JP2003261543A - Crystal modification of 2,2'-methylenebis[4-(1,1,3,3- tetramethylbutyl)-6-benxotriazolylphenol], method for producing the same, mixture containing the same and ultraviolet absorber produced by using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a type-II crystal modification of 2,2'-methylenebis[4-(1,1,3,3- tetramethylbutyl)-6-benzotriazolylphenol] as a crystal easily handleable in use, and generating little dust, to provide a method for the production of crystal modification, a mixture containing the same and an ultraviolet absorber produced by using the crystal modification. <P>SOLUTION: The crystal modification of 2,2'-methylenebis[4-(1,1,3,3- tetramethylbutyl)-6-benzotriazolylphenol] is an amorphous substance developing no definite diffraction peak and developing a halo by powder X-ray diffraction analysis with Cu-Kα X-ray. The invention further provides a method for producing the crystal modification, a mixture containing the same and an ultraviolet absorber, an emulsion composition and a polymer material produced by using the crystal modification. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

The present invention relates to 2,2'-methylenebis [4- (1,1,3,2) having a novel type II crystal modification.
3-Tetramethylbutyl) -6-benzotriazolylphenol], a process for producing the same, a mixture containing the same, and an ultraviolet absorber using the same.

[0002]

2. Description of the Related Art In recent years, there has been a growing demand for additives such as flame retardants, antioxidants, and ultraviolet absorbers as the use of polymer products such as various plastics, synthetic rubbers, nylon fibers, and resin coatings has become widely used. It has increased. In particular, the use of UV absorbers has become an important issue in order to prevent deterioration phenomena such as cracks and discoloration of polymer products due to UV rays as polymer products are being differentiated and added value is increasing. A stable supply of agents is required. Furthermore, in many cases when handling with powder, scattering of dust,
There are problems such as fluidity and storage stability, and improvement of powder characteristics is required.

2,2'-methylenebis [4- (1,1,
3,3-Tetramethylbutyl) -6-benzotriazolylphenol] is generally known to be effective as an ultraviolet absorber for plastics, paints, oils, fibers and the like. 2,2'-methylenebis [4- (1,1,3,
3-Tetramethylbutyl) -6-benzotriazolylphenol] is disclosed in JP-A-61-1150.
No. 73 discloses 4- (1,1,3,3-tetramethyl).
A method of reacting butyl-6-benzotriazol-2-ylphenol with dialkylamine with formalin and crystallizing a reaction crude product obtained by treating the obtained Mannich base with a base from heptane is disclosed in JP-A-4-29087. Is 4- (1,1,3,3-tetramethyl) butyl-6
A method of reacting benzotriazol-2-ylphenol with a dialkylamine with formalin and crystallizing a reaction crude product obtained by treating the obtained Mannich base with xylene, and JP-A-5-213908. , 4- (1,1,3,3-tetramethyl) butyl-6
-A method is disclosed in which a reaction crude product obtained by reacting benzotriazol-2-ylphenol and formalin with concentrated sulfuric acid is crystallized from methanol. However, there is no description about powder properties such as scattering property, fluidity, stability during storage, etc. of the obtained solid substance, and crystal state of the solid substance. Nothing is described in the examples of the above-mentioned patent publications except that methanol, xylene and heptane are used as a solvent.

It is generally known that when handling a solid substance, problems such as dust scattering, fluidity, and solidification during storage occur, and in order to solve these problems, the crystalline state of the solid substance is to be solved. Various studies have been conducted on the above. For example, JP-A-6-128195 and JP-A-6-72.
Japanese Patent Laid-Open No. 960 discloses that the same compound has different bulk specific gravities, particle size distributions and fluidity for each crystal modification. As described above, it is known that even the same compound has different functions and physical properties depending on the difference in crystal state. Obtaining such knowledge is important for improving the added value and quality of products. In addition, X-ray diffraction analysis and differential scanning calorimetry, which are practical methods for analyzing substances from the viewpoint of crystals, are used in many fields such as distinction of crystalline states and development of functional new materials.

2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6 obtained by a known method
-Benzotriazolylphenol] is in the form of fine powder, and has problems in workability such as powder scattering and partial agglomeration during handling such as drying, packing process, weighing during use, and preparation. It is desired to provide a solid with good fluidity that does not affect workability during body handling.

[0006]

The object of the present invention is to provide 2,2'-methylenebis [4- (1,1,1) as a crystal which is easy to handle such as workability during use and generates little dust.
3,3-Tetramethylbutyl) -6-benzotriazolylphenol] type II crystal modification, a method for producing the same, a mixture containing the same, and an ultraviolet absorber using the same.

[0007]

The first aspect of the present invention is Cu-
In the powder X-ray diffraction analysis by Kα ray, 2,2′-methylenebis [4- (1, which is a compound represented by the following formula (1) characterized by an amorphous form showing no halo and showing a clear diffraction peak 1,3,3-tetramethylbutyl) -6-
Benzotriazolylphenol] crystal modification (this crystal modification may be hereinafter referred to as type II).

[Chemical 2] The second aspect of the present invention is that, in a powder X-ray diffraction analysis using Cu-Kα rays, diffraction angles (2θ ± 0.1 °) of 7.1 ° and 8.6.
°, 14.3 °, 16.1 °, 18.1 °, 23.0 °
2. A crystal modification showing a diffraction peak in (in which the crystal modification is sometimes referred to as type I hereinafter),
2,2'-Methylenebis [4- (1,1) containing 1% by weight or more of methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-benzotriazolylphenol] type II crystal modification , 3,3-Tetramethylbutyl) -6-
Benzotriazolylphenol] mixture. The third aspect of the present invention is 2,2′-methylenebis [4- (1,1,
3,3-Tetramethylbutyl) -6-benzotriazolylphenol] is melted at 195 ° C. or higher and cooled to be solidified, and 2,2′-methylenebis [4- (3) is used. 1,1,3,3-tetramethylbutyl) -6-benzotriazolylphenol]. A fourth aspect of the present invention is to contain 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-benzotriazolylphenol] according to claim 1 or 2. It relates to a characteristic ultraviolet absorber. A fifth aspect of the present invention is 2, 2'of claim 1 or 2.
-Methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-benzotriazolylphenol]. A sixth aspect of the present invention is the method according to claim 1, 2 or 5,
It relates to a polymeric material containing 2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-benzotriazolylphenol].

2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -obtained by a known method
6-benzotriazolylphenol] is a fine powder and has problems in workability and working environment such as dust scattering during handling. The present inventors have conducted repeated research
As a result of various investigations, the substance obtained by melting the crystal and cooling and solidifying was obtained as a solid with less generation of dust, and had the ability as an original ultraviolet absorber, and was especially used as an emulsified composition to form fibers. They found that they have an excellent ability to absorb ultraviolet rays when they are used after being adsorbed, and have solved the problem. In the same compound, physical properties rarely change due to such difference in crystallization conditions, and it does not apply to all compounds. That is, the present invention provides 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-
Benzotriazolylphenol],
Regarding 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-benzotriazolylphenol], there is no knowledge on crystal analysis until now, and the result of the present invention is Not easy to find.

Further, the present inventors conducted powder X-ray diffraction analysis by Cu-Kα ray in order to further clarify the characteristics of the obtained crystal. As a result, those obtained by the known method have diffraction angles (2θ ± 0.1 °) of 7.1 °, 8.6 °,
The crystal obtained in the present invention has a clear crystal while the crystal has a clear diffraction peak at 14.3 °, 16.1 °, 18.1 ° and 23.0 ° (see FIG. 3). It was found to be a type II of a novel crystal modification which is an amorphous form showing no halo and showing a diffraction peak. In addition, the inventors of the present invention II
The type II crystal modification is repeatedly studied, and the type II crystal modification is 2,2′-methylenebis [4- (1,1,3,3-
[Tetramethylbutyl) -6-benzotriazolylphenol] is melted at a temperature of 195 ° C. or higher and solidified by cooling, whereby a solid with less dust can be obtained. Found that you can get as well. Depending on the conditions of the heat treatment, it may contain an I-type crystal modification in addition to the II-type crystal modification.
It is possible to obtain a mixture of type II crystal modification and type II crystal modification. The mixing ratio is a crystal modification mixture containing 1% by weight or more of type II, and similarly, it can be obtained as a solid with less dust generation.

In the powder X-ray diffraction analysis, the mixture of the type I crystal modification and the type II crystal modification obtained in the present invention shows a clear difference from the diffraction pattern of the type I 100% crystal modification depending on the mixing ratio. It may or may not exist, but the differential scanning calorimeter (TA
Instrument 2920 DSC, sample volume 1.3m
g, nitrogen atmosphere in the furnace atmosphere is 50 ml / min, temperature rising rate is 10.0 ° C./min, hereinafter referred to as DSC). The measurement can clarify the mixing of the I-type crystal transformation and the II-type crystal transformation. In DSC measurement, the crystalline modification of 100% of Form I showed an endothermic peak due to melting at around 200 ° C., II
Since the crystal modification of 100% type has an exothermic peak around 130 ° C. (due to the transition from type II to type I) and an endothermic peak around 200 ° C. (due to melting of type I after the transformation),
The mixing ratio of type II and type I by DSC measurement was determined by preparing a calibration curve from the calorific ratio of the type II exothermic peak and the type I endothermic peak using the respective pure crystal modifications.

That is, according to the present invention, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-benzotriazolylphenol] is used without solvent or with a solvent. Not only under normal pressure but also under reduced pressure,
Alternatively, under pressure, it is 195 ° C. or higher, preferably 200 ° C. or higher.
By melting in the range of 250 ° C and then cooling, Cu
-Amorphous type II crystal modification and a mixture of type II and type I, which do not show a clear diffraction peak and show a halo in powder X-ray diffraction analysis by -Kα ray, can be obtained as a solid with little dust generation. . Further, a flaky substance can be easily obtained by using a flaker or the like.

The 2,2'-methylenebis [4- of the present invention
Examples of the solvent contained in the production of (1,1,3,3-tetramethylbutyl) -6-benzotriazolylphenol include water and n-butanol, cyclohexanol,
Alcohols such as ethylene glycol and propylene glycol, ethers such as dioxane, dibutyl ether, ethyl isoamyl ether and ethyl phenyl ether, n-decane, 3-ethylhexane, methylcyclohexane, toluene, ethylbenzene, cumene, o-cymene, p -Cymene, m-cymene, o-xylene, m-xylene, p-xylene, t-butylbenzene, 1-butyl-4-methylbenzene, 1-butyl-2-methylbenzene, 1,2,3-trimethylbenzene , 1, 2, 4-
Hydrocarbons such as trimethylbenzene, 1,3,5-trimethylbenzene, 1,2,4,5-tetramethylbenzene, carboxylic acid esters such as butyl acetate and ethyl propionate, ketones such as methyl ethyl ketone and methyl isobutyl ketone , Carbon tetrachloride, chlorobenzene, organic halides such as o-dichlorobenzene, nitrogen-containing compounds such as dimethylformamide, dimethylacetamide, quinoline, n-butylamine, 2-methylpyrrolidone, and one or a mixture thereof. It can be used in a solvent.

The 2,2'-methylenebis [4- of the present invention
(1,1,3,3-Tetramethylbutyl) -6-benzotriazolylphenol] is mixed with a polymer material in the form of powder, flakes, suspension or emulsion composition by a conventional method as an ultraviolet absorber. The polymer material may be a resin composition, fiber, rubber, paper or the like, and an emulsified composition effective for dyeing is often used especially for the fiber. Examples of the resin composition include phenol resin, melamine resin, epoxy resin, polyurethane, polyimide,
Vinyl chloride, polyvinyl acetal, polyethylene, polypropylene, polybutylene, polymethylpentene, polystyrene, polybutadiene resin, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene-methyl acrylate (ethyl) copolymer, polyester, Acrylonitrile-styrene resin (AS), acrylonitrile-butadiene-styrene resin (ABS), polyethylene terephthalate (PET), polybutylene terephthalate, polycarbonate (PC), PC / AB
S alloys, PC / PET alloys, polyphenylene ether resins, polyphenylene sulfide resins, methacrylic resins, polyamide resins, diallyl phthalate resins, silicone resins, unsaturated polyesters, etc. are listed as automobile-related parts as polymer materials with excellent weather resistance, It can be used in office automation equipment, electronic parts, home appliances parts, machine parts, building parts, medical parts, household sundries, etc.

The 2,2'-methylenebis [4- of the present invention
(1,1,3,3-Tetramethylbutyl) -6-benzotriazolylphenol] can be effectively added to a resin or the like to obtain an effective UV absorbing performance and prevent deterioration of quality. You may use together with a well-known antioxidant and a light stabilizer, and you may mix a hygroscopic agent, an antifungal agent, an antifoaming agent, etc. The emulsified composition of the present invention can be obtained by using an emulsifying and dispersing machine such as a homogenizer, a colloid mill and a bead mill in the presence of an emulsifier, and as the emulsifier, various surfactants are used without particular limitation. Moreover, a hygroscopic agent, an antifungal agent, an antifoaming agent, an antioxidant, a light stabilizer and the like may be mixed as usual additives.

Specific examples of the emulsifier that can be used in the present invention include sodium stearate, sodium lauryl sulfate ester, sodium lauryl ether sulfate ester, sodium dodecylbenzenesulfonate,
Anionic surfactants such as sulfosuccinic acid di-2-ethylhexyl ester sodium salt, alkyl trimethyl ammonium chloride, cationic surfactants such as triethanolamine monostearate formate, amphoteric surfactants such as sodium lauryl aminopropionate,
Nonionic surfactants such as polyethylene glycol lauric acid monoester, polyethylene glycol lauric acid diester, polyoxyethylene stearic acid ester, diethylene glycol monooleyl ether, and glycerin lauric acid monoester can be mentioned, and they can be used alone or as a mixture. can do.

Examples of the hygroscopic agent which can be mixed with the emulsion composition and the polymer material of the present invention include propylene glycol, ethylene glycol, d-sorbit, urea and the like. Examples of the fungicide that can be mixed with the emulsion composition and the polymer material of the present invention include p-hydroxybenzoic acid and chloroacetamide. Examples of the defoaming agent that can be mixed with the emulsion composition and the polymer material of the present invention include silicone type such as silicone resin and organic polar compound type such as 2-ethylhexanol and polypropylene glycol.

Examples of the antioxidant that can be mixed with the emulsion composition and the polymer material of the present invention include 2,6-di-ter.
t-butyl-4-methylphenol, 2-tert-butyl-4,6-di-methylphenol, 2,6-di-t
ert-Butyl-4-ethylphenol, 2,6-di-
tert-butyl-4-n-butylphenol, 2,6
-Di-tert-butyl-4-isobutylphenol,
2,6-di-cyclopentyl-4-methylphenol,
2- (α-methylcyclohexyl) -4,6-di-methylphenol, 2,6-di-octadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-nonyl-4 -Methylphenol, 2,
6-di-tert-butyl-4-methoxymethylphenol, 2,4-di-methyl-6- (1'-methyl-undec-1'-yl) -phenol, 2,4-di-methyl-6- (1'-Methyl-trideca-1'-yl) -phenol and mixtures thereof; 2,4-di-octylthiomethyl-6-tert-butylphenol, 2,4-
Di-octylthiomethyl-6-methylphenol, 2,
4-di-octylthiomethyl-6-ethylphenol,
2,6-di-dodecylthiomethyl-4-nonylphenol and mixtures thereof; 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-
Butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-di-phenyl-4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4 −
Hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-
Butyl-4-hydroxyphenyl stearate, bis (3,5-di-tert-butyl-4-hydroxyphenyl) adipate and mixtures thereof; 2,4-bis-octylmercapto-6- (3,5-di- tert-
Butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis (3,3)
5-di-tert-butyl-4-hydroxyanilino)
-1,3,5-triazine, 2-octyl mercapto-
4,6-bis (3,5-di-tert-butyl-4-hydroxyphenoxy) -1,3,5-triazine, 2,
4,6-Tris (3,5-di-tert-butyl-4-
Hydroxyphenoxy) -1,2,3-triazine,
1,3,5-tris (3,5-di-tert-butyl-
4-hydroxybenzyl) -isocyanurate, 1,
3,5-Tris (4-tert-butyl-3-hydroxy-2,6-di-methylbenzyl) -isocyanurate, 2,4,6-Tris (3,5-di-tert-butyl-4-hydroxy) Phenylethyl) -1,3,5-triazine, 1,3,5-tris (3,5-di-tert)
-Butyl-4-hydroxyphenylpropionyl) -hexahydro-1,3,5-triazine, 1,3,5-tris (3,5-di-cyclohexyl-4-hydroxybenzyl) -isocyanurate, and 2,2 ' -Methylenebis (6-tert-butyl-4-methylphenol), 2,2'-methylenebis (6-tert-butyl-4-ethylphenol), 2,2'-ethylidenebis (4,6-di-tert-) Butylphenol), 2,
2'-ethylidene bis (6-tert-butyl-4-isobutylphenol), 4,4'-methylenebis (2,2
6-di-tert-butylphenol), 4,4'-methylenebis (6-tert-butyl-2-methylphenol), 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane , Ethylene glycol bis [3,3'-bis (3'-tert-butyl-4'-hydroxyphenyl) butyrate], and 1,3,5-tris (3,5-di-tert-butyl-4-). Hydroxybenzyl) -2,4,6-trimethylbenzene, 1,4-bis (3,5-di-tert-butyl-4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene, 2,4 , 6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -phenol and the like can be mentioned.

Examples of the light stabilizer that can be mixed with the emulsion composition and the polymer material of the present invention include 2- (2'-hydroxy-5'-methylphenyl) benzotriazole and 2- (2'-hydroxy-5'-methylphenyl) benzotriazole.
(3 ′, 5′-di-tert-butyl-2-hydroxyphenyl) benzotriazole, 2- (5′-tert)
-Butyl-2'-hydroxyphenyl) benzotriazole, 2- [2'-hydroxy-5 '-(1,1,3,
3-Tetramethylbutyl) phenyl] benzotriazole, 2- (3 ', 5'-di-tert-butyl-2'-
Hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-4'-oct Xyphenyl) benzotriazole, 2- (3 ', 5'-di-t
benzo such as ert-amyl-2′-hydroxyphenyl) benzotriazole and 2- [3′-tert-butyl-2′-hydroxy-5 ′-(n-octyloxycarbonylethyl) phenyl] -5-chlorobenzotriazole. Triazoles; 4-hydroxy-, 4-methoxy-, 4-octoxy-, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy-, 4,2 ',
4'-trihydroxy-, 2'-hydroxy-4,4 '
-Benzophenones such as di-methoxy- or 4- (2-ethylhexyloxy) -2-hydroxybenzophenone; 4-tert-butylphenyl salicylate,
Salicylates such as phenyl salicylate and octylphenyl salicylate; Resorcinols such as dibenzoylresorcinol, bis (4-tert-butylbenzoylresorcinol) and 2,4-di-tert-butylphenylresorcinol; 3,5-di-ter
Benzoates such as t-butyl-4-hydroxybenzoate and hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate; ethyl α-cyano-β, β-diphenyl acrylate, isooctyl α
Acrylates such as -cyano-β, β-diphenylacrylate; cinnamates such as methyl α-carbomethoxycinnamate and methyl α-cyano-β-methyl-p-methoxycinnamate; bis (2,2,6,6)
6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, Acid esters such as bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis (1,2,2,6,6-pentamethyl-4-piperidyl) adipate; 4 , 4'-di-octyloxy oxanilide, 2,
2'-di-ethoxyoxy oxanilide, 2,2'-di-octyloxy-5,5'-di-tert-butyl oxanilide, 2,2'-di-dodecyloxy-5,5 '
-Di-tert-butyl oxanilide, 2-ethoxy-
2'-ethyl oxanilide, N, N'-bis (3-di-
Methylaminopropyl) oxanilide, 2-ethoxy-
Oxalinides such as 5-tert-butyl-2'-ethoxyoxanilide; 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2- (2- Hydroxy-4-octyloxyphenyl) -4,6-bis (2,4-di-methylphenyl) -1,3,5-triazine, 2- (2,4-di-hydroxyphenyl) -4,6- Bis (2,4-di-methylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6
-(2,4-di-methylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4,6-bis (2,4-di-methylphenyl)- Examples thereof include triazines such as 1,3,5-triazine.

[0019]

EXAMPLES The present invention will be described below with reference to examples.
The present invention is not limited to these.

The mixing ratio of the type II and the type I was determined by DSC measurement using the respective pure crystal modifications and preparing a calibration curve from the calorific ratio of the type II exothermic peak and the type I endothermic peak. The DSC measurement was performed using a TA Instruments 2920 type DSC with a sample amount of 1.3 mg, a furnace atmosphere of a nitrogen stream of 50 ml / min, and a temperature rising rate of 10.0 ° C./mi.
It was performed under the condition of n. The powder X-ray diffraction analysis by Cu-Kα ray was performed using TFD-18kw manufactured by Mac Science,
Anticathode Cu-Kα (1.5405Å), 40kV-50
mA, scanning speed 2.000 ° / min. It went on condition of. Further, if the diffraction angle (2θ) by powder X-ray diffraction analysis is that of the same crystal type, they coincide with each other with an error of about ± 0.1 °, which clearly shows the difference in crystal transformation. , The relative intensity of the diffraction line depends on the particle size of the measurement sample,
The intensity ratio may change. As a method for evaluating the ultraviolet absorbent, a sample obtained by treating a dyed polyester cloth with the ultraviolet absorbent (emulsion composition) was prepared, an exposure test was conducted, and the sample was evaluated after the discoloration and fading of the sample after 300 hours. For the exposure test, Table Sun TS-1 manufactured by Suga Test Instruments Co., Ltd. was used.

Synthesis Example 1 4- (1,1,3,3-tetramethylbutyl) -6-benzotriazolylphenol 63.4k in a stirred vessel.
g, paraformaldehyde 5.2 kg, diethylamine 11.0 kg, and xylene 60 L were added, and the mixture was heated at 95 ° C to 100 ° C.
The reaction was carried out at ℃ for 24 hours, then 3.1 kg of 28% sodium methylate methanol solution was added, and the reaction was carried out at 145 to 150 ℃ for 10 hours while bubbling nitrogen gas. By washing the reaction solution with water and cooling the xylene layer to 10 ° C,
It was crystallized. The obtained crystals were filtered to obtain a white fine powdery solid (dust is generated) of 2,2'-methylenebis [4-
(1,1,3,3-Tetramethylbutyl) -6-benzotriazolylphenol] 56.8 kg (88% yield)
Got The powder X-ray diffraction analysis by Cu-Kα ray of the obtained crystal showed the diffraction angle (2θ ± 0.1 °) as shown in FIG.
7.1 °, 8.6 °, 14.3 °, 16.1 °, 18.
As shown in FIG. 4, it was confirmed that the I type had a diffraction peak at 1 ° and 23.0 °, and the result of DSC measurement was I type 1
It was 100%.

Example 1 2,2'-methylenebis [4- obtained in Synthesis Example 1
(1,1,3,3-Tetramethylbutyl) -6-benzotriazolylphenol] is melted at 220 ° C. to 240 ° C. and cooled to 10 ° C. by a flaker to form flaky crystals (dust is generated. Not) got. As a result of powder X-ray diffraction analysis of the obtained flakes by crushing the crystals with Cu-Kα ray, as shown in FIG. 1, no clear diffraction peak was shown and it was amorphous type II showing a halo. According to the result of the powder X-ray diffraction analysis, that of Example 1 was II type 100.
%belongs to. In addition, the II type 100% obtained in Example 1
As shown in FIG. 2, the DSC measurement result of the crystal modification of
It exhibited one exothermic peak at 0.2 ° C and one endothermic peak at 198.2 ° C.

Example 2 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-obtained in the same manner as in Synthesis Example 1
Benzotriazolylphenol] at 205 ° C to 210 ° C
It was melted in, and was cooled to 10 ° C. with a flaker to obtain flaky crystals (no dust was generated). The result of the powder X-ray diffraction analysis by the Cu-Kα line of the crystal obtained by crushing the obtained flakes shows the diffraction angle (2θ ± 0.
1 °) 7.1 °, 8.6 °, 14.3 °, 16.1 °,
Although the I type having a diffraction peak at 18.1 ° and 23.0 ° was shown, as shown in FIG. 6, the DSC measurement results showed that the heat quantity ratio between the endothermic peak of type I and the exothermic peak of type II was 75 .7
(Type I): 24.3 (type II)], the mixing ratio of the type I crystal modification and the type II crystal modification of the obtained flakes is
The type I was 51.0% by weight and the type II was 49.0% by weight.

Example 3 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-obtained in the same manner as in Synthesis Example 1
Benzotriazolylphenol] at 210 ° C to 215 ° C
It was melted in, and was cooled to 10 ° C. with a flaker to obtain flaky crystals (no dust was generated). The results of the powder X-ray diffraction analysis by Cu-Kα ray of the crystals obtained by crushing the obtained flakes show the diffraction angles (2θ ± 0.
1 °) 7.1 °, 8.6 °, 14.3 °, 16.1 °,
Although the I type having a diffraction peak at 18.1 ° and 23.0 ° was shown, the DSC measurement result of the obtained flakes [the calorific ratio of the endothermic peak of type I and the exothermic peak of type II was 64.9.
(I type): 35.1 (II type)], the mixing ratio of the I type crystal modification and the II type crystal modification of the obtained flakes is
Type I was 16.9% by weight and type II was 83.1% by weight.

Example 4 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-obtained in the same manner as in Synthesis Example 1
Benzotriazolylphenol] at 195 ° C to 200 ° C
It was melted in, and was cooled to 10 ° C. with a flaker to obtain flaky crystals (no dust was generated). The result of the powder X-ray diffraction analysis by the Cu-Kα ray of the crystal obtained by crushing the obtained flakes shows that the diffraction angle (2θ ± 0.1 °) was 7.1 °,
8.6 °, 14.3 °, 16.1 °, 18.1 °, 2
Form I showed a diffraction peak at 3.0 °, but DSC
Measurement result [The heat quantity ratio between the endothermic peak of type I and the exothermic peak of type II was 93.9 (type I): 6.1 (type II)]
As a result, the mixing ratio of the type I crystal modification and the type II crystal modification of the obtained flakes was 90.0% by weight for type I and 10.0 for type II.
% By weight.

Preparation Example 1 (emulsion composition) 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-obtained in Example 1 was added to 51.6 parts by weight of water. Benzotriazolylphenol] 25.0 parts by weight, sodium dodecylbenzenesulfonate 7.5 parts by weight, glycerin lauric acid monoester 2.0 parts by weight, sodium laurylaminopropionate 1.0 part by weight, propylene glycol 12.7 By weight, 0.2 part by weight of chloroacetamide was added with stirring, and an emulsified composition A was obtained using a bead mill. Similarly, 2,2′-methylenebis [4- (1,1,3,3) obtained in Example 1 was used.
-Tetramethylbutyl) -6-benzotriazolylphenol], but 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) obtained in Example 2 was used.
-6-benzotriazolylphenol] was used to emulsify composition B, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-obtained in Synthesis Example 1.
Benzotriazolylphenol] and emulsified composition C and 2,2'-methylenebis [4- (1,1,3,3)
3-Tetramethylbutyl) -6-benzotriazolylphenol] was not added to obtain Emulsion Composition D.

Adjustment Example 2 (Sample for Evaluation) Kayalon Polyester Yellow
BRL-S200 (trade name of Nippon Kayaku Co., Ltd.), Kay
alon Polyester Navy Blue
EX-SF200 (trade name of Nippon Kayaku Co., Ltd.), Kay
alon Polyester Light Scar
A polyester cloth dyed with let G-S200 (trade name of Nippon Kayaku Co., Ltd.) was dipped in the emulsified composition A obtained in Preparation Example 1, washed with water and dried to prepare a sample A for evaluation. Similarly, an evaluation sample B using the emulsified composition B instead of the emulsified composition A, an evaluation sample C using the emulsified composition C, and an evaluation sample D using the emulsified composition D were prepared.

Example 5 An exposure test [Table Sun TS-1 manufactured by Suga Test Instruments Co., Ltd.] was conducted on the evaluation sample prepared in Preparation Example 2, and the degree of discoloration after 300 hours of ultraviolet irradiation was visually irradiated. Compared with the previous hues, the order of good fastness is almost four (4): almost unchanged (evaluation 4), extremely fading (evaluation 3), slightly fading (evaluation 2), and obviously fading (evaluation 1). did. The results are shown in Table 1.

[0029]

[Table 1]

Example 6 (Light Stabilizing Effect on Polymer Material) Example 1 (II type 100) was added to 100 parts by weight of polyethylene powder.
%) Compounded in an amount of 2.0 parts by weight and thoroughly mixed in a mixer.
Pellets were prepared by melt mixing with an m-diameter extruder. The obtained pellets were compression molded at 180 ° C. to prepare a sheet having a thickness of 0.25 mm. The obtained sheet is
It was punched out into a dumbbell shape corresponding to the tensile test. Further, by the same method as described above, the compound produced in Synthesis Example 1 (type I 100%) and a test piece for comparison without addition of a light stabilizer were prepared, and the light stabilizing effect was evaluated. When X-ray diffraction analysis was performed on these test pieces,
The X-ray diffraction analysis of the sheet prepared by blending the compound prepared in Example 1 (type II 100%) as the light stabilizer is as shown in FIG. 8, and the diffraction peak of the light stabilizer does not appear. The same diffractogram as the X-ray diffraction analysis of the sheet without addition was shown.
On the other hand, the X-ray diffraction analysis of the sheet prepared by blending the compound prepared in Synthesis Example 1 (I type 100%) as the light stabilizer is as shown in FIG. Diffraction angle (2θ ± 0.1 °) that is characteristic of the produced compound
Diffraction peaks were shown at 7.1 °, 8.6 °, and 14.3 °. To evaluate the light-stabilizing effect, these test pieces were irradiated with light at a black panel temperature of 80 ° C. using a xenon sunshine long life weather ometer, and a tensile tester was used for each test piece to measure the decrease in the tensile test. The changes were compared. The tensile test is performed at a temperature of 23 ± 2 ° C., a relative humidity of 50 ± 5%, and a test speed of 50 ± 5.0 mm / min.
I went there. The tensile strength was determined by the following method.

[Formula 1] Ts = S / T · W Ts = tensile strength (kgf / mm ² ) T = thickness of sample (mm) W = width of sample (mm) S = maximum strength of sample (kgf) Was as shown in Table 2.

[Table 2] As is clear from the results shown in Table 2, the present invention is 2,
2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-benzotriazolylphenol] II
The type crystal modification exhibits a stabilizing effect (that is, extension of deterioration time) superior to that of the type I crystal modification.

[0031]

EFFECTS OF THE INVENTION The type II crystal modification and the crystalline modification mixture containing the type II crystal modification in an amount of 1% by weight or more, which are obtained by the present invention, are UV absorbers which are less likely to cause dust scattering and are advantageous in the working environment. .

[Brief description of drawings]

1 is an X-ray diffraction pattern of type II, which is the novel crystal modification of the present invention obtained in Example 1. FIG.

2 is a novel crystal modification of the present invention obtained in Example 1. FIG.
It is a II type DSC chart.

FIG. 3 is an X-ray diffraction pattern of Form I, which is the crystal modification obtained in Synthesis Example 1.

FIG. 4 is an I-type DSC chart which is a crystal modification obtained in Synthesis Example 1.

5 is an X-ray diffraction pattern of the mixture of type I and type II of the present invention obtained in Example 2. FIG.

6 is a DSC chart of the mixture of type I and type II obtained in Example 2. FIG.

7 is an X-ray diffraction pattern of the mixture of type I and type II of the present invention obtained in Example 3. FIG.

FIG. 8 is an X-ray diffraction pattern of a sheet prepared by blending the compound produced in Example 1 (type II 100%) as a light stabilizer.

FIG. 9 is an X-ray diffraction pattern of a sheet prepared by compounding the compound produced in Synthesis Example 1 (type I 100%) as a light stabilizer.

Continued front page    (72) Inventor Yuichi Kaneko             1-3-3 Higashikawasaki-cho, Chuo-ku, Kobe-shi, Hyogo             No. Kemipro Kasei Co., Ltd. (72) Inventor Masayuki Nishimatsu             1-3-3 Higashikawasaki-cho, Chuo-ku, Kobe-shi, Hyogo             No. Kemipro Kasei Co., Ltd. F-term (reference) 4J002 BB031 BB121 BB171 BC031                       BD041 BE031 BE061 BN141                       CC031 CC181 CF061 CF071                       CG001 CK021 CL001 CM041                       EU176 FD056

Claims (6)

[Claims] 1. A compound represented by the following formula (1) characterized by an amorphous form showing no halo in powder X-ray diffraction analysis by Cu-Kα ray and showing a halo, 2,2′- Methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-benzotriazolylphenol] crystal modification (this crystal modification may be referred to as type II hereinafter). [Chemical 1] 2. A diffraction angle (2θ ± 0.1 °) of 7.1 ° and 8.6 in a powder X-ray diffraction analysis by Cu-Kα ray.
°, 14.3 °, 16.1 °, 18.1 °, 23.0 °
2. A crystal modification showing a diffraction peak in (in which the crystal modification is sometimes referred to as type I hereinafter),
2,2'-Methylenebis [4- (1,1) containing 1% by weight or more of methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-benzotriazolylphenol] type II crystal modification , 3,3-Tetramethylbutyl) -6-
Benzotriazolylphenol] mixture. 3. 2,2′-methylenebis [4- (1,
1,3,3-Tetramethylbutyl) -6-benzotriazolylphenol] is melted at 195 ° C. or higher and then solidified by cooling, 2,2 ′.
A method for producing methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-benzotriazolylphenol]. 4. A composition containing 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-benzotriazolylphenol] according to claim 1 or 2. UV absorber to do. 5. A composition comprising 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-benzotriazolylphenol] according to claim 1 or 2. Emulsified composition. 6. The 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-benzotriazolylphenol] according to claim 1, 2 or 5 is obtained. A polymeric material characterized by containing.