JP2002371193A - Ultraviolet-absorbing resin composition, vessel and ultraviolet-absorbing coating agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce an ultraviolet-absorbing composition and an coating agent by using an ultraviolet-absorbing agent absorbable over the whole wavelength range and having high safety and stability in the environment, and provide an excellent ultraviolet-absorbing vessel produced by using the composition or the coating agent and effective for preventing the discoloration and degradation of the contents of the vessel by ultraviolet rays. SOLUTION: The ultraviolet-absorbing resin composition is produced by compounding a pyridazine derivative of the general formula (R1 , R2 , R3 and R4 are not H at the same time) or its salt as an ultraviolet-absorbing agent. A coating agent is produced by compounding the pyridazine derivative of the formula or its salt as the ultraviolet-absorbing agent and the ultraviolet- absorbing vessel produced by using the resin composition or the coating agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ultraviolet absorbing resin composition containing an ultraviolet absorbing agent, a container, a coating agent, and more particularly to an improvement of an ultraviolet absorbing component thereof.

[0002]

2. Description of the Related Art Various containers represented by resin molded containers are widely used as containers for cosmetics, foods and the like. These containers are often subjected to various treatments for the purpose of preventing a change in the physical properties of the contents, and are provided with functions according to the purpose of use. When used as a container for a substance that undergoes discoloration or deterioration due to irradiation with ultraviolet rays, it is necessary to protect the contents from ultraviolet rays and maintain the quality by blocking external ultraviolet rays. Further, in the case of a container made of a resin molded product, irradiation of ultraviolet rays may cause deterioration, discoloration, and decrease in mechanical strength of the resin, and therefore, it is necessary to prevent this.

In such a case, a container having an ultraviolet absorbing ability is used by blending a resin material with an ultraviolet absorber or coating the surface of the container with a coating agent containing the ultraviolet absorber. As these ultraviolet absorbers, benzotriazole derivatives, benzophenone derivatives, salicylic acid derivatives and the like are used.

[0004] As an ultraviolet absorber to be added to these ultraviolet absorbing containers or ultraviolet absorbing coating agents, those capable of absorbing ultraviolet rays over a wide wavelength range are desirable in order to protect the contents from ultraviolet irradiation. It is also important that they are not degraded by sunlight exposure,
Further, those with low toxicity and high safety are preferable.

[0005]

However, conventional UV absorbers have not always been satisfactory in the above points. In addition, when blending and coating an ultraviolet absorber in a container, it can be sublimated and volatilized by heating at the time of baking of a coating film or molding of a resin, etc. There is also a problem that the effect is reduced.

It is an object of the present invention to provide an ultraviolet absorbing resin composition and an ultraviolet absorbing coating agent which absorb ultraviolet rays over all wavelengths and further use an ultraviolet absorber which is highly safe and stable in the environment. An object of the present invention is to provide an excellent ultraviolet-absorbing container which can be manufactured and further made into an ultraviolet-absorbing container using the same, thereby preventing the contents in the container from being discolored or deteriorated by ultraviolet light.

[0007]

Means for Solving the Problems As a result of extensive studies by the present inventors to achieve the above object, an ultraviolet absorbing container containing a certain pyridazine derivative as an ultraviolet absorbing agent is extremely excellent. Thus, the present invention has been completed. That is, the present invention uses a pyridazine derivative of the following general formula and / or a salt thereof, which has excellent absorption ability over a wide ultraviolet wavelength range, and is highly stable and safe, and which is a synthetic resin as an ultraviolet absorber. UV-absorbing container, UV-absorbing resin composition, a pyridazine derivative of the following general formula and / or a salt thereof as a UV-absorbing agent, and coating with the coating agent The container is an ultraviolet absorbing container.

[0008]

Embedded image[Wherein, R₁And R₄Is independently a hydrogen atom,
Hydroxyl group, lower alkyl group, lower alkoxy group, or N
(R₅) R₆The group [R₅And R₆Are the same or different, water
Atom, lower alkyl group, lower hydroxyalkyl group, etc.
Or R₅And R ₆Together with the nitrogen atom
Lysinyl, azetidinyl, pyrrolidinyl, piperi
Dino group, hexahydroazepinyl group, heptamethylene
Mino group, octamethyleneimino group, morpholino group, thio
Morpholino group, piperazinyl group, 4-lower alkyl pipe
Represents a heterocyclic group selected from the group consisting of a radinyl group]
And R₂And R₃Is independently a hydrogen atom,
Bromine atom, chlorine atom, hydroxyl group, lower alkyl group, lower
Alkoxy group or N (R₇) R₈The group [R₇And R₈Is
Same or different, hydrogen atom, lower alkyl group, lower
A droxyalkyl group or R₇And R₈Together
Aziridinyl group, azetidinyl group,
Loridinyl group, piperidino group, hexahydroazepinyl
Group, heptamethyleneimino group, octamethyleneimino
Group, morpholino group, thiomorpholino group, piperazinyl
A 4-lower alkylpiperazinyl group
Represents a selected heterocyclic group]. Where R₁,
R₂, R₃And R₄Are not simultaneously hydrogen atoms. ]

The ultraviolet-absorbing resin composition according to the present invention is characterized by comprising the above-mentioned pyridazine derivative and / or its salt. The ultraviolet absorbing container according to the present invention is characterized by comprising the above-mentioned pyridazine derivative and / or salt thereof. The ultraviolet absorbent coating agent according to the present invention is characterized by comprising an ultraviolet absorbent containing the above-mentioned pyridazine derivative and / or a salt thereof. The ultraviolet absorbing container according to the present invention is characterized by being coated with a coating agent containing the above-mentioned pyridazine derivative and / or salt thereof.

In the ultraviolet absorbing resin composition of the present invention, the amount of the pyridazine derivative and / or salt thereof is preferably 0.001 to 20% by mass. In addition, in the ultraviolet absorbing coating agent of the present invention, the amount of the pyridazine derivative and / or salt thereof is preferably 0.001 to 20% by mass.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTIONPyridazine derivatives and salts thereof  Pyridazine represented by the general formula (1) used in the present invention
Derivatives, under certain conditions, equilibrium
It can be a compound in a sex form. In the present invention, for convenience,
Only the pyridazine derivative represented by the general formula (1) is described.
But it may be its tautomer or its mixture.
No.

The pyridazine derivatives used in the present invention are represented by chemical names such as 4,5-dimorpholino-3-hydroxypyridazine, 4,5-dipyrrolidinyl-3-hydroxypyridazine, 4,5-dipiperidino-3-hydroxypyridazine, 4,5-dihexahydroazepinyl-3-hydroxypyridazine, 4,5-dipiperazinyl-3-hydroxypyridazine, 4,5-bis (4-methylpiperazinyl) -3-hydroxypyridazine, 4,5- Bis (bis (2-hydroxyethyl) amino) -3-hydroxypyridazine, 4,5-bis (tris (hydroxymethyl) methylamino) -3-hydroxypyridazine, 3
-Hydroxy-4-pyrrolidinylpyridazine, 3-hydroxy-5-pyrrolidinylpyridazine, 3-hydroxy-4-piperidinopyridazine, 3-hydroxy-5-piperidinopyridazine, 3-hydroxy-4-morpholino Pyridazine, 3-hydroxy-5-morpholinopyridazine, 4-bis (2-hydroxyethyl) amino-3-hydroxypyridazine, 5-bis (2-hydroxyethyl) amino-3-hydroxypyridazine, 3-hydroxy-4-tris (Hydroxymethyl) methylaminopyridazine, 3-hydroxy-5-tris (hydroxymethyl) methylaminopyridazine, 3-hydroxy-6-morpholinopyridazine, 3,6-bis (2-hydroxyethylamino) pyridazine, 3,6- Dimorpholinopyridazine, 4,5-dipi Lysinyl-3-hydroxypyridazine hydrochloride, 4,5-dipiperidino-3-hydroxypyridazine hydrochloride, 3-hydroxy-5-piperidinopyridazine hydrochloride, 3-hydroxy-5-morpholinopyridazine hydrochloride, 5-bis ( 2-hydroxyethyl) amino-3-hydroxypyridazine hydrochloride, 3-hydroxy-
5-tris (hydroxymethyl) methylaminopyridazine hydrochloride, 3-hydroxy-6-morpholinopyridazine hydrochloride, 3,6-bis (2-hydroxyethylamino)
Pyridazine hydrochloride, 4,5-bis (bis (2-hydroxyethyl) amino) -3-hydroxypyridazine hydrochloride, 4,5-bis (tris (hydroxymethyl) methylamino) -3-hydroxypyridazine hydrochloride, etc. is there.

The pyridazine derivative used in the present invention comprises:
It is commercially available from ALDRICH, SIGMA, Tokyo Chemical Industry Co., Ltd., etc., and can be easily obtained, or can be synthesized by a known method. The typical production method is shown below.

Embedded image (1) (2) (3)

In the above reaction formula, A represents a chlorine atom or a bromine atom. Compound (2) (when A is a chlorine atom;
When 4,5-dichloro-3-hydroxypyridazine / A is a bromine atom; 4,5-dibromo-3-hydroxypyridazine is a compound (1) which is easily available (when A is a chlorine atom; mucochloric acid / When A is a bromine atom; mucobromic acid) and according to the above reaction formula, Chemische Beric
hte, 32 , 543 (1899). That is, the compound (2) (A is a chlorine atom or a bromine atom) can be easily obtained by subjecting the compound (1) (A is a chlorine atom or a bromine atom) to a ring-closing reaction with hydrazine. Compound (2) (A is a chlorine atom) is commercially available from ALDRICH and the like, and can be easily obtained. Then, the pyridazine derivative of the present invention can be obtained by reacting compound (2) (A is a chlorine atom or a bromine atom) with an amine such as piperidine.

The pyridazine derivative used in the present invention can be converted into an inorganic acid salt or an organic acid salt by a known method. Examples of the inorganic acid include hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid and the like. Acetic acid, lactic acid,
Maleic acid, fumaric acid, tartaric acid, citric acid, methanesulfonic acid, p-toluenesulfonic acid and the like can be mentioned.

The pyridazine derivative used in the present invention has excellent thermal stability and does not volatilize, so that its efficacy can be maintained for a long time. Therefore, when compounded or coated in a container as various resin compositions or coating agents, it exhibits an excellent effect as an ultraviolet absorber.

Examples of the synthetic resin used in the resin composition of the present invention include polyethylene, polyvinyl chloride,
Polyvinylidene chloride, polyvinyl alcohol, polystyrene, polypropylene, fluororesin, polycarbonate, polyethylene terephthalate, polyamide, cellulose acetate, polybutadiene, polyisoprene, and the like, and copolymers, mixtures, and polymer alloys of these monomers can be given. Etc. may be used.

The production of the resin composition of the present invention can be carried out by a known method. That is, in the synthetic resin raw material,
The pyridazine derivative used in the present invention may be blended as an ultraviolet absorber and mixed and molded by a known method. Examples of the mixing method include mixing by a mixing roll, a Banbury mixer, and an extruder, and examples of the method of molding include an inflation method, an extrusion method (melt extrusion method) such as a T-die method, and a stretching method. .

The coating agent of the present invention is a coating agent obtained by blending a pyridazine derivative used in the present invention as an ultraviolet absorber with a commonly used known coating agent. -Ketone-polyvinyl chloride-polyvinyl acetate copolymer, ketone-vinylidene chloride resin and the like.

The coating of the container with the ultraviolet absorbing coating agent can be carried out by a known method. That is, the container may be coated with the pyridazine derivative used in the present invention as an ultraviolet absorber by a known method. Examples of the method for coating the ultraviolet absorbing coating agent include gravure roll coating, Meyer bar coating, doctor blade coating, dip coating, and air knife coating.

The compounding amount of the ultraviolet absorber in the resin composition of the present invention is usually preferably 0.001 to 20% by mass,
More preferably, it is 0.01 to 10% by mass. 0.00
If the amount is less than 1% by mass, the ultraviolet ray protection effect may not be sufficient, and if the amount is more than 20% by mass, molding may be difficult, which is not preferable.

Hereinafter, the present invention will be described in detail with reference to specific examples.
explain. The present invention is not limited to these.
Absent. First, a production example of the pyridazine derivative of the present invention will be described.
You.Production Example 1 4,5-Dimorpholino-3-hydroxypyridazine  4,5-dichloro-3-hydroxypyridazine (25.0 g, 0.151 m
ol = corresponding to about 17% by weight in the reaction solution) with morpholine (120 ml)
= 100% by volume) and dissolved at 70 ° C or higher for 24 hours
Heated to reflux. After cooling, the precipitated crystals were filtered, and
White crystals of morpholino-3-hydroxypyridazine (37.2
g, yield 92%). Melting point: 256-257 ° C (decomposition) (Capil.) The chemical analysis values of the obtained compound are as follows. Elemental content
Table 1 shows the results of the analysis.¹H-NMR,¹³C-NMR, MS spec
The results are shown in the order of Torr.

[0023]

[Table 1] *: C₁₂H₁₈N₄O₃Calculated as

¹ H-NMR (DMSO-d ₆ , TMS, ppm) δ: 3.21 (dd, 4H, J = 4.4 & 4.9 Hz: -CH ₂ -N-CH _2- ), 3.23
(Dd, 4H, J = 4.4 & 4.9Hz: -CH 2 -N-CH 2 -), 3.62 (dd, 4
H, J = 4.4 & 4.9Hz: -CH ₂ -O-CH _2- ), 3.70 (dd, 4H, J = 4.4 &
4.9Hz: -CH ₂ -O-CH _2- ), 7.67 (s, 1H: pyridazine ring H-
6), 12.38 (s, 1H: OH) ¹³ C-NMR: (DMSO-d ₆ , TMS, ppm) δ: 47.8 (-CH ₂ -N-CH _2- ), 48.5 (-CH ₂ -N-CH _2- ), 6
_{6.1 (-CH 2 -O-CH 2} -), 66.6 (-CH 2 -O-CH 2 -), 131.1, 13
2.6, 141.0 (Hybrid ring C-4, C-5, C-6), 160.7
(Hydraulic ring C-3) MS spectrum: MW = 266 (C ₁₂ H ₁₈ N ₄ O ₃ = 266.30)

[0025]Production Example 2 4,5-dipiperidino-3-hydroxy
Cypyridazine  4,5-dichloro-3-hydroxypyridazine (25.0 g, 0.151 m
ol) in piperidine (120 ml) and heat to reflux for 24 hours
did. After standing to cool, the precipitated crystals were filtered, and 4,5-dipiperidi
White crystals of no-3-hydroxypyridazine (30.3 g, yield 75)
%).

[0026] ^{1 H-NMR (DMSO-d} 6, TMS, ppm) δ: 1.56~1.78 (m, 12H ,: piperidine ring -N-CH ₂ - CH ₂ -CH
₂ -CH ₂ -CH ₂ -N- × 2), 3.16 (t, 4H, J = 5.2 Hz: piperidine ring -CH ₂ -N-CH _2- ), 3.26 (t, 4H, J = 5.2 Hz: piperidine ring
-CH ₂ -N-CH _2- ), 7.57 (s, 1H: pyridazine ring H-6), 10.3
2 (s, 1H: OH) MS _{spectrum: MW = 262 (C 14 H} 22 N 4 O = 262.36)

[0027]Production Example 3 6-morpholino-3-hydroxypi
Redazin  6-chloro-3-hydroxypyridazine (25.0 g, 0.191 mol)
Was dissolved in morpholine (120 ml) and heated under reflux for 24 hours.
Was. After standing to cool, the precipitated crystals were filtered and 6-morpholino-3-
White crystals of hydroxypyridazine (25.8 g, 74% yield)
Obtained.

¹ H-NMR (DMSO-d ₆ , TMS, ppm) δ: 3.15 (t, 4H, J = 4.8 Hz: -CH ₂ -N-CH _2- ), 3.67 (t, 4
H, J = 4.8Hz: -CH ₂ -O-CH _2- ), 6.79 (d, 1H, J = 10.4Hz,
Pyridazine ring H-4 or H-5), 7.49 (d, 1H, J
= 10.4Hz, pyridazine ring H-4 or H-5), 12.13
(S, 1H: OH) MS _{spectrum: MW = 181 (C 8 H} 11 N 3 O 2 = 181.19)

[0029]Production Example 4 3,6-Dimorpholinopyridazine  3,6-Dichloropyridazine (25.0 g, 0.168 mol)
It was dissolved in phosphorus (120 ml) and heated under reflux for 24 hours. Cooling
Then, the precipitated crystals were filtered and 3,6-dimorpholinopyridazi
White crystals (33.7 g, 80% yield) were obtained.

¹ H-NMR (DMSO-d ₆ , TMS, ppm) δ: 3.42 (t, 8H, J = 4.8 Hz: -CH ₂ -N-CH _2- ), 3.80 (t, 8
H, J = 4.8 Hz: -CH ₂ -O-CH _2- ), 6.92 (s, 2H, pyridazine ring H-4 and H-5) MS spectrum: MW = 250 (C ₁₂ H ₁₈ N ₄ O ₂ = 250.30)

Next, the pyridazine derivative used in the present invention
The test regarding the ultraviolet absorption capacity of the body is shown.Test Example 1 Absorbance  4,5-dimorpholino-3-hydroxypyridazine, 4,
5-dipiperidino-3-hydroxypyridazine, 3-hi
Droxy-4-piperidinopyridazine, 3-hydroxy
-5-piperidinopyridazine, 3-hydroxy-4-mo
Rufolinopyridazine, 3-hydroxy-5-morpholino
Pyridazine, 5-bis (2-hydroxyethyl) amino
-3-hydroxypyridazine, 3-hydroxy-6-mo
Ruholinopyridazine, 3,6-bis (2-hydroxyd
Tylamino) pyridazine, 3,6-dimorpholinopyrida
Ultraviolet absorption spectrum of gin (solvent: water, concentration 10pp
m, optical path length 1cm) with a spectrophotometer (U
best-55). The results are shown in FIGS.

From FIG. 1 to FIG. 10, the pyridazine derivative of the present invention can strongly absorb ultraviolet light of 290 nm to 400 nm reaching the surface of the earth over almost all wavelength regions, and has a visible region longer than 400 nm. Has almost no absorption, it can be said that it has excellent transparency.

[0033]Test Example 2 Light stability test  Exposure of the pyridazine derivative aqueous solution of the present invention to sunlight for 2 weeks
After the solar radiation exposure (80 MJ), the residual rate and changes in appearance were adjusted.
UV absorption spectrum (solvent: water, concentration 1)
0 ppm, optical path length 1 cm) was measured with a spectrophotometer.
In the range of 290 nm to 400 nm of the external absorption spectrum,
The area value was obtained by integration processing and compared with that before sunlight exposure.

(Judgment) The residual ratio and the change in the area value of the ultraviolet absorption spectrum were judged according to the following criteria. ：: 95% or more before exposure to sunlight. ：: 90% or more and less than 95% before sun exposure. Δ: 70% or more and less than 90% before sun exposure. X: Less than 70% before sun exposure.

(Results) The results are shown in the following table.

[Table 2]  UV absorber Residual rate UV absorption spectrumOf area value of  4,5-dimethyl morpholino-3-human hydroxylamine ◎ ◎  4,5-shear helicino-3-human oxyrhitacin ◎ ◎  3-Humanoxy-5-morpholino peritone ◎ ◎  3-Hydroxy-4-heritage filter ◎ ◎

As can be seen from Table 2, the pyridazine derivative of the present invention was not decomposed by prolonged exposure to direct sunlight, and showed a very high residual ratio. In addition, there was no change in the shape or area value of the ultraviolet absorption spectrum, and no coloring or precipitation was observed in the appearance.

[0037]

Now, the present invention will be described in detail with reference to specific examples.
I will tell. The present invention is not limited to these.
No. Next, the ultraviolet ray for the ultraviolet ray absorbing container of the present invention
The test regarding the absorption capacity is shown.Example 1 UV-absorbing polyethylene terephthalate
container  As a polyethylene terephthalate resin, Unipet R
T-513 (Nihon Unipet Co., Ltd.), UV absorber
4,5-dimorpholino-3-hydroxypyridazine
0.1% by mass, and used as a molding machine
Model ASD50EX (Nissei Plastic Industry Co., Ltd.)
A container made of UV-absorbing polyethylene terephthalate
Produced. In a container, mixed water and ethyl alcohol
Colored with brilliant blue and tartrazine
And store it in a carbon arc filter from outside the container.
Irradiated with UV light for 20 hours with a dometer and generated on the contents
The color difference was measured. The results are without UV absorber
Compared.

(Results) The results are shown in the following table.

[Table 3]  20 hours after UV irradiationColor difference of contents  4,5-dimorpholino-3-hydroxypyridazine 8.18  No combination 16.01

As can be seen from Table 3, in the ultraviolet absorbing container of the present invention, the effect of the external ultraviolet irradiation on the contents was reduced to about half by adding the pyridazine derivative as the ultraviolet absorbing agent. Showed excellent ultraviolet absorbing ability.

[0040]Example 2 UV absorbing coating agent  Cured by lacquer isocyanate and the main solvent is toluene
・ Ultraviolet absorber for coating of methyl ethyl ketone
4,5-dimorpholino-3-hydroxypyridazine
1.5% by mass, UV-absorbing coating agent
Fabricated, 100 μm polyethylene terephthalate filter
A dry coating pressure of 3μm is formed on the lum with a bar coater.
And measured the transmittance at 365 nm and 380 nm.
Was. The results were compared to those without the UV absorber.

(Results) The results are shown in the following table.

[Table 4]  At 365 nm at 380 nmTransmittance (%) Transmittance (%)  4,5-dimorpholino-3-hydroxypyridazine 0 40  No combination 68 80

As can be seen from Table 4, the UV-absorbing container coated with the UV-absorbing coating agent containing the pyridazine derivative as the UV-absorbing agent of the present invention completely shields against ultraviolet rays of 365 nm, and
In the case of 80 nm ultraviolet light, the transmittance was reduced to about half that in the case where no ultraviolet absorber was added, indicating excellent ultraviolet absorbing ability.

[0043]Example 3 Ultraviolet absorbing low density polyethylene
In  4,5-Dipipe as UV absorber in low density polyethylene
0.1% by mass of lysino-3-hydroxypyridazine
And after mixing, by injection molding, plate-shaped UV absorption
Low density polyethylene was obtained.

[0044]Example 4 UV absorbing polypropylene  4,5-dipiperidi as an ultraviolet absorber in polypropylene
0.1% by mass of no-3-hydroxypyridazine
After mixing, a plate-shaped ultraviolet absorbing polyp
Lopylene was obtained.

[0045]Example 4 UV-absorbing polyvinyl chloride  30% by mass of plasticizer and ultraviolet absorber in vinyl chloride
To give 4,5-dimorpholino-3-hydroxypyridazine
0.1% by mass is blended and mixed.
Thus, a soft vinyl chloride film was obtained.

[0046]Example 5 UV absorbing polypropylene  Ester, ketone-polyvinyl chloride-polyvinyl acetate
4,5-Dimorpholino-3-hi as an ultraviolet absorber for polymers
Contains 10% by weight of droxypyridazine and absorbs ultraviolet rays
A coating agent was obtained. This coating agent is
Coated with Meyer bar coating on propylene film
UV absorbing polypropylene
A film was obtained.

[Brief description of the drawings]

FIG. 1 is a diagram showing an ultraviolet absorption spectrum of a pyridazine derivative, 4,5-dimorpholino-3-hydroxypyridazine, used in the present invention.

FIG. 2: Pyridazine derivatives of the invention, 4,5-dipiperidino
It is a figure which shows the ultraviolet-ray absorption spectrum of -3-hydroxypyridazine.

FIG. 3. Pyridazine derivative of the present invention, 3-hydroxy-4-
It is a figure which shows the ultraviolet-ray absorption spectrum of piperidino pyridazine.

FIG. 4 shows a pyridazine derivative of the present invention, 3-hydroxy-5-
It is a figure which shows the ultraviolet-ray absorption spectrum of piperidino pyridazine.

FIG. 5: Pyridazine derivative of the present invention, 3-hydroxy-4-
It is a figure which shows the ultraviolet-ray absorption spectrum of morpholinopyridazine.

FIG. 6: Pyridazine derivative of the present invention, 3-hydroxy-5-
It is a figure which shows the ultraviolet-ray absorption spectrum of morpholinopyridazine.

FIG. 7 shows an ultraviolet absorption spectrum of the pyridazine derivative of the present invention, 5-bis (2-hydroxyethyl) amino-3-hydroxypyridazine.

FIG. 8: Pyridazine derivative of the present invention, 3-hydroxy-6-
It is a figure which shows the ultraviolet-ray absorption spectrum of morpholinopyridazine.

FIG. 9 is a view showing an ultraviolet absorption spectrum of a pyridazine derivative of the present invention, 3,6-bis (2-hydroxyethylamino) pyridazine.

FIG. 10 is a view showing an ultraviolet absorption spectrum of a pyridazine derivative of the present invention, 3,6-dimorpholinopyridazine.

 ────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Masaru Suetsugu 2-2-1 Hayabuchi, Tsuzuki-ku, Yokohama-shi, Kanagawa F-term in Shiseido Research Center (Shinyokohama) (reference) 3E033 BA13 BB08 CA20 EA10 4J002 AB021 AC021 AC061 BB041 BB121 BC031 BD041 BD10 BD121 BE011 CF061 CG001 CL001 EU136 FD056 GG01 GH00

Claims (7)

[Claims] 1. A resin component and a pyridazine derivative represented by the following general formula:
An ultraviolet absorber characterized by containing a conductor and / or a salt thereof.
Absorptive resin composition. Embedded image[Wherein, R₁And R₄Is independently a hydrogen atom,
Hydroxyl group, lower alkyl group, lower alkoxy group, or N
(R₅) R₆The group [R₅And R₆Are the same or different, water
Atom, lower alkyl group, lower hydroxyalkyl group, etc.
Or R₅And R ₆Together with the nitrogen atom
Lysinyl, azetidinyl, pyrrolidinyl, piperi
Dino group, hexahydroazepinyl group, heptamethylene
Mino group, octamethyleneimino group, morpholino group, thio
Morpholino group, piperazinyl group, 4-lower alkyl pipe
Represents a heterocyclic group selected from the group consisting of a radinyl group]
And R₂And R₃Is independently a hydrogen atom,
Bromine atom, chlorine atom, hydroxyl group, lower alkyl group, lower
Alkoxy group or N (R₇) R₈The group [R₇And R₈Is
Same or different, hydrogen atom, lower alkyl group, lower
A droxyalkyl group or R₇And R₈Together
Aziridinyl group, azetidinyl group,
Loridinyl group, piperidino group, hexahydroazepinyl
Group, heptamethyleneimino group, octamethyleneimino
Group, morpholino group, thiomorpholino group, piperazinyl
A 4-lower alkylpiperazinyl group
Represents a selected heterocyclic group]. Where R₁,
R₂, R₃And R₄Are not simultaneously hydrogen atoms. ] 2. An ultraviolet absorbing container formed of the resin composition according to claim 1. 3. An ultraviolet absorbing coating agent comprising a pyridazine derivative of the general formula and / or a salt thereof. 4. An ultraviolet absorbing container, wherein the coating agent according to claim 3 is coated on the container. 5. The ultraviolet absorbing resin composition according to claim 1, wherein the pyridazine derivative of the general formula and / or a salt thereof is compounded in an amount of 0.001 to 20% by mass. Composition. 6. The ultraviolet absorbing container according to claim 2, wherein the pyridazine derivative of the general formula and / or a salt thereof is compounded in an amount of 0.001 to 20% by mass. 7. The ultraviolet absorbing coating agent according to claim 3, wherein the pyridazine derivative of the general formula and / or a salt thereof is compounded in an amount of 0.001 to 20% by mass. .