JP2980999B2 - UV absorber, additive for fluororesin, and fluororesin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ultraviolet absorbent , fluorine
Additive resins, and about the fluororesin composition.

[0002]

BACKGROUND ART Fluorine-based resin, as a representative of polytetrafluoroethylene, copolymers of tetrafluoroethylene and perfluorovinyl ether, a copolymer of tetrafluoroethylene and hexafluoropropylene, ethylene and tetrafluoroethylene and copolymers such as are known in the heat resistance, chemical resistance, has been widely utilized as an excellent moldable material electrical properties. In addition, it has excellent weather resistance and is effective as a protective covering material for various articles.

[0003] However, fluororesins by themselves have little ability to absorb ultraviolet rays, so that they have poor weather resistance .
If Ru is used as protective covering for the purpose of addition of the ultraviolet absorber or UV shielding agent are essential. And only, the resin, to the moldable lower limit temperature is 280 and at 300 ° C. or higher, whereas, boiling or vaporization starting temperature of conventional UV absorbers are the 150 to 250 ° C., were mixed during heating molding A large amount of the ultraviolet absorber volatilized, and it was not possible to exhibit a sufficient ultraviolet absorbing ability. In addition, even when the ultraviolet absorbent slightly enters the resin, the resin has poor compatibility with the resin and bleeds out due to long-term use, so that the ultraviolet absorbing ability cannot be exhibited.

Further, polyvinyl fluoride resin is disclosed in
As shown in 7-11224 and JP-dissolved UV absorbers in the latent solvent, by cast molding, it is also known that it is possible allowed to produce a composition having sufficient ultraviolet absorbing ability I have. However,
The applications have been limited due to the complexity of the process and the difficulty in the chemical resistance and flame retardancy of the composition.

[0005]

SUMMARY OF THE INVENTION The object of the present invention is to solve the problems of the prior art as described above. The present invention does not volatilize during heat molding of a fluororesin and does not bleed out even during long-term use. To provide an ultraviolet absorbing agent having an ultraviolet absorbing ability.

[0006]

DISCLOSURE OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and has a polymerization unit (A) of a reactive ultraviolet absorbing compound having a radical reactive double bond.
And the polyfluoroalkyl group has 4 to 21 carbon atoms
Polyfluoroalkyl group or polyfluoroether group
Acrylate or methacrylate having a polyfluoroether group having 4 to 21 carbon atoms (hereinafter, specified as
Also referred to as (meth) acrylate. ) Is a copolymer containing the polymerized unit (B), wherein the polymerized unit (A) and the polymerized unit (B)
Has a molar composition ratio of 90:10 to 10:90,
The weight average molecular weight measured by gel permeation chromatography (GPC) is 1,000 to 100,000
And a UV absorber comprising a UV-absorbing copolymer.

[0007] As reactive UV absorbing compounds having a radically reactive double bond in the present invention, the following formula 1
In benzophenone compound represented by full represented by the formula 2
E sulfonyl Sari expressed in shea rate based compound or Formula 3, behenate <br/> benzotriazole Keika compound compound shall be the basic structure is good
Good .

[0008]

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[0009]

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[0010]

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The reactive ultraviolet absorbing compound has a radical-reactive double bond in addition to the above basic structure. As the group having a radical reactive double bond, a vinyl group,
Examples include an allyl group, an acryloyl group, and a methacryloyl group. As a group having a radical-reactive double bond, an acryloyl group or a methacryloyl group is preferable from the viewpoint of copolymerizability with a specific (meth) acrylate described below. Specifically, a compound represented by Chemical Formula 4, Chemical Formula 5, or Chemical Formula 6, or the like is employed.

[0012]

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[0013]

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[0014]

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In the chemical formulas (4) , (5) and (6), R
^1, R ² are each independently a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an aryl group, a halogen atom, an aralkyl group, carboxyl group, an amino group, acryloyl
A group-containing group or a methacryloyl group-containing group;
^At least ^one of R ¹ and R ² is an acryloyl group-containing group or a methacryloyl group-containing group. R ³ is acryloyl
Or group-containing group is a methacryloyl group-containing group. R ⁴ is a halogen atom or a hydrogen atom . R ⁵ is a hydrogen atom,
Alkyl group, an alkoxy group, an alkylsulfonyl group, scan <br/> sulfo group, a carboxylic hexyl group, a halogen atom, an acryloyl group-containing group, or a methacryloyl group-containing group der
You . R ^6, R ⁸ are each independently a hydrogen atom, an alkyl group, an alkoxy group, an aralkyl group, haloaryl
Group, or a cycloalkyl group. R ⁷ is a hydrogen atom,
A hydroxyl group, an alkoxy group, an alkyl group or also an acryloyl group-containing group, is a methacryloyl group-containing group.

Further, reactive UV absorbing compounds having a radically reactive double bond in the present invention, a hydroxyl group (excluding a hydroxyl group in the basic structure described above) or benzophenone compounds having an amino group, phenyl salicylate-based compound, method or to introduce a benzotriazole compound, a or acrylic acid acryloyl group or a methacryloyl group by reacting a methacrylic acid, benzophenone having a sulfonic acid group or carboxylic acid group
Compounds, phenyl salicylate-based compound, or the benzotriazole compounds, vinyl alcohol, aminoalkyl acrylates or how an aminoalkyl methacrylate by reacting introducing a radical reactive double bond, Ru can be synthesized by.

[0017] In the present invention, polymerized units (B), the
Ru polymerized units der specific (meth) acrylate.

A polyfluoroalkyl group or a polyfluoroether group having an extremely small number of carbon atoms is not preferred because compatibility with a fluororesin or the like may not be sufficiently obtained. Further, those having a large number of carbon atoms are not preferred because the polymerization reactivity is increased.

Specific examples of the specific (meth) acrylate include the compounds listed in Chemical formula 7, and these are the same as the above-mentioned reactive UV-absorbing compounds having a radical-reactive double bond. It has preferable from the viewpoint of copolymerizability.

[0020]

Embedded image CH ₂ = C (CH ₃ ) COOCH ₂ (CF ₂ ) ₄ CF ₃ CH ₂ = C (CH ₃ ) COOCH ₂ CH ₂ (CF ₂ ) ₆ CF ₃ CH ₂ = CHCOO (CF ₂ ) ₆ CF ₃ CH ₂ = CHCOOCH ₂ CH ₂ (CF ₂ ) ₇ CF ₃ CH ₂ = CHCOOCH ₂ CH ₂ (CF ₂ ) ₅ CF (CF ₃ ) ₂ CH ₂ = C (CH ₃ ) COOCH (OCOCH ₃ ) CH ₂ (CF ₂ ) ₆ CF (CF ₃ ) ₂ CH ₂ = CHCOOCH ₂ CH (OH) CH ₂ (CF ₂ ) ₆ CF (CF ₃ ) ₂ CH ₂ = CHCOOCH ₂ CH ₂ (CF ₂ ) ₈ CF ₃ CH ₂ = C ( CH ₃ ) COOCH ₂ CH ₂ NHCO (CF ₂ ) ₈ CF ₃ CH ₂ = CHCOOCH ₂ CH ₂ N (C ₃ H ₇ ) SO ₂ (CF ₂ ) ₇ CF ₃ CH ₂ = CHCOOCH ₂ CH ₂ CH ₂ CH ₂ ( CF ₂ ) ₇ CF ₃ CH ₂ = C (CH ₃ ) COOCH ₂ CH ₂ N (C ₂ H ₅ ) SO ₂ (CF ₂ ) ₇ CF ₃ CH ₂ = CHCOOCH ₂ CH ₂ NHCO (CF ₂ ) ₇ CF ₃ CH ₂ = CHCOO (CH ₂ ) ₃ (CF ₂ ) ₆ CF (CF ₃ ) ₂ CH ₂ = CHCOOCH ₂ (CF ₂ ) ₁₀ H CH ₂ = C (CH ₃ ) COOCH ₂ (CF ₂ ) ₁₀ CF ₂ Cl

The copolymerization of the reactive ultraviolet absorbing compound having a radical-reactive double bond with a specific (meth) acrylate is carried out by a usual method, for example, Japanese Patent Publication No. 59-47716 and Japanese Patent Application Laid-Open No. 58-118882. It can be performed by a method described in a gazette or the like.

The reactive ultraviolet ray absorbing compound having a radical reactive double bond and the specific (meth) acrylate may be copolymerized by one kind or two or more kinds.
The molar composition ratio of the polymerization unit (A) of the reactive ultraviolet absorbing compound having a radical reactive double bond and the polymerization unit (B) of the specific (meth) acrylate is 90:10 to 10: 9.
Must be 0. If it deviates from this ratio,
Compatibility between the fluorine resin and the ultraviolet absorption performance undesirably not both.

Further , the polymerization unit (A) in the copolymer
Other monomers may be copolymerized as long as the proportion of the total amount of the units (B) is at least 50 mol%. Other alkyl acrylates as a monomer, and an alkyl methacrylate, hydroxyalkyl acrylate, glycidyl methacrylate, aminoalkyl acrylate, such as functional group-containing monomers such as methacrylic acid.

[0024] The ultraviolet absorbent of the present invention, G
The weight average molecular weight measured by PC is 1000 to 100
000. Those too small weight average molecular weight, Re emesis that volatilized during mixing with the fluororesin not preferable. On the other hand, too large ones are not preferred because uniform mixing becomes difficult.

The method of adding the ultraviolet absorbent of the present invention to various resins can be carried out by adding an additive to a usual resin. For example, there is a method in which an appropriate amount of an ultraviolet absorber is added to a resin and the mixture is melt-kneaded.

The ultraviolet absorbent of the present invention has a polyfluoroalkyl group or a polyfluoroether group and a basic structure of ultraviolet absorption, so that an additive or treatment which simultaneously achieves water and oil repellency and ultraviolet absorption is provided. It can be used as an agent. When the treatment agent is not good when using dissolved or dispersed brought in a suitable solvent.

Further, since the ultraviolet absorber of the present invention has a polyfluoroalkyl group or a polyfluoroether group, it is expected that the ultraviolet absorber will be oriented near the surface of the coating film when blended in a paint. An ultraviolet absorption effect can be expected. Therefore, it is useful as an additive for pigmented paints and transparent topcoats.

[0028]

The present invention will be specifically described below with reference to examples.
The present invention is no limited of Lena had by such examples.

[0029] [Example 1] 2- (3'-hydroxy-4'-benzyl) - 100 parts of acetone in Synthesis Example stirrer with autoclave copolymer of phenoxyethyl methacrylate and perfluoroalkylethyl acrylate, a reduction 8 71 parts of 2- (3'-hydroxy-4'-benzyl) -phenoxyethyl methacrylate (hereinafter may be abbreviated as T-17) , perfluoroalkylethyl acrylate (hereinafter abbreviated as FA) (perfluoroalkyl group) Has 6 to 14 carbon atoms , and the carbon number is 6: 8: 10:
12: 14 = 1: 59: 30: 8: mixture) 126 parts of 2 (molar ratio), were charged 0.1 parts of peroxy isobutyrate, was replaced in the autoclave with nitrogen,
The temperature in the autoclave was raised to 65 ° C. while stirring, and the temperature was maintained for 5 hours, followed by cooling to take out a polymer solution.

The obtained polymer solution was mixed with 20 times the amount of methanol to precipitate a polymer, which was filtered through a glass filter and dried at 150 ° C. for 8 hours to obtain a polymer. The conversion was 81% based on the amount of the charged monomers and the amount of the obtained polymer. Dimethylforma
GPC measurement using mide (DMF) as a solvent revealed a weight average molecular weight of about 5,000. From the analysis of the fluorine content, the T-17 / FA molar ratio of the copolymer was 76.6 / 23.4.

[0031]

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[0032] [Comparative Example 1] 2- (3'-hydroxy-4'-benzyl) - 71 parts of phenoxyethyl methacrylate polymer of Synthesis Example 1 in T-17, a T-17 instead of FA126 parts T-17 homopolymer 111 was prepared using the same polymerization method and post-treatment method as in Example 1 except that 142 parts were charged.
Parts were synthesized. GPC measurement using DMF as a solvent revealed a weight average molecular weight of about 5,500.

[ Test Example ] The content molar ratios of tetrafluoroethylene , chlorotrifluoroethylene and ethylene were 45 , 24 and 31, the volume flow rate at 300 ° C. was 90 mm ³ / sec,
A copolymer obtained in Example 1, a polymer obtained in Comparative Example 1 , or 2-hydroxy-4-n was added to 100 parts by weight of a fluororesin having a melting point of 201 ° C., a thermal decomposition point of 367 ° C., and an oxygen index of 76.
5 parts by weight of octoxybenzophenone (indicated as UVA in Table 1) was added, mixed and extruded at 220 ° C. to form a 25 μm film. Table 1 shows the results of evaluating the compatibility of the ultraviolet absorbent , the processability , the ultraviolet transmittance , and the ultraviolet transmittance after 1000 hours of the sunshine weatherometer with respect to this film.

[0034]

[Table 1]

[0035]

The ultraviolet absorbent according to the present invention is effective as an additive for a fluororesin, and sufficient ultraviolet absorption performance can be achieved with a small amount of addition. In addition, the performance does not decrease over a long period of time. Further, it is useful as a paint additive.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08F 20/34 C08F 20/34 20/38 20/38 20/58 20/58 20/60 20/60 G03F 7/027 G03F 7 / 027 7/029 7/029 7/031 7/031 (56) References JP-A-62-296117 (JP, A) JP-A-58-84843 (JP, A) (58) Fields investigated (Int. . Cl ^6, DB name) C09K 3/00 104 C08F 20/00 - 20/70 C08L 33/00 - 33/26

Claims (4)

(57) [Claims] 1. A polymerized unit (A) of a reactive UV-absorbing compound having a radical-reactive double bond, and a polyfluoroalkyl having a polyfluoroalkyl group having 4 to 21 carbon atoms.
And the polyfluoroether group has 4 to 21 carbon atoms.
Acrylates with polyfluoroether groups
Or a copolymer containing a polymerized unit (B) of methacrylate , wherein the molar composition ratio of the polymerized unit (A) to the polymerized unit (B) is in the range of 90:10 to 10:90, and gel permeation chromatography An ultraviolet absorbent comprising an ultraviolet absorbent copolymer, wherein the weight average molecular weight measured by the method is in the range of 1,000 to 100,000. 2. A reactive UV absorbing compounds having a radically reactive double bond is a benzophenone compound also acryloyl group properly is having a methacryloyl group, also is properly acryloyl phenyl salicylate-based compound having a methacryloyl group or acryloyl, ultraviolet absorbent described in even groups properly claim 1 is a benzotriazole compound having a methacryloyl group. 3. An additive for a fluororesin comprising the ultraviolet absorbent according to claim 1. 4. A fluororesin composition comprising the fluororesin additive according to claim 3 and a fluororesin.