JP2002284819A - Fluoropolymer containing ultraviolet-absorbent segment - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel fluoropolymer which can effectively distribute an ultraviolet absorbent compounded thereinto over the surface of a molded article or coating prepared therefrom, thus enabling an effective ultraviolet absorption action to be realized; and a production method for the same. SOLUTION: This fluoropolymer contains ethylenically unsaturated monomer units having ultraviolet-absorbing groups in the polymer chain and has fluoroalkyl and/or oxafluoroalkyl groups at the molecular terminals.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fluorine-containing polymer having an ultraviolet absorbing segment and a method for producing the same, and more particularly, to a fluorine-containing polymer having excellent surface transferability and excellent ultraviolet absorbing effect. The present invention relates to coalescence and a method for producing the same.

[0002]

2. Description of the Related Art Polymer molded articles and coatings include:
Ultraviolet absorbers are widely used for the purpose of preventing oxidative deterioration due to light. This ultraviolet absorber absorbs ultraviolet rays harmful to plastics, converts them into harmless heat and kinetic energy, and suppresses the generation of radicals. Representative examples include benzotriazole-based ultraviolet absorbers and benzophenone. Ultraviolet absorbers are known.

[0003]

Such an ultraviolet absorber is used for the purpose of imparting light resistance by blending with a polymer. However, the ultraviolet absorber present on the surface of a molded article or a coating is not resistant to light. Even if it contributes to the application, there is a problem that the one existing inside the molded article or coating does not contribute to the light resistance, and the effective utilization rate of the added ultraviolet absorber is low.

Accordingly, it is an object of the present invention to provide a novel ultraviolet absorbing component which can be effectively disposed on a surface of a molded article or a coating so that an effective ultraviolet absorbing effect can be obtained even with a small amount. An object of the present invention is to provide a fluoropolymer and a method for producing the same.

[0005]

According to the present invention, an ethylenically unsaturated monomer unit having a UV-absorbing group is contained in a polymer chain, and a fluoroalkyl group and / or an oxafluoroalkyl group is terminated at the terminal. Is provided. In the fluoropolymer of the present invention: 1. the number average molecular weight (Mn) is in the range of 500 to 20,000; Molecular weight distribution (Mw / Mn) of 1.01 to 3.00
2. 3. the ethylenically unsaturated monomer unit comprises a (meth) acrylate unit; 4. the ultraviolet absorbing group is a group having a benzotriazole-based ultraviolet absorber skeleton, a benzophenone-based ultraviolet absorber skeleton, a salicylate-based ultraviolet absorber skeleton, or a cyanoacrylate-based ultraviolet absorber skeleton; The following equation (1) In the formula, Rf is a fluoroalkyl group or a fluorooxaalkyl group, R is a hydrogen atom or a methyl group, X is a benzotriazole-based ultraviolet absorber skeleton, a benzophenone-based ultraviolet absorber skeleton, a salicylate-based ultraviolet absorber skeleton, Alternatively, it is an alkyl group having a cyanoacrylate-based ultraviolet absorber skeleton, and n is a number giving a number average molecular weight (Mn) of 1 to 100, or has a chemical structure represented by the following formula (2): In the formula, Rf is a fluoroalkyl group or a fluorooxaalkyl group, R is a hydrogen atom or a methyl group, X is a benzotriazole-based ultraviolet absorber skeleton, a benzophenone-based ultraviolet absorber skeleton, a salicylate-based ultraviolet absorber skeleton, Alternatively, Y is a hydrophilic group or an antibacterial functional group, and n and m are 500 to 5 as a whole.
A number giving a number average molecular weight (Mn) of 0000,
n: m is preferably in the range of 1:99 to 99: 1, and preferably has a chemical structure represented by the following formula. According to the present invention, it is also preferred that the (meth) acrylate having an ultraviolet absorbing group is polymerized in the presence of a peroxide having a fluoroalkyl group and / or an oxafluoroalkyl group. A method of making a coalescence is provided. According to the present invention, there is further provided an ultraviolet absorber characterized by comprising the above fluoropolymer. According to the present invention, further, the fluorine-containing polymer is 0.0
An ultraviolet absorbing polymer composition is provided which is contained in an amount of 5 to 5% by weight.

[0006]

DESCRIPTION OF THE PREFERRED EMBODIMENTS [Action] The fluoropolymer of the present invention contains an ethylenically unsaturated monomer unit having an ultraviolet absorbing group, for example, a (meth) acrylate unit in a polymer chain; It is characterized by having a fluoroalkyl group and / or an oxafluoroalkyl group at the terminal.

The fluorine-containing polymer contains an ethylenically unsaturated monomer unit having a UV-absorbing group (also referred to as a UV-absorbing segment). Has a fluoroalkyl group and / or an oxafluoroalkyl group,
Due to the surface bleeding property, there is an advantage that the ultraviolet-absorbing segments are efficiently arranged on the object surface, whereby an effective ultraviolet-absorbing action is exhibited even with a small blending amount.

The surface bleeding property of the fluoropolymer of the present invention can be confirmed by photoelectron spectroscopy (ESCA). FIG. 1 shows a sheet in which 2- [3- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] ethyl methacrylate {BTHPEMA} is blended in polystyrene, the above-mentioned BTHPEMA and perfluoro-2-methyl peroxide. For a sheet in which a fluoropolymer derived from 3-oxahexanoyl was blended with polystyrene, the photoelectron spectroscopic analysis described above changed the etching time to change the fluorine (F), oxygen (O) and nitrogen (N) atoms. Are shown. In this analysis,
Since each atom is measured while etching from the sheet surface, the result of FIG. 1 shows the distribution of atoms in the thickness direction. According to the results, in the case where BTHPEMA was simply added, the distribution of nitrogen atoms between triazoles was almost uniform in the thickness direction, whereas in the case of blending in the form of a fluoropolymer, nitrogen atoms and The distribution of the fluorine atoms is large on the surface and gradually decreases in the thickness direction, and it is clear that the distribution structure is such that the fluorine atoms are efficiently distributed on the surface.

Further, when the compounded sheet is subjected to accelerated exposure treatment, as shown in the examples described later, BTHPEM
Compared with the case where A was simply added (Comparative Example 2), in the case of blending in the form of a fluoropolymer, the color difference value (ΔE) was suppressed to a considerably low value, and in terms of actual weather resistance, It is understood that there are significant differences. Furthermore, it is understood that, in accordance with the present invention, those containing a fluoropolymer are also excellent in oil repellency.

The fluorine-containing polymer of the present invention can of course be blended with various polymers as it is, but is soluble in various solvents, as shown in the examples described below, and can be used in the form of a solution such as paint. It can be blended in various coatings.

[Fluorine-Containing Polymer] The fluorine-containing polymer of the present invention contains an ethylenically unsaturated monomer unit having a UV-absorbing group, particularly a (meth) acrylate unit in a polymer chain, and The terminal has a fluoroalkyl group and / or an oxafluoroalkyl group.

Examples of the above-mentioned ultraviolet-absorbing group include groups having a benzotriazole-based ultraviolet absorber skeleton, a benzophenone-based ultraviolet absorber skeleton, a salicylate-based ultraviolet absorber skeleton, or a cyanoacrylate-based ultraviolet absorber skeleton. Specifically, the following equation (4)

Embedded image In the formula, Y is an alkylene group, X is a hydrogen atom or an alkyl group, a benzotriazole-containing group represented by the following formula (5)

Embedded image In the formula, Y is an alkylene group, X is a hydrogen atom, an alkyl group, a hydroxyl group, or an alkoxy group, a benzophenone-containing group represented by the following formula (6)

Embedded image Wherein Y is an alkylene group, a salicylate-containing group represented by the following formula (7):

Embedded image In the formula, a cyanoacrylate-containing group represented by R ₂ is an alkyl group and Y is an alkylene group is exemplified, but the invention is not limited thereto.

The ethylenically unsaturated monomer containing an ultraviolet absorbing group may be any radically polymerizable ethylenically unsaturated monomer, and may be a vinyl monomer,
Styrene monomers, acrylic monomers, vinyl ester monomers, vinyl ether monomers and the like,
Among them, (meth) acrylic acid ester monomers are preferable because the synthesis of the monomers themselves and the polymerization are easy.
The (meth) acrylate is a term commonly used, but means an acrylate or a methacrylate.

The (meth) acrylate monomer preferably used in the present invention has an ultraviolet absorbing skeleton and a (meth) acrylate.
It has a structure in which an acryloyl group and an acryloyl group are linked via an alkylene group.

Embedded image Has a structure represented by

The above-mentioned ethylenically unsaturated monomers having an ultraviolet absorbing group can be used alone or in combination of two or more. Further, the ethylenically unsaturated monomer having an ultraviolet absorbing group can be used in combination with an ethylenically unsaturated monomer having no ultraviolet absorbing group.

Such comonomers include, for example,
Methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, n-amyl (meth) acrylate, (meth) acryl (Meth) acrylates such as isoamyl acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and n-octyl (meth) acrylate; styrene, vinyltoluene, acrylonitrile, and methacrylonitrile , Vinyl acetate and the like.

Preferred examples of the comonomer include monomers containing a hydrophilic functional group or an antibacterial functional group, such as a carboxyl group, a salt group thereof, an amide group, a hydroxyl group, an amino group, and the like.
It has an epoxy group, a methylol group, and an etherified methylol group, and specific examples thereof include the following. Ethylenically unsaturated carboxylic acids or anhydrides; acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, maleic anhydride,
Itaconic anhydride and the like. Amide group to imide group-containing monomer; (meth) acrylamide, dimethyl (meth) acrylamide, morpholino (meth) acrylimide and the like. Hydroxyl group-containing monomers; hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, propylene glycol monoester acrylate, and the like. Amino group-containing monomer; dimethylaminoethyl (meth) acrylate, t-butylaminoethyl (meth) acrylate, vinylpyridine, 2-vinyl-5-ethylpyridine, oxazolylethyl (meth) acrylate, (meth) Hydroxyethylaminoethyl acrylate and the like. Epoxy group-containing monomers: (meth) acrylic acid glycidyl ether, allyl glycidyl ether, butane monoxide and the like. A monomer having a methylol group and an etherified methylol group; a dimethylol compound of (meth) acrylamide and an ether compound thereof, for example, an ethyl ether compound or a butyl ether compound; By using these comonomers, it is possible to impart hydrophilicity, impart antibacterial properties, improve the sustainability of hydrophilicity and oil repellency, improve the adhesion to a substrate, and the like.

In the case of the above copolymer, the UV-absorbing group-containing ethylenically unsaturated monomer unit is at least 1 mol%, particularly preferably at least 10 mol%, based on the repeating unit in the polymer.
The presence of the above amount is preferable from the viewpoint of ultraviolet absorption.

The fluoroalkyl group and / or oxafluoroalkyl group bonded to the terminal of the polymer generally includes a linear or branched fluoroalkyl group and / or oxafluoroalkyl group having 5 to 20 carbon atoms. Perfluoroalkyl groups and oxaperfluoroalkyl groups are preferred. Suitable groups represented by the following formula _{(9) -CF (CF 3)} O [CF 2 CF (CF 3) O] mC 3
In formula ( ₇₎ , m is zero or one.

The fluorine-containing polymer of the present invention has a number average molecular weight (Mn) of 500 to 20,000, particularly 1000 to 5
000, and a molecular weight distribution (Mw / Mn) of 1.01 to 3.00, particularly 1.01.
To 2.00.

Preferred examples of the fluoropolymer of the present invention include:
The following equation (1) In the formula, Rf is a fluoroalkyl group or a fluorooxaalkyl group, R is a hydrogen atom or a methyl group, X is a benzotriazole-based ultraviolet absorber skeleton, a benzophenone-based ultraviolet absorber skeleton, a salicylate-based ultraviolet absorber skeleton, Alternatively, it is an alkyl group having a cyanoacrylate-based ultraviolet absorber skeleton, and n is a number giving a number average molecular weight (Mn) of 1 to 100, or a chemical structure represented by the following formula (2): In the formula, Rf is a fluoroalkyl group or a fluorooxaalkyl group, R is a hydrogen atom or a methyl group, X is a benzotriazole-based ultraviolet absorber skeleton, a benzophenone-based ultraviolet absorber skeleton, a salicylate-based ultraviolet absorber skeleton, Alternatively, it is an alkyl group having a cyanoacrylate-based ultraviolet absorber skeleton, Y is a hydrophilic group or an antibacterial functional group, and n and m are 500 to 5 as a whole.
A number giving a number average molecular weight (Mn) of 0000,
n: m is in the range of 1:99 to 99: 1.

[Production Method] The fluoropolymer of the present invention comprises a (meth) acrylic acid ester having an ultraviolet-absorbing group and, if necessary, a fluoroalkyl group and / or an oxafluoroalkyl group together with another comonomer. It is obtained by polymerizing in the presence of a peroxide. As the monomer having an ultraviolet absorbing group and other comonomers, those described above are used. On the other hand, as the fluoroalkyl group-containing peroxide, a compound represented by the formula (9) Is used.

The polymerization is preferably carried out by solution polymerization in an inert atmosphere such as nitrogen. As the solvent, a fluorinated organic solvent is preferably used, and the polymerization temperature is preferably in the range of 0 to 70 ° C. Since the obtained polymer is soluble in an aromatic solvent such as benzene, it can be purified by dissolving it in a good solvent and adding a poor solvent such as hexane to cause reprecipitation.

[Use] The fluoropolymer of the present invention is useful as an ultraviolet absorber having surface transferability. By blending this fluoropolymer in a molding resin, paint, or the like, the fluoropolymer migrates to the surface of the molded article or coating, and excellent ultraviolet absorption is exhibited.

Examples of the thermoplastic resin containing a fluoropolymer as an ultraviolet absorber include low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, polypropylene, poly 1-butene, and the like.
Α such as poly 4-methyl-1-pentene or ethylene, propylene, 1-butene, 4-methyl-1-pentene, etc.
Polyolefins such as random or block copolymers of olefins, ethylene / vinyl acetate copolymers,
Ethylene / (meth) acrylic acid copolymer, ethylene /
(Meth) acrylic ester copolymers, ethylene / vinyl compound copolymers such as ethylene / vinyl chloride copolymers,
Polystyrene, acrylonitrile-styrene copolymer,
ABS, styrene resins such as α-methylstyrene / styrene copolymer, polyvinyl chloride, polyvinylidene chloride,
Polyvinyl chloride / vinylidene chloride copolymer, polyvinyl compounds such as polymethyl acrylate, polymethyl methacrylate, nylon 6, nylon 6-6, nylon 6-10,
The resin may be any of polyamide such as nylon 11 and nylon 12, thermoplastic polyester such as polyethylene terephthalate and polybutylene terephthalate, polycarbonate, polyphenylene oxide and the like, or a mixture thereof. Examples of the elastomer polymer containing the fluorine-containing polymer include nitrile-butadiene rubber (NBR), styrene-butadiene rubber (SBR),
Chloroprene rubber (CR), polybutadiene (BR),
Polyisoprene (IIB), butyl rubber, natural rubber, ethylene-propylene rubber (EPR), ethylene-propylene-diene rubber (EPDM), polyurethane, silicone rubber, acrylic rubber, etc .; thermoplastic elastomer, for example, styrene-butadiene-styrene block copolymer Styrene-isoprene-styrene block copolymer, hydrogenated styrene-butadiene-styrene block copolymer, hydrogenated styrene-isoprene-styrene block copolymer, and the like.

On the other hand, as a paint containing a fluoropolymer as an ultraviolet absorber, a thermosetting resin paint, for example,
Phenol-formaldehyde resin, furan-formaldehyde resin, xylene-formaldehyde resin, ketone-formaldehyde resin, urea formaldehyde resin, melamine-formaldehyde resin, alkyd resin,
Unsaturated polyester resin, epoxy resin, bismaleimide resin, triallyl cyanurate resin, thermosetting acrylic resin, silicone resin, oily resin, or thermoplastic resin paint, for example, vinyl chloride-vinyl acetate copolymer, vinyl chloride -Maleic acid copolymer, vinyl chloride-maleic acid-vinyl acetate copolymer, acrylic polymer, saturated polyester resin and the like. These resin coatings may be used alone or in combination of two or more.

The fluorinated polymer of the present invention is used in an amount of 0.05% based on 100 parts by weight of the above-mentioned polymer or resin solid content.
It is preferable to mix in an amount of from 5 to 5 parts by weight, especially from 0.1 to 3 parts by weight.

When the fluoropolymer of the present invention is used in combination with a hindered amine light stabilizer (HALS), a more excellent synergistic effect is exhibited. The hindered amine light stabilizer (HALS) has a function of capturing radicals generated by ultraviolet rays, and a known one is used. For example, 2,2,6,6-tetramethyl-4-piperidylbenzoate, N- (2,2,
6,6-tetramethyl-4-piperidyl) dodecylsuccinimide, 1-[(3,5-ditert-butyl-4-hydroxyphenyl) propionyloxyethyl] -2,
2,6,6-tetramethyl-4-piperidyl- (3,5
Di-tert-butyl-4-hydroxyphenyl) propionate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetra (2,2,6,6-tetramethyl-4-piperidyl) butane Tetracarboxylate, tetra (1,2,2,6,6-pentamethyl-4-
Piperidyl) butanetetracarboxylate, bis (2,2,6,6-tetramethyl-4-piperidyl).
And di (tridecyl) butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) di (tridecyl) butanetetracarboxylate. The HALS is preferably blended in an amount of 0.05 to 5 parts by weight, particularly 0.1 to 3 parts by weight, based on 100 parts by weight of the polymer or resin solid content described above.

[0029]

The present invention is further described by the following examples.
The present invention is not limited to the following examples.

Example 1 A. Synthesis of a fluoroalkyl group-containing homo-oligomer having a benzotriazole segment: 2- [3- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] ethyl methacrylate represented by the following formula (10) (9 mmol; 3.00 g) ) And perfluoro-2-methyl-3-oxahexanoyl peroxide (0.9 mmol
1; 7.61 g) containing AK-225 (1,1,2-
A solution (121 g) of a 1: 1 mixed solution of dichloro-2,2,3,3,3-pentafluoropropane and 1,3-dichloro-1,2,2,3,3-pentafluoropropane was added, and nitrogen was added. The reaction was carried out at 45 ° C./5 hr under an air stream. After the reaction, the solvent was removed under reduced pressure, and the obtained crude product was dissolved in benzene and reprecipitated with hexane. As a result, a fluoroalkyl group-containing homo-oligomer having a benzotriazole segment was obtained in a yield of 1.36 g.

2- [3- (2H-benzotriazole-
Structure of 2-yl) -4-hydroxyphenyl] ethyl methacrylate (BTHPEMA):

Embedded image

The resulting polymer has the following formula: Rf- (BTHPEMA) n-Rf Rf: CF (C
F ₃ ) having a structure represented by OC ₃ F ₇ and having a number average molecular weight (Mn) of 270
0, molecular weight distribution (Mw / Mn) was 2.19. This is called compound A1.

Example 2 In Example 1, perfluoro-2,5-dimethyl-3, peroxide was used in place of perfluoro-2-methyl-3-oxahexanoyl peroxide.
A fluoroalkyl group-containing oligomer was obtained in a yield of 33% in the same manner as in Example 1 except for using 6-dioxano nanoyl.

The resulting polymer has a structure represented by the following formula: Rf- (BTHPEMA) n-Rf Rf: CF (CF ₃ ) OCF ₂ (CF ₃ ) OC ₃ F ₇ , and has a number average molecular weight (Mn) of 390
0, molecular weight distribution (Mw / Mn) was 2.16. This is called compound A2.

Example 3 Synthesis of fluoroalkyl group-containing acrylic acid cooligomer having benzotriazole segment: 2- [3
-(2H-benzotriazol-2-yl) -4-hydroxyphenyl] ethyl methacrylate (1.6 mmol
0.50 g) and perfluoro-2-methyl-3-oxahexanoyl peroxide (1.6 mmol;
AK-225 (1,1,2-dichloro-2,2,3,3,3-pentafluoropropane and 1,2 g) containing
(1: 1 mixed solution of 3-dichloro-1,2,2,3,3-pentafluoropropane and 1,3-dichloro-1,2,2,3,3-pentafluoropropane) solution (128 g)
And then acrylic acid (16 mmol; 1.14)
g) was added and reacted at 45 ° C./5 hr under a nitrogen stream. After the reaction, the solvent was removed under reduced pressure, and the obtained crude product was dissolved in methanol and reprecipitated with ethyl acetate. As a result, a fluoroalkyl group-containing acrylic acid cooligomer having a benzotriazole segment was obtained in a yield of 0.55 g.

The resulting polymer has the following formula: Rf- (BTHPEMA) n (CH ₂ —CHCO ₂ H) n
-Rf Rf: CF (CF ₃₎ has a structure represented by OC ₃ F _7, a number average molecular weight (Mn) of 680
0, molecular weight distribution (Mw / Mn) was 1.27. This is called compound B1.

Example 4 In Example 3, perfluoro-2,5-dimethyl-3, peroxide was used instead of perfluoro-2-methyl-3-oxahexanoyl peroxide.
A fluoroalkyl group-containing oligomer was obtained in a yield of 16% in the same manner as in Example 3 except for using 6-dioxano nanoyl.

The resulting polymer has the following formula: Rf- (BTHPEMA) n (CH ₂ —CHCO ₂ H) m
_{-Rf Rf: CF (CF 3)} OCF 2 (CF 3) has a structure represented by OC ₃ F _7, a number average molecular weight (Mn) of 780
0, molecular weight distribution (Mw / Mn) was 1.22. This is called compound B2.

Example 5 C.I. Synthesis of fluoroalkyl group-containing dimethylacrylamide co-oligomer having benzotriazole segment: 2- [3- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] ethyl methacrylate (1.6 mmol; 0.53 g) Perfluoro-2-methyl-3-oxahexanoyl oxide (1.6 m
mol: 13.89 g) of AK-225 (1,
1,2-dichloro-2,2,3,3,3-pentafluoropropane and 1,3-dichloro-1,2,2,3,3-
1: 1 mixed solution of pentafluoropropane) solution (12
1 g), and then add dimethylacrylamide (16 m
mol; 1.54 g) at 45 ° C. /
The reaction was performed for 5 hours. After the reaction, the solvent was removed under reduced pressure, and the obtained crude product was dissolved in benzene and reprecipitated with hexane. As a result, a fluoroalkyl group-containing dimethylacrylamide cooligomer having a benzotriazole segment was obtained in a yield of 2.77 g.

The resulting polymer has the following formula: Rf- (BTHPEMA) n (CH ₂ —CHCONM)
e ₂ ) m-Rf Rf: has a structure represented by CF (CF ₃ ) OC ₃ F ₇ and has a number average molecular weight (Mn) of 570
0, molecular weight distribution (Mw / Mn) was 1.30. This is called compound C1.

Example 6 In Example 5, perfluoro-2,5-dimethyl-3, peroxide was used instead of perfluoro-2-methyl-3-oxahexanoyl peroxide.
A fluoroalkyl group-containing oligomer was obtained in a yield of 97% in the same manner as in Example 5 except that 6-dioxanonanoyl was used.

The produced polymer has the following formula: Rf- (BTHPEMA) n (CH ₂ —CHCONM)
e ₂₎ m-Rf Rf: has a _{CF (CF 3) OCF 2 CF} (CF 3) structure represented by OC ₃ F _7, a number average molecular weight (Mn) of 400
0, molecular weight distribution (Mw / Mn) was 1.23. This is called compound C2.

[Embodiment 7] Synthesis of acryloylmorpholine co-oligomer containing fluoroalkyl group having benzotriazole segment: 2- [3- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] ethyl methacrylate (1.6 mmol; 0.50 g) Perfluoro-2-methyl-3-oxahexanoyl oxide (1.6 m
mol: 13.54 g) of AK-225 (1,
1,2-dichloro-2,2,3,3,3-pentafluoropropane and 1,3-dichloro-1,2,2,3,3-
1: 1 mixed solution of pentafluoropropane) solution (11
7 g) and then acryloyl morpholine) (16
mmol; 2.20 g) at 45 ° C. under a nitrogen stream.
/ 5 hr. After the reaction, the solvent was removed under reduced pressure, and the obtained crude product was dissolved in benzene and reprecipitated with hexane. As a result, a fluoroalkyl group-containing acryloylmorpholine co-oligomer having a benzotriazole segment was obtained in a yield of 3.52 g.

The polymer produced has the following formula And has a number average molecular weight (Mn) of 730
0, molecular weight distribution (Mw / Mn) was 1.30. This is called compound D1.

Example 8 In Example 7, perfluoro-2,5-dimethyl-3, peroxide was used instead of perfluoro-2-methyl-3-oxahexanoyl peroxide.
A fluoroalkyl group-containing oligomer was obtained in a yield of 94% in the same manner as in Example 7 except for using 6-dioxanonanoyl.

The polymer produced has the following formula Having a number average molecular weight (Mn) of 820
0, molecular weight distribution (Mw / Mn) was 1.29. This is called compound D2.

[Examples 9 to 16 and Comparative Examples 1 to 4] (1) Preparation of Sample Various compounds of the present invention (A1 to D2) were added to a solution of polystyrene.
And the respective sheets obtained by the cast molding are referred to as “Example samples”. <No. <Contents> Example 9 0.5% of “Compound A1” was added to polystyrene Example 10 0.5% of “Compound A2” was added to polystyrene Example 11 0.1% of “Compound B1” was added to polystyrene. Example 12 "Compound B2" 0.5% added to polystyrene Example 13 "Compound C1" 0.5% added to polystyrene Example 14 "Compound C2" 0.5% to polystyrene Addition Example 15 Addition of 0.5% of “Compound D1” to polystyrene Example 16 Addition of 0.5% of “Compound D2” to polystyrene Also, a “Comparative sample” is prepared in the same manner as described below. <No. ><Contents> “Comparative Example 1” No additive “Comparative Example 2” 0.5% of “BTHPEMA monomer” added to polystyrene “Comparative Example 3” 1.0% of “BTHPEMA monomer” added to polystyrene “ Comparative example 4 "polystyrene to the 'ultraviolet absorbing section Bu instrument having no fluorine-containing compound E" added 0.5% * "fluorinated compound E having no ultraviolet absorbing segment" _{Rf- (CH 2 = CH-COOH} ) -Rf Mn = 4800 Rf: CF (CF ₃ ) OC ₃ F ₇

(2) Evaluation of weather resistance-Accelerated exposure treatment method Accelerated exposure treatment with WS-type sunshine carbon was performed in accordance with JIS A 1415 (accelerated exposure test method for plastic building materials), and the color difference after 200 hours had elapsed. Measure. Black panel temperature: 63 ± 3 ° C Spray cycle: 18 minutes out of 120 minutes ・ Color difference measurement method Accelerated exposure treatment using a colorimeter (Karacom C type, manufactured by Dainichi Seika Kogyo Co., Ltd.) based on the initial state of each sample The subsequent color difference value (ΔE) is determined by measurement. Here, the larger the ΔE value is, the more discoloration is → the poorer the weather resistance is. The smaller the ΔE value is, the less the discoloration is → the better the weather resistance is.

(3) Evaluation of hydrophilicity and oil repellency • After dropping the reagent on the surface of each sample, the contact angle (°) after 3 minutes was measured and evaluated. Measuring instrument: CA-D evaluation standard manufactured by Kyowa Interface Science Co., Ltd. Hydrophilicity: water → hydrophilicity decreases as contact angle (°) decreases Oil-repellent: dodecane → oil repellency increases as contact angle (°) increases ・ Evaluation Results Also shown in Table 1.

[0050]

[Table 1]

(4) Evaluation of surface bleeding property An elemental analysis of the prepared sample was performed by a photoelectron spectrometer (ESC).
A) is performed. At this time, the elements present in the depth direction are sequentially analyzed while etching the sample surface. The results are shown in FIG.

In Example 9, a large amount of fluorine atoms and nitrogen atoms were detected at the start of etching (the surface of the sample), which was derived from the fluoroalkyl group and benzotriazole group of compound A1. Therefore, it can be seen that when this compound is used as an additive, the ultraviolet absorbing segments are also efficiently arranged on the material surface due to the surface bleeding property of the fluoroalkyl group.

On the other hand, in Comparative Example 1, the detection amount of nitrogen atoms was almost constant irrespective of the change in the etching time, and it was found that the ultraviolet absorber was present uniformly from the surface to the inside of the substance. Those present in the interior are meaningless due to the nature of the additive, which causes the effect corresponding to the added amount to be hardly obtained.

(5) Solubility test in various solvents Table 2 shows the results of confirming the solubility in various solvents. Although a general fluorine-based compound does not melt in various solvents, this compound was confirmed to be soluble in various solvents as shown in the table. The molecular structure mainly composed of hydrocarbons, which is a feature of this compound,
Affinity to various solvents is enhanced, and excellent melting properties are exhibited as compared with general fluorine compounds. The feature of easy melting is expected to be applied to various uses including a modifier in the form of paint.

[0055]

[Table 2]

[0056]

EFFECTS OF THE INVENTION Since the fluorine-containing polymer of the present invention contains an ethylenically unsaturated monomer unit having a UV-absorbing group (also referred to as a UV-absorbing segment), it has a UV-absorbing effect and Since a fluoroalkyl group and / or an oxafluoroalkyl group are present at the polymer terminal, due to the surface bleeding property, the ultraviolet absorbing segments are efficiently arranged on the surface of the object, so that the effective ultraviolet absorbing action can be achieved even with a small blending amount. Is advantageous.

[Brief description of the drawings]

FIG. 1 is a graph showing the results of performing photoelectron spectroscopy on a polystyrene sheet containing the fluoropolymer of the present invention and BTHPEMA.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (reference) C08L 33:14) F-term (reference) 4J002 AA011 AA021 BB031 BC031 BG072 4J100 AL08P BA03P BA12P BA15P BA40P BB07H BB07P BB18H BB18P BC53H BC53P BC75P CA01 CA31 DA61 FA02 FA03 HA27

Claims (11)

[Claims] 1. A fluorine-containing polymer containing an ethylenically unsaturated monomer unit having an ultraviolet absorbing group in a polymer chain and having a fluoroalkyl group and / or an oxafluoroalkyl group at a terminal. Coalescing. 2. A number average molecular weight (Mn) of 500 to 20.
The fluorinated polymer according to claim 1, which is in the range of 000. 3. The fluoropolymer according to claim 1, wherein the molecular weight distribution (Mw / Mn) is in the range of 1.01 to 3.00. 4. The fluorine-containing polymer according to claim 1, wherein the ethylenically unsaturated monomer unit comprises a (meth) acrylate unit. 5. The ultraviolet absorbing group is a group having a benzotriazole-based ultraviolet absorber skeleton, a benzophenone-based ultraviolet absorber skeleton, a salicylate-based ultraviolet absorber skeleton, or a cyanoacrylate-based ultraviolet absorber skeleton. The fluoropolymer according to any one of claims 1 to 4. 6. The following formula (1) In the formula, Rf is a fluoroalkyl group or a fluorooxaalkyl group, R is a hydrogen atom or a methyl group, X is a benzotriazole-based ultraviolet absorber skeleton, a benzophenone-based ultraviolet absorber skeleton, a salicylate-based ultraviolet absorber skeleton, Alternatively, it is an alkyl group having a cyanoacrylate-based ultraviolet absorber skeleton, and has a chemical structure represented by the following formula: n is a number giving a number average molecular weight (Mn) of 1 to 100. 5. The fluorine-containing polymer according to any one of 5. 7. The following formula (2) In the formula, Rf is a fluoroalkyl group or a fluorooxaalkyl group, R is a hydrogen atom or a methyl group, X is a benzotriazole-based ultraviolet absorber skeleton, a benzophenone-based ultraviolet absorber skeleton, a salicylate-based ultraviolet absorber skeleton, Alternatively, it is an alkyl group having a cyanoacrylate-based ultraviolet absorber skeleton, Y is a hydrophilic group or an antibacterial functional group, and n and m are 500 to 5 as a whole.
A number giving a number average molecular weight (Mn) of 0000,
The fluorine-containing polymer according to any one of claims 1 to 5, wherein n: m is in the range of 1:99 to 99: 1. 8. The (meth) acrylate unit represented by the following formula (3): In the formula, R is a hydrogen atom or a methyl group, Y is an alkylene group, X is a hydrogen atom or an alkyl group,
The fluoropolymer according to any one of claims 1 to 7, comprising a unit represented by the following formula: 9. A fluorine-containing polymer obtained by polymerizing an ethylenically unsaturated monomer having an ultraviolet absorbing group in the presence of a peroxide having a fluoroalkyl group and / or an oxafluoroalkyl group. Manufacturing method. 10. An ultraviolet absorbent comprising the fluorinated polymer according to claim 1. Description: 11. An ultraviolet-absorbing polymer composition comprising the fluorine-containing polymer according to claim 1 in an amount of 0.05 to 5% by weight.