate and 0.328 g (2 mmol) of 2,2'-azobisisobutyronitrile were charged under a nitrogen atmosphere. The reaction was carried out at 70 ° C. for 6 hours with stirring. After completion of the reaction, the reaction mixture was dropped into a large excess water bath, and the deposited precipitate was collected by filtration and subjected to a heat-drying treatment under vacuum to convert the fluorine-containing phenol resin (Ia) into a pale yellow. 32. as a solid
4 g were obtained (88% yield). Table 2 below shows the physical properties and the like of the fluorinated phenol resin (Ia).

Examples 2 to 8 Fluorine-containing phenolic resins (Ib) (Examples 2) to (I) were prepared according to the procedure shown in Table 1 below according to the procedure of Example 1.
h) (Example 8) was prepared. Fluorine-containing phenolic resin (I
Table 2 below shows the physical properties and the like of b) to (Ih).

Comparative Examples 1 and 2 Fluorine-free phenolic resins (I'a) and (I'b) were prepared according to the procedure shown in Table 1 below according to the procedure of Example 1.
And their physical properties are shown in Table 2 below.

[0018]

[Table 1]

[0019]

[Table 2]

[0020]

The fluorinated phenolic resin according to the present invention is not only superior in mechanical strength (in particular, toughness) and heat resistance in comparison with conventional general phenolic resins, but also
Phenolic resin has the characteristics of water and oil repellency, antifouling property, and sliding property, etc. that are lacking in phenolic resin, so it is particularly suitable for parts for electric and electronic products, parts for vehicles such as automobiles and aircraft, and various mechanical parts. Useful as

Continuation of the front page (72) Inventor Akitoku Fukuda 6-21, Shinkomadai, Ikoma City, Nara Prefecture (72) Inventor Masashi Takeshita 6-2-1, Kano-cho, Chuo-ku, Kobe City, Hyogo Prefecture Neos Co., Ltd. (72) Inventor Hideyuki Tomoda 6-2-1, Kano-cho, Chuo-ku, Kobe City, Hyogo Prefecture Neos Co., Ltd. (56) References JP-A-6-116331 (JP, A) (58) Fields investigated (Int. Cl. ⁷⁾ , DB name) C08F 222/40 C08F 220/22-220/24 C08F 220/40 CA (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] 1. A compound of the general formula (I): (Wherein, R represents a hydrogen atom or a methyl group, Rf represents a monovalent residue having a perfluoroalkyl group or a perfluoroalkenyl group having 1 to 10 carbon atoms, and p represents 1
And n is an integer of from 1 to 100
Of the fluorinated phenolic resin represented by
A granulation method, general formula (II): ## STR2 ## (Wherein p is as defined above)
Hydroxyphenyl maleimide and formula (III): ## STR3 ## (Wherein, R and Rf are as defined above)
Polymerizable fluorine-containing acrylate monomer
Solvent or mixed solvent of fluorinated solvent and polar organic solvent
Among the possible to reaction in the presence of a radical initiator
A method for producing the fluorine-containing phenol resin . 2. A compound represented by the general formula (I) according to claim 1.
Fluorinated phenol resin [provided that it has the general formula (I)
Wherein Rf is a perfluoroalkyl having 1 to 10 carbon atoms
-Containing phenolic tree showing monovalent residue having a group
Except for fat) .