JPH08904B2 - Cationic polymer UV absorber - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention treats a plastic plate, a plastic film, glass, a textile product, etc. with durability to photo-deterioration to these substances or ultraviolet rays passing through these substances. The present invention relates to a cationic polymer ultraviolet absorber capable of cutting off the harmful effects of ultraviolet rays.

[0002]

2. Description of the Related Art Textile products such as plastics, plastic films, beach umbrellas, golf wear and other clothing, and curtains are used by being exposed to sunlight outdoors. Therefore, due to the ultraviolet rays of sunlight, these themselves are photo-deteriorated, or the dyes and pigments coloring these are photo-deteriorated to cause discoloration. Alternatively, ultraviolet rays that pass through the fibers may cause sunburn and photodegradation of indoor equipment products.

Further, although a glass plate, an acrylic plate and the like hardly cause photo-deterioration by themselves, they cause sunburn due to ultraviolet rays transmitted through the glass plate and the acrylic plate and photo-deterioration of the contents. Traditionally, as a measure to prevent light deterioration of plastic products,
Alternatively, as a measure for photodegradation of a textile product and improvement of fastness to sunlight, it is possible to knead a low molecular weight ultraviolet absorber such as a benzophenone compound or a benzotriazole compound into the product, or to adsorb the ultraviolet absorber to the fiber. Has been done.

Conventionally, as the ultraviolet absorber, 2,4
-Dihydroxybenzophenone, 2,2 ', 4,4'-
Tetrahydroxybenzophenone, 2-hydroxy-4
2-hydroxybenzophenones such as octoxybenzophenone; 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl)- 5
2-Hydroxyphenylbenzotriazoles such as -chlorobenzotriazole and 2- (2'-hydroxy-3 ', 5'-dibutylphenyl) -5-chlorobenzotriazole are widely used.

[0005]

However, since all of the conventional ultraviolet absorbers are low molecular weight compounds, when kneaded into a plastic, the long-term effect is inferior due to bleed-out over time. Further, when it is adsorbed on a textile product or used in combination with a binder, it immediately flows out by washing and the effect is extremely poor in sustaining. Also, in the case of treating a glass plate or the like for the purpose of preventing ultraviolet light transmission, it is necessary to apply these ultraviolet absorbers to the glass plate in combination with a binder such as acrylic or urethane to form a film, which is troublesome to operate. However, the current situation is that the ultraviolet absorber bleeds out from the binder with the passage of time and loses its effect.

Since the present invention is a polymer, it does not bleed out as compared with a low molecular weight ultraviolet absorber, and since it has a cationic group in the molecule, it is strongly adsorbed to plastics, glass, fibers and the like. The present invention provides a cationic polymer UV absorber having excellent durability.

[0007]

The cationic polymeric UV absorber of the present invention comprises a UV absorbing copolymer unit and a fourth
It is characterized by comprising a copolymer containing a copolymer unit having a primary ammonium group.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The cationic polymer UV absorber of the present invention is typically a polymerizable vinyl compound having a UV-absorbing compound residue UV bonded to its main chain as a side chain, as shown in Chemical Formula 1 below. It is a copolymer of a monomer and a polymerizable vinyl compound monomer having a quaternary ammonium group bonded to the main chain.
The structure of Chemical formula 1 is UV (ultraviolet absorbing compound residue)
It does not necessarily mean that the quaternary ammonium group and the quaternary ammonium group are directly bonded to the main chain of the vinyl compound, and generally has a structural unit for bonding in the middle thereof.

[0009]

Embedded image (UV: benzophenone type, benzotriazole type, etc. ultraviolet absorbing compound residues R ₁ , R ₂ : hydrogen or a lower alkyl group R ₃ , R ₄ , R ₅ : substituted or inorganic alkyl or alkenyl groups, and May combine with each other to form a ring X: counter ion of quaternary ammonium group m / n: copolymerization ratio)

The copolymerization ratio m / n can be set arbitrarily, and by changing the copolymerization ratio of the copolymer units, a cationic property of any property from water-soluble ones to self-dispersible ones can be obtained. A polymeric UV absorber is obtained. Specifically, when the proportion of the copolymer unit containing a quaternary ammonium group is lowered, the water solubility is shifted to the self-dispersing side. The quaternary ammonium group in the present invention includes betaine type and the like.

Typical examples of the ultraviolet absorbing compound residue are a 2-hydroxybenzophenone derivative and a 2-hydroxybenzotriazole derivative. Specific examples of the monomer forming the ultraviolet absorbing copolymer unit (ultraviolet absorbing monomer) in the present invention include the following. Further, both of the following 2-hydroxybenzophenone derivative and 2-hydroxybenzotriazole derivative can be used together as monomers. As described above, by using two or more kinds having different ultraviolet absorption characteristics in combination, the ultraviolet absorption effect is further improved.

(1) 2-hydroxybenzophenone derivative represented by Chemical formula 2

Embedded image

The monomer represented by the formula 2 is, for example, BP
An ultraviolet absorbing compound having a functional group such as —R ₂ —OH (BP: 2-hydroxybenzophenone skeleton), and CH ₂
It can be obtained by reacting a polymerizable vinyl compound having a functional group such as ═CR ₃ COOH and the like, and bonding and introducing an ultraviolet absorbing compound residue into the polymerizable vinyl compound through an ester bond X (—COO—).

Specific examples of the monomer compound represented by the above chemical formula 2 include 2-hydroxy-4-acryloyloxybenzophenone, 2-hydroxy-4-methacryloyloxybenzophenone and 2-hydroxy-4- (2-.
Acryloyloxy) ethoxybenzophenone, 2-hydroxy-4- (2-methacryloyloxy) ethoxybenzophenone, 2-hydroxy-4- (2-methyl-)
2-acryloyloxy) ethoxybenzophenone and the like.

(2) 2-hydroxybenzotriazole derivative represented by Chemical formula 3

[Chemical 3]

Specific examples of the monomer compound represented by the above chemical formula 3 include 2- [2'-hydroxy-5 '-(methacryloyloxy) phenyl] benzotriazole and 2
-[2'-hydroxy-5 '-(acryloyloxy) phenyl] benzotriazole, 2- [2'-hydroxy-3'-t-butyl-5'-(methacryloyloxy)
Phenyl] benzotriazole, 2- [2'-hydroxy-3'-methyl-5 '-(acryloyloxy) phenyl] benzotriazole, 2- [2'-hydroxy-
5 '-(methacryloyloxypropyl) phenyl]-
5-chlorobenzotritriazole, 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] benzotriazole, 2- [2'-hydroxy-
5 '-(acryloyloxyethyl) phenyl] benzotriazole, 2- [2'-hydroxy-3'-t-butyl-5'-(methacryloyloxyethyl) phenyl] benzotriazole, 2- [2'-hydroxy-
3'-methyl-5 '-(acryloyloxyethyl) phenyl] benzotriazole, 2- [2'-hydroxy-5'-(methacryloyloxypropyl) phenyl]
-5-chlorobenzotriazole, 2- [2'-hydroxy-5 '-(acroyloxybutyl) phenyl]-
5-methylbenzotriazole, [2-hydroxy-3
-T-butyl-5- (acryloyloxyethoxycarbonylethyl) phenyl] benzotriazole and the like.

The copolymer unit having a quaternary ammonium group is alkylated by copolymerizing a polymerizable vinyl compound having a tertiary amino group in the molecule as a monomer with an ultraviolet absorbing monomer. In the polymeric ultraviolet absorber of the present invention, by quaternizing this amino group with an agent or by previously converting the tertiary amino group of the monomer into a quaternary ammonium salt with an alkylating agent and then copolymerizing the same. Can be introduced to.

As the copolymerizable vinyl compound having a tertiary amino group in the molecule, N, N-dimethylaminopropyl acrylamide, N, N-dimethylaminoethyl acrylamide, N, N-dimethylaminopropyl acrylate, N , N-diethylaminoethyl acrylate, acryloylmorpholine, N-2-hydroxy-3
-Acryloyloxypropyl-N, N-dimethylamine, N-3-methacryloyloxy-2-hydroxypropyl-N, N-diethylamine and the like can be mentioned.

The alkylating agent for converting the amino group of the tertiary amino group-containing copolymerizable vinyl compound into a quaternary ammonium salt includes halogenated alkyls such as benzyl chloride and methyl chloride; dimethylsulfate and diethyl. Examples thereof include sulfuric acid esters such as sulfuric acid and the like, and a betaine type quaternary ammonium group can be obtained by reacting with monochloroacetic acid, β-propiolactone and the like.

As the quaternary ammonium salt group-containing copolymerizable vinyl compound, N-2-hydroxy-3-acryloyloxypropyl-N, N, N-trimethylammonium chloride, N-methacryloylaminoethyl-
Examples include N, N, N-dimethylbenzylammonium chloride, N-methacrylooxy-N, N, N-triethylammonium ethylsulfate and the like.

When a halohydrin compound having an epoxy group in the molecule such as epichlorovidrin is used as the alkylating agent, a cationic polymer UV absorber which becomes an insoluble polymer by heat treatment can be obtained. This polymeric UV absorber is insolubilized by the reaction of the epoxy group in the molecule with the active group such as the hydroxyl group in the copolymer by heat treatment and crosslinking.

Therefore, for example, a durable ultraviolet absorbing film is formed on the glass plate by applying an aqueous solution of the cationic polymer ultraviolet absorbing agent to a glass plate and the like, drying and further heat setting. Therefore, it is possible to prevent the ultraviolet rays transmitted through the glass plate, so that it can be applied to window glass of a car.

Further, the third copolymer component can be introduced to the extent that the effects of the present invention are not impaired, and other copolymerizable vinyl compounds used therein are acrylic acid, methacrylic acid, Examples thereof include alkyl esters of acrylic acid, methacrylic acid alkyl esters, alkyl vinyl ethers, and alkyl vinyl esters.

The polymer ultraviolet absorber of the present invention preferably has a weight average molecular weight of 5,000 to 1,000,000,
It is preferably 10,000 to 800,000.

[0025]

Since the polymeric ultraviolet absorber of the present invention is water-soluble, it can be easily added and utilized in various aqueous substances or aqueous products. For example, by adding it to a water-based paint, it is possible to prevent photo-deterioration of the paint film.

Further, by varying the copolymerization ratio of the quaternary ammonium group-containing monomer, it is possible to easily obtain various forms from a water-soluble polymeric UV absorber to a self-dispersing polymeric UV absorber. You can Therefore, it is advantageous not only when it is added to a product in the form of a transparent aqueous solution but also because of the product form.

Further, the polymeric ultraviolet absorber of the present invention comprises
Since it has a quaternary ammonium group in the molecule and exhibits a cationic property and exhibits adsorptivity to all substances, it can be used for various purposes. One example is a textile product such as clothing, Applications include hair care products, paints and pigments.

Since fiber products generally have a negative charge, the cationic polymeric UV absorber of the present invention is strongly adsorbed on these fibers to form a strong film having wash resistance. However, it is possible to carry out a continuous ultraviolet ray transmission preventing treatment.

Hair is tanned by sunlight (ultraviolet rays),
To prevent this, the addition of an ultraviolet absorber is effective. Since the ultraviolet absorbent of the present invention is water-soluble and cationic, it is easily adsorbed on hair and has a long-lasting effect, and excellent hair care products such as hair cosmetics can be obtained.

Many dyes and pigments are faded by ultraviolet rays, but by adsorbing the ultraviolet absorbent of the present invention on the surface of the particles of the dye or pigment, a dye or pigment having an ultraviolet resistance effect can be easily produced. .

[0031]

Examples Example 1: Polymerization and cationization reaction of a copolymer of 2-hydroxy-4-methacryloyloxybenzophenone and N, N-dimethylaminoethyl acrylate Dimroth, dropping funnel, thermometer, nitrogen introducing tube, stirring In a separable flask equipped with a device, 2-hydroxy-4
-Methacryloyloxybenzophenone 30 g, N, N
-70 g of dimethylaminoethyl acrylate and 100 g of ethyl cellosolve are added, and the temperature is raised to 80 ° C while blowing nitrogen from the nitrogen introducing pipe. Thereafter, azobisisobutyronitrile (hereinafter referred to as “A”) dissolved in a small amount of ethyl cellosolve.
(Abbreviated as “IBN”) 0.1 g is divided into 4 portions and added dropwise at intervals of 30 minutes. After completion of the dropping, the reaction was carried out for 2 hours under a nitrogen atmosphere to obtain a polymer type ultraviolet absorber solution. Further, 30 g of diethyl sulfuric acid is added dropwise thereto over 30 minutes, and the reaction is carried out for 2 hours under a nitrogen atmosphere. The stirring speed was 150 rpm. After completion of the reaction, the mixture was cooled to room temperature, diluted with water and solid content
An aqueous solution of 0% cationic polymer type ultraviolet absorber was obtained.

Example 2: Polymerization and cationization reaction of copolymer of 2-hydroxy-4-acryloyloxybenzophenone and N, N-dimethylaminopropyl acrylamide 30 g of 2-hydroxy-4-acryloyloxybenzophenone, N, N -Dimethylaminopropyl acrylamide 70 g, ethyl cellosolve 100 g, AIBN0.
Polymerization is carried out in the same manner as in Example 1 using 12 g, and a cationization reaction is carried out in the same manner as in Example 1 using 30 g of dimethylsulfate. After completion of the reaction, the mixture was cooled to room temperature and diluted with water to obtain an aqueous solution of a cationic polymer ultraviolet absorber having a solid content of 20%.

Example 3: Polymerization and cationization reaction of a copolymer of 2-hydroxy-4- (acryloyloxy) ethoxybenzophenone and N-2-hydroxy-acryloyloxypropyl-N, N-dimethylamine 2-hydroxy -4- (acryloyloxy) ethoxybenzophenone 30 g, N-2-hydroxy-acryloyloxypropyl-N, N-dimethylamine 70 g,
Using 1000 g of ethyl cellosolve and 0.12 g of AIBN, polymerization was carried out in the same manner as in Example 1, and 30 g of benzyl chloride was used to carry out a cationization reaction in the same manner as in Example 1. After completion of the reaction, the mixture was cooled to room temperature and diluted with water to obtain an aqueous solution of a cationic polymer ultraviolet absorber having a solid content of 20%.

Example 4: 2-Hydroxy-4- (2-methacryloyloxy) ethoxybenzophenone and N-3
-Methacryloyloxy-2-hydroxypropyl-
Polymerization and cationization reaction of copolymer with N, N-diethylamine 2-hydroxy-4- (2-methacryloyloxy) ethoxybenzophenone 30 g, N-3-methacryloyloxy-2-hydroxypropyl-N, N-diethylamine 80 g , Ethyl cellosolve 100 g, AIBN0.
Polymerization is carried out in the same manner as in Example 1 using 12 g, and a cationization reaction is carried out in the same manner as in Example 1 using 30 g of methyl chloride. After completion of the reaction, the mixture was cooled to room temperature and diluted with water to obtain an aqueous solution of a cationic polymer ultraviolet absorber having a solid content of 20%.

Example 5: Polymerization and cationization reaction of a copolymer of 2-hydroxy-4- (2-methyl-acryloyloxy) ethoxybenzophenone and N, N-dimethylaminopropylacrylamide 2-hydroxy-4- ( 2-acryloyloxy) ethoxybenzophenone 30 g, N, N-dimethylaminopropyl acrylamide 70 g, ethyl cellosolve 100
g and AIBN 0.12 g are polymerized in the same manner as in Example 1, and the cationization reaction is carried out in the same manner as in Example 1 using 30 g of monochloroacetic acid. After completion of the reaction, the mixture was cooled to room temperature and diluted with water to obtain an aqueous solution of a cationic polymer ultraviolet absorber having a solid content of 20%.

Example 6: 2- [2'-hydroxy-5 '
Polymerization and cationization reaction of copolymer of-(methacryloyloxy) phenyl] benzotriazole and N, N-dimethylaminopropyl acrylate 30 g of 2- [2'-hydroxy-5 '-(methacryloyloxy) phenyl] benzotriazole, 70 g of N, N-dimethylaminopropyl acrylate, 100 g of ethyl cellosolve and 0.12 g of AIBN were used for polymerization in the same manner as in Example 1, and 30 g of β-propiolactone was used for cationization in the same manner as in Example 1. Carry out the reaction. After completion of the reaction, the mixture was cooled to room temperature and diluted with water to obtain an aqueous solution of a cationic polymer ultraviolet absorber having a solid content of 20%.

Example 7: 2- [2'-hydroxy-5 '
Polymerization and cationization reaction of copolymer of-(acryloyloxy) phenyl] benzotriazole and N, N-diethylaminoethyl acrylate 2- [2'-hydroxy-5 '-(acryloyloxy) phenyl] benzotriazole 30 g, N , N-diethylaminoethyl acrylate (70 g), ethyl cellosolve (100 g) and AIBN (0.12 g) were used for polymerization in the same manner as in Example 1, and 30 g of dimethyl sulfate was used for cationization reaction in the same manner as in Example 1. After completion of the reaction, the mixture was cooled to room temperature and diluted with water to obtain an aqueous solution of a cationic polymer ultraviolet absorber having a solid content of 20%.

Example 8: 2- [2'-hydroxy-3 '
Polymerization and cationization reaction of copolymer of -t-butyl-5 '-(methacryloyloxy) phenyl] benzotriazole and acryloylmorpholine 2- [2'-hydroxy-3'-t-butyl-5'-
(Methacryloyloxy) phenyl] benzotriazole 30 g, acryloylmorpholine 70 g, ethyl cellosolve 100 g, and AIBN 0.12 g were polymerized by the same procedure as in Example 1, and monochloroacetic acid 30 g was used by the same procedure as in Example 1. The chemical reaction is performed. After completion of the reaction, the mixture was cooled to room temperature and diluted with water to obtain an aqueous solution of a cationic polymer ultraviolet absorber having a solid content of 20%.

Example 9: 2- [2'-hydroxy-5 '
Polymerization and cationization reaction of copolymer of-(methacryloyloxy) phenyl] -5-chlorobenzotriazole and N, N-diethylaminoethyl acrylate 2- [2'-hydroxy-5 '-(methacryloyloxy) phenyl]- 5-chlorobenzotriazole 30
g, N, N-diethylaminoethyl acrylate 70
g, ethyl cellosolve 100 g, and AIBN 0.12 g are polymerized in the same manner as in Example 1, and benzyl chloride 30 g is subjected to the cationization reaction in the same manner as in Example 1. After completion of the reaction, the mixture was cooled to room temperature and diluted with water to obtain an aqueous solution of a cationic polymer ultraviolet absorber having a solid content of 20%.

Example 10: 2-Hydroxy-4- (2-
Methacryloyloxy) ethoxybenzophenone and 2-
Polymerization and cationization reaction of a copolymer of [2'-hydroxy-5 '-(acryloyloxy) phenyl] benzotriazole and N, N-diethylaminoethyl acrylate 2-hydroxy-4- (2-methacryloyloxy) ethoxybenzophenone 15 g, 2- [2'-hydroxy-5 '-(acryloyloxy) phenyl] benzotriazole 15 g, N, N-diethylaminoethyl acrylate 70 g, ethyl cellosolve 100 g, AIBN
Polymerization is carried out in the same manner as in Example 1 using 0.12 g, and a cationization reaction is carried out in the same manner as in Example 1 using 30 g of dimethylsulfate. After completion of the reaction, the mixture was cooled to room temperature and diluted with water to obtain an aqueous solution of a cationic polymer ultraviolet absorber having a solid content of 20%.

Example 11: Polymerization of N-2-hydroxy-3-acryloyloxypropyl-N, N-dimethylamine cationization reaction product with 2-hydroxy-4-methacryloyloxybenzophenone Dimroth, dropping funnel, thermometer , N-2-hydroxy-in a separable flask equipped with a nitrogen introduction tube and a stirring device.
70 g of 3-acryloyloxypropyl-N, N-dimethylamine and 100 g of ethyl cellosolve were added, to which 30 g of epichlorohydrin was added dropwise over 30 minutes.
Stir for 2 hours. Then, 30 g of 2-hydroxy-4-methacryloyloxybenzophenone and 50 g of ethyl cellosolve, which had been heated and dissolved in advance, were added, and 30
Blow nitrogen through the nitrogen introduction tube for a minute. After that, AIBN 0.1 g dissolved in a small amount of ethyl cellosolve is divided into 4 parts,
Add dropwise at 30 minute intervals. After the dropping is completed, the reaction is performed for 2 hours in a nitrogen atmosphere. The stirring speed was 150 rpm.
After completion of the reaction, the mixture was cooled to room temperature and diluted with water to a solid content of 20% to obtain an aqueous solution of a cationic polymer type ultraviolet absorber.

Comparative Example 1 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole 500
g, 1500 g of water, and 50 g of formaldehyde condensate of sodium naphthalene sulfonate were dispersed and stirred for 1 hour with a Mega Gapper Glen Mill (manufactured by Asada Iron Works Co., Ltd.) to obtain a dispersion solution of an ultraviolet absorber.

Comparative Example 2 2,2,4,4'-tetrahydroxybenzophenone 5
00 g, water 1500 g, and formaldehyde condensate 35 g of sodium naphthalene sulfonate were dispersed and stirred for 1 hour with a Mega Gapper Glen Mill (manufactured by Asada Iron Works Co., Ltd.) to obtain a dispersion solution of an ultraviolet absorber.

Test Example 1 3 w of the cationic polymer UV absorber of Examples 1-11
100% by immersing in 3 kinds of fibers, cotton broad, cotton taffeta, and cotton knit, in a solution diluted with water to t%
After forming the aperture, the ultraviolet transmittance of a sample dried at 100 ° C. for 2 minutes was measured with a spectrophotometer. 3 of Examples 1 to 11
The measurement results of the transmittance (T%) at 05 nm and 360 nm are shown in Table 1. Further, as a measurement example, the spectral transmittance of Example 1 is shown in FIG. As a measuring device, an integrating sphere (diameter 6
0 mm) self-spectrophotometer U-3300 type (Hitachi, Ltd.) was used.

[0045]

[Table 1]Table 1: Transmittance (T%) Example No. 1 2 3 4 5 6 7 8 9 10 11 Untreated Cotton broad: T% (305nm) 3.1 3.0 2.9 3.2 3.0 3.1 3.0 3.3 3.0 2.9 2.9 17.9 T% (360nm) 9.2 9.0 8.9 9.2 9.1 9.0 9.0 9.2 8.9 8.7 8.9 22.8 Cotton taffeta: T% (305nm) 3.0 3.5 3.4 3.3 3.5 3.1 3.2 3.3 3.0 3.0 3.0 18.9 T% (360nm) 10.5 10.0 10.5 10.6 10.8 10.4 9.9 9.8 9.7 10.0 10.8 23.5 Cotton knit: T% (305nm) 2.9 2.9 3.0 2.8 3.0 3.1 2.9 2.8 3.0 2.8 2.8 15.6 T% (360nm) 9.7 9.6 9.9 9.5 9.9 9.7 9.8 9.5 9.8 9.5 9.8 20.5

Test Example 2 After the cotton broads were immersed for 2 minutes in a solution prepared by diluting the cationic polymeric UV absorbers of Examples 1 to 11 and Comparative Examples 1 to 2 with water to a concentration of 0.05 wt%, The ultraviolet transmittance of the sample dried at 100 ° C. for 2 minutes was measured with a spectrophotometer. 305n of Examples 1-11 and Comparative Examples 1-2
Table 2 shows the measurement results of the transmittance (T%) at m and 360 nm.
And shown in Table 3. Further, as a measurement example, the spectral transmittance of Example 1 is shown in FIG. A self-spectrophotometer U-3300 (Hitachi, Ltd.) with an integrating sphere (diameter 60 mm) was used as the measuring device.

[0047]

[Table 2]Table 2: Transmittance (T%) Example No. 1 2 3 4 5 6 7 8 9 10 11 Untreated Cotton broad: T% (305nm) 6.6 6.5 6.7 6.4 6.5 6.6 6.4 6.7 6.5 6.5 6.3 17.9 T% (360nm) 16.1 16.0 16.1 15.9 16.0 16.1 15.8 16.2 16.0 15.8 15.7 22.8

[0048]

[Table 3] Table 3: Transmittance (T%) Comparative Example No. 1 2 Cotton broad: T% (305 nm) 15.5 14.8 T% (360 nm) 20.9 20.0

Test Example 3 After dyeing acrylic fibers under the following conditions, Examples 1 to 1
11 and Comparative Examples 1 and 2 are diluted with water so as to have a solid content of 1% to obtain a treatment bath. The closed acrylic fiber was immersed in this treatment bath, treated with mangle so that the squeezing ratio was 80%, and then dried at 120 ° C. for 2 minutes. The light resistance of the acrylic fiber sample obtained by the above mutual production was measured according to JIS L 08.
04 (Dyeing fastness test method against carbon arc light)
Table 4 shows the results of the test according to the above. Dyeing conditions Dye C. I. BASIC RED56 1% owf acetic acid 0.2cc / l sodium acetate 0.4g / l CATIBON LK 1% owf (leveling agent: produced by Yatasha Yushi-Seiyaku Co., Ltd.) Bath ratio: 20 Dyeing temperature / time: 100 ° C x 30 minutes

[0050]

[Table 4]Table 4 Example Comparative example  1 2 3 4 5 6 7 8 9 9 11 11 1 2 Light resistance 5 5 5 to 4 5 to 4 5 5 5 to 4 5 5 to 4 5 5 to 4 2 to 3 3 (Class)

Test Example 4 100 g of methyl methacrylate, 60 g of n-butyl methacrylate, 35 g of 2-hydroxyethyl methacrylate, 5 g of methacrylic acid and 150 g of ethyl acetate were taken, and AIBN 2 g and dodecyl mercaptan 0.4 g with heating and stirring at 70 ° C. And a solution of 50 g of ethyl acetate was added dropwise over 1 hour. Then, the mixture was stirred at the same temperature for 7 hours to prepare an acrylic resin solution having a resin solid content of 50%. 100 g of this acrylic resin solution, butoxylated methylol melamine (manufactured by Mitsui Toatsu Chemicals Inc .; Uvan 20SE60; resin solid content 6)
0%) 30 g, cellulose acetate (20% butyl acetate solution) 500 g, and Examples 1 to 11 in advance.
And a pigment (BASF
(Lithol Scarlet K 4300)
After soaking in 100g, dehydrated and dried, crushed to 5
A test sample was prepared by mixing 0 g and 100 g of xylene. This test sample was applied to a primer-treated steel sheet with a dry film thickness of 30.
It was sprayed so as to have a thickness of μ, left for 15 minutes, and then baked at 140 ° C. for 30 minutes to prepare a test piece. The test piece was put in a weathermeter to test the light resistance of the pigment. Table 5 shows the evaluation results of the light resistance.

[0052]

[Table 5]Table 5 Example Comparative example  1 2 3 4 5 6 7 8 9 9 11 11 1 2 Light resistance 5 5 5 5 5 to 4 5 5 5 to 4 5 5 5 to 4 2 3 (Class)

Test Example 5 The cationic polymeric UV absorbers of Example 11 and Comparative Examples 1-2 were placed on a glass plate (thickness 1.2-1.5 mm).
Cast this test sample to a dry film thickness of 5μ,
After being left for 30 minutes, it was dried at 150 ° C. for 5 minutes to prepare a test piece. The ultraviolet transmittance of the test piece was measured and is shown in FIG. Also,
The whitening state of the film when this test piece was immersed in water for 2 hours was observed, and the results are shown in Table 6.

[0054]

[Table 6]

[Brief description of drawings]

FIG. 1 is a graph showing a spectral transmittance of a test example.

FIG. 2 is a graph showing a spectral transmittance of a test example.

FIG. 3 is a graph showing a spectral transmittance of a test example.

Claims (2)

[Claims] 1. A cationic polymer ultraviolet absorber comprising a copolymer containing an ultraviolet absorbing copolymer unit and a copolymer unit having a quaternary ammonium group. 2. A polymerizable vinyl compound having a UV-absorbing 2-hydroxybenzophenone residue bonded thereto and / or a polymerizable vinyl compound having a 2-hydroxybenzotriazole residue bonded thereto, wherein the UV-absorbing copolymer unit is bonded to the polymerizable vinyl compound. The cationic polymer UV absorber according to claim 1, which is derived from the above.