JPH02180909A - Benzophenone compound and its homopolymer or copolymer - Google Patents

Abstract

NEW MATERIAL:A benzophenone compound of formula I [wherein R is H or methyl; A is a group of the formula: R<1>-XR<2>, R<1>-X, X-R<2> or X (wherein X is a urethane or ester bond; and R<1> and R<2> are each a 1-10C linear or branched alkyl residue); Y and Z are each H, OH, a 1-10C linear or branched alkyl residue or a group of formula II; R<3> is H or a 1-10C linear or branched alkyl residue; and n is 1-3]. EXAMPLE:2-Hydroxy-4-vinyloxycarbonylmethoxybenzophenone USE:Use as an ultrabiolet-absorbing compound copolymerizable with a double bond-containing monomer; or use of a copolymer composition containing a relatively large amount of said compound units as a high-MW ultraviolet absorber of excellent long-term stability PREPARATION:The purpose compound is obtained, for example, by esterifying a benzophenone having at least two hydroxyl groups on at least either of the benzene rings with (meth)acrylic acid or its derivative.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application J] The present invention relates to benzophenone compounds and homopolymers or copolymers thereof. More specifically, a benzophenone compound having a double bond in the molecule that can act as a monomer for homopolymerization or copolymerization, a homopolymer of the benzophenone compound, or a combination of the benzophenone compound and a vinyl thread yarn. The present invention relates to a polymer composition comprising a copolymer. The most effective application of these compounds is the UV protection of polymeric and other organic materials.

[Prior Art] Polymeric materials used outdoors are exposed to sunlight on a daily basis, and exposed to fluorescent lamp light indoors. These sunlight and fluorescent lamp lights contain ultraviolet rays with a wavelength of 290 to 40 Dnm that are harmful to polymer materials, etc., and these ultraviolet rays excite functional groups in polymer chains and remaining polymerization catalysts, resulting in light A decomposition reaction occurs and degrades the polymer material.

Furthermore, there is also the problem of UV deterioration of the contents stored in containers and packaging bags made of polymeric materials.

In order to protect polymeric materials from such harmful light, ultraviolet absorbers are usually added to polymeric materials.

UV absorbers absorb all or most of the light in the harmful region and convert the energy into harmless energy, such as non-radiative transitions, and emit it, protecting the polymer from photodegradation reactions.

By the way, as conventional ultraviolet absorbers, benzophenone and benzotriazole compounds, which are highly effective in suppressing and delaying photodecomposition of polymeric materials, have been widely used. However, since these are low-molecular compounds, they have poor compatibility with polymeric materials, and over time they bleed out from the polymeric material and scatter or elute into various media. Photodeterioration is gradually accelerated. Furthermore, since molding of polymeric materials is carried out at high temperatures, the UV absorber mixed in often evaporates or decomposes, leaving almost no UV absorber in the final product. Furthermore, dissolution into various media also creates hygiene problems when polymeric materials are used in food banks.

In order to overcome these drawbacks, it has been attempted to increase the molecular weight of UV absorbers. For example, 2-hydroxy-4-long-chain alkoxybenzophenone has improved compatibility with polymeric materials, resulting Improved scattering and dissolution properties. As examples of these, 2-hydroxy-4-octoxybenzophenone and 2-hydroxy-4-dodecyloxybenzophenone are mentioned above. Furthermore, benzotriazole ultraviolet absorbers have also been made to have higher molecular weights, and alkyl and aralkyl substituted products of 2-(2'-hydroxyphenyl)benzotriazole are well known.

[Problem to be solved by the invention, Ill These high-molecular-weight ultraviolet absorbers certainly have improved bleed-out resistance after molding when compared with conventional low-molecular-weight ones. However, there still remain problems such as poor heat resistance and the volatilization or decomposition of the ultraviolet absorber during high-temperature molding of polymeric materials. Particularly in the case of polymeric materials such as ABS resins that are molded at considerably high temperatures, it is difficult to say that even the above-mentioned polymeric ultraviolet absorbers remain sufficiently to exert the desired effect after molding. for example,
The boiling point of 2-hydroxy-4-octoxybenzophenone is 235°C. Therefore, when adding an ultraviolet absorber, the current situation is that an extra amount is added in consideration of volatilization and decomposition during processing.

Furthermore, at present, it is common for ultraviolet absorbers to be added to polymeric materials in weight percent. Therefore, the higher the molecular weight of the polymer-type UV absorbers mentioned above, the smaller the proportion of the UV-absorbing skeleton per molecule. A larger amount is required than low molecular weight UV absorbers,
The cost will be high.

Introducing a UV-absorbing skeleton directly into the polymer chain is a possible way to improve the drawbacks of currently used UV absorbers, including low-molecular UV absorbers and polymer-type UV absorbers, as described above. . That is, by introducing a reactive group into the ultraviolet absorber and incorporating it into the polymer chain, the attempt is made to prevent the ultraviolet absorber from scattering, elution, thermal decomposition, or volatilization.

This research has been carried out for a long time, and several proposals have been made (for example, in the case of benzophenone, Japanese Patent Laid-Open No. 58-1
32039, JP-A-56-92914, etc., and for benzotriazole series, JP-A-60-38411, etc.). However, there are many cases where the performance is poorer than that of the conventional type, and the current situation is that there are almost no complaints.

Furthermore, the present invention provides a homopolymer of the above novel ultraviolet absorbing compound or a copolymer composition containing a relatively large amount of novel ultraviolet absorbing compound units as a high molecular weight ultraviolet absorber having excellent stability over time. The purpose is to

The novel compound of the present invention is a reactive benzophenone compound represented by formula (1).

[Means for Solving the Problems] As a result of intensive research into the above-mentioned reactive ultraviolet absorbers, the present inventors succeeded in developing a benzophenone compound with excellent performance and a polymer thereof.

That is, the present invention provides a novel ultraviolet absorbing compound that can be copolymerized with monomers having various double bonds.
It is an object of the present invention to provide a copolymer composition having improved ultraviolet absorption properties derived from the novel ultraviolet absorbing compound.

However, in formula (1), R represents hydrogen or a methyl group, and A is either R-X-R2, R1-X, X-R2 or The groups R1 and R2 represented by bonds each represent a C1 to CIO linear or branched alkyl residue.

Further, Y and Z are hydrogen, a hydroxyl group, a straight chain or branched chain alkyl residue of CI""CIO, or a group consisting of a group represented by O-'A-^-CH2 in formula (f). selected atoms or groups, R
3 represents hydrogen or a linear or split chain alkyl residue of 01 to CIO, and n represents an integer of 1 to 3 (however, in the case of 2 to 3, R3 may be different from each other).

Examples of compounds represented by general formula (1) are shown below. For example, 2-hydroxy-4-vinyloxycarbonylmethoxybenzophenone, 2-hydroxy-4-[β-(
Vinyloxycarbonylmethoxy)ethoxy]benzophenone, 2,2' dihydroxy-4-vinyloxycarbonylmethoxybenzophenone, 2,4,4'-1-lyhydroxybenzophenone monochlorovinyl acetate 1 ether, 2-hydroxy-4'-methoxy~3' 5
'-Bismethyl-4-vinyloxycarbonylmethoxybenzophenone, 2,2',4-trihydroxy-4-
Vinyloxycarbonylmethoxybenzophenone, 2-
Hydroxy-4,4'-divinyloxycarbonylmethoxybenzophenone, 2,2'-dihydroxy-4,4
'-Di(vinyloxycarbonylmethoxy)benzophenone, 2-hydroxy-2', 4,4'-tri(vinyloxycarbonylmethoxy)benzophenone, 2-hydroxy-4-acryloxybenzophenone, 2-hydroxy-4-methacryloxy Benzophenone, 2-hydroxy-4-(β-acryloxyethoxy)benzophenone, 2-hydroxy-4-(β-methacryloxyethoxy)benzophenone, 2,2'-dihydroxy-4-acryloxybenzophenone, 2,2'-dihydroxy −
4-methacryloxybenzophenone, 2-hydroxy-
4'-methoxy-3', 5'-bismethyl-4-acryloxybenzophenone, 2-hydroxy-4'-methoxy-3', 5'-bismethyl-4-methacryloxybenzophenone, 2,4゜4'-tri Hydroxybenzophenone-acrylic acid monoester, 2. 4. 4'-
) Lihydroxybenzophenone-methacrylic acid 1 ester, 2.2', 4-) Lihydroxy-4'-acryloxybenzophenone, 2.2', 4-trihydroxy-4'-methacryloxybenzophenone, 2-hydroxy-4 Vinylacetoxybenzophenone, 2-hydroxy-4-allylacetoxybenzophenone, 2-hydroxy-4-(β-vinylacetoxy)ethoxybenzophenone, 2-hydroxy-4-(β-allylacetoxy)ethoxybenzophenone, 2.2' -dihydroxy-
4-vinylacetoxybenzophenone, 2.2'-dihydroxy-4-allylacetoxybenzophenone, 2.
4-dihydroxy-4'-methoxy-3',5'-bismethyl-4-vinylacetoxybenzophenone, 2,4
-dihydroxy-4'-methoxy-3',5'-bismethyl-4-allylacetoxybenzophenone, 2,4.
4'-) Lihydroxybenzophenone-vinyl acetic acid monoester and diester, 2.4.4'-) Lyhydroxybenzophenone-allylacetic acid monoester and diester, 2.2',4-trihydroxy- 4
'-vinylacetoxybenzophenone, 2.2' 4
-1-lyhydroxy-4'-allylacetoxybenzophenone, 2-hydroxy-4゜4'-diacryloxybenzophenone, 2-hydroxy-4,4'-dimethacrylokydibenzophenone, 2-hydroxy-4,4 '-divinylacetoxybenzophenone, 2-hydroxy-4,
4'-Diallylacetoxybenzophenone, 2.2'-
Dihydroxy-4,4'-bisacryloxybenzophenone, 2,2'-dihydroxy-4,4'-bismethacryloxybenzophenone, 2,2'-dihydroxy-4
, 4'-vinylacetoxybenzophenone, 2.2'-
Dihydroxy-4,4'-triacetoxybenzophenone, 2-hydroxy-2', 4.4'-triacryloxybenzophenone, 2-hydroxy-2', 4.4'
-trimethacryloxybenzophenone, 2-hydroxy-2'4.4'-)divinylacetoxybenzophenone, 2-hydroxy-3'4.4'-triallylacetoxybenzophenone, 2.2'.

4-trihydroxybenzophenone-acrylic acid diester, 2.2',4'-trihydroxybenzophenone-methacrylic acid diester, 2.2',4'
-) Lihydroxybenzophenone-vinyl acetate 2 ester (11,2,2',4' trihydroxybenzophenone-allylacetic acid 2 ester, 2-hydroxy-4-
(β-(methacryloxyethylcarbamoyloxy)ethoxy)benzophenone, 2-hydroxy-4-[β-
(methacryloylcarbamoyloxy)ethoxybenzophenone, 2-hydroxy-4-methacryoxyethylcarbamoyloxybenzophenone, 2-hydroxy-
4-methacryloylcarbamoyloxybenzophenone, 2.2'-dihydroxy-4-methacryloylcarbamoyloxybenzophenone, 2.2'-dihydroxy-4-methacryloylcarbamoyloxybenzophenone, 2-hydroxy-4'-methoxy-3'5'
-Bismethyl-4-methacryloylcarbamoyloxybenzophenone, 2-hydroxy-4'-methoxy-3'5'-bismethyl 4-methacryloylcarbamoyloxybenzophenone, 2.4.4'-1-dihydroxybenzophenone-methacryloxethyl isocyanate Nato 1-urethane compound and di-urethane compound, 2.4.
4' trihydroxybenzophenone-methacryloyl isocyanate monourethane and diurethane, 2.
2',4-)rihydroxy-4'-methacryloxyethylcarbamoyloxybenzophenone, 2.2' 4
1-dihydroxy-4,4'-methacryloylcarbamoyloxybenzophenone, 2-dihydroxy-4,4'-dimethacrylokydiethylcarbamoyloxybenzophenone, 2-hydroxy-4,4'-dimethacryloylcarbamoyloxybenzophenone, 2,2'- Dihydroxy-4,4'-bismethacryloxyethylcarbamoyloxybenzophenone, 2,2'-dihydroxy-4,4
'-Bismethacryloylcarbamoyloxybenzophenone, 2-hydroxy-2',4.4'-1-rimethacryloylcarbamoyloxybenzophenone, 2
-Hydroxy-2,4,4'-1-rimethacryloylcarbamoyloxybenzophenone and the like.

These new benzophenones are benzophenones that have at least two hydroxyl groups on one or both of the benzene rings, or those that have a hydroxyl group at the 2-position of the benzene ring and other substitution positions are substituted with alkyl residues that have a hydroxyl group at the end. Numerical esterification or etherification reaction between benzophenones and acrylic acid, acrylic acid derivatives, methacrylic acid, methacrylic acid derivatives, vinyl acetic acid, vinyl acetic acid derivatives, allyl acetic acid, allyl acetic acid derivatives, etc. By a general etherification reaction with a halogen-substituted carboxylic acid vinyl ester or a general urethane reaction with an isocyanate having a double bond,
Easily synthesized.

Since the above-mentioned 2-hydroxybenzophenone monomer has a polymerizable unsaturated group, it can be used in the presence of a polymerization initiator, for example an azo initiator such as azobisisobutyronitrile, or a peroxide such as benzoyl peroxide. In addition, it can be homopolymerized or copolymerized with a hexamer having other polymerizable unsaturated groups.

In the copolymerization, the type of hexamer to be copolymerized is not particularly limited, and monomers having polymerizable unsaturated groups, such as acrylic esters, methacrylic esters, styrene, methylstyrene, acrylonitrile, methacrylonitrile,
Acrylamide, vinyl acetate, vinyl chloride, vinylidene chloride and other vinyl monomers are used for larel.

One or more types of these monomers may be used. Also, 2-
Among the hydroxybenzophenone monomers, one or more types of 2-hydroxybenzophenone monomers can also be used.

A homopolymer of this 2-hydroxybenzophenone monomer or a copolymer having a relatively large number of 2-hydroxybenzophenone monomer units can be used as an additive type ultraviolet absorber. These polymers show equivalent or higher ultraviolet absorbing ability at the same concentration than 2-hydroxy-4-octoxybenzophenone, a conventional polymeric ultraviolet absorber. Since it has a higher decomposition temperature than octoxybenzophenone, it is highly likely that when high-temperature molding of polymeric materials is performed, the residual concentration in the molded product will be higher than in conventional products.

On the other hand, the copolymers of the present invention in which the 2-hydroxybenzophenone monomer is present in a relatively low proportion are useful as ultraviolet absorbing polymers. In this case, the 2-hydroxybenzophenone monomer is interpreted as a reactive ultraviolet absorber, and its proportion in the polymer is 0.01% or more, preferably 1% or more by weight. Although there is no upper limit, it is used to the extent that the physical properties and mechanical strength required in the situation in which the copolymer is used can be obtained.

When the 2-hydroxybenzophenone monomer is used as a copolymer component of a polymer as described above, the stability of the polymeric material against ultraviolet rays is improved, and a polymeric material having excellent weather resistance over a long period of time can be obtained.

In addition, homopolymers of 2-hydroxybenzophenone monomers or copolymers containing a relatively large amount (approximately 20 to 80% by weight) of 2-hydroxybenzophenone monomers are useful as additive-type polymeric ultraviolet absorbers with heat resistance. It is.

[Example] Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these descriptions. In addition, the molar absorption coefficient in the examples is determined from the transmittance measured by dissolving each monomer in methanol and using an ultraviolet spectrophotometer (Model UV-320Q: manufactured by Hitachi), based on the Lambert-Beer law, that is, the following formula: Calculated using

Here, ε: molar extinction coefficient C: molar concentration of sample solution l: cell length (cm) T: transmittance Example 1 Synthesis of 2-hydroxy-4-vinyloxycarbonylmethoxybenzophenone This yellow particle has the formula A compound represented by (II), 325
It has maximum ultraviolet absorption at 285 nm and 285 nm.
The molar extinction coefficient at that wavelength is 8476.1 respectively.
It was 5203.

Examples 2 to 6 In the same manner as in Example 1, the compounds shown in Table 1 were obtained.

2.4-dihydroxybenzophenone 32.0g (0,
15 mol), monochlorovinyl acetate 32.0 g (0,3
0 mol), sodium hydrogen carbonate 26.0 g (0.30 mol), acetonitrile 38.0 g (0.70 mol),
0.1 g (0.8×10 −3 mol) of methoquinone was placed in a 30-meter flask equipped with a stirrer and a Dimroth, and the reaction was carried out at 80° C. for 5 hours with stirring. After the reaction is complete,
The contents were filtered, the filtrate was evaporated to remove the solvent, and the residue was recrystallized from methanol to obtain one yellow particle.

Example 7 Synthesis of 2-hydroxy-4,4'-divinyloxycarbonylmethoxybenzophenone Stirring device, Dimroth,
In a 3-meter flask equipped with a temperature needle, add 2,4.4'-1-
34.5 g (0.15 mol) of dihydroxybenzophenone, 64.0 g (0.60 mol) of monochlorovinyl acetate, 52.0 g (0.60 mol) of thorium hydrogen carbonate, 41.0 g (0.60 mol) of acetonitrile. Og (1,0 mol), methoquinone 0.2 g
(1°6 x 10-3 mol) and reacted for 10 hours with stirring.

After the reaction was completed, the contents were filtered, the filtrate was concentrated, and the residue was recrystallized from methanol to obtain yellow particles of the target product. This yellow particle is a compound represented by formula (III),
It has maximum ultraviolet absorption at 333 nm and 298 nm, and the molar absorption coefficient at those wavelengths is 929, respectively.
It was 1.9810.

Example 8 Synthesis stirring device for 2.2'-dihydroxy-4,4'-di(vinyloxycarbonylmethoxy)benzophenone and 2-hydroxy-2'4.4'-)li(vinyloxycarbonylmethoxy)benzophenone, Dimroth, 34.5 g (0.15 mol) of 2,2'4,4'-tetrahydroxybenzophenone, 96.0 g (0.90 mol) of vinyl monochloroacetate, 78 g of sodium bicarbonate in a 3-Turf flask equipped with a temperature needle. .0g (0.90 mol), acetonitrile 95
．． 4g (2,40 mol), methoquinone 0゜2g (
1,6×10'mol) and reacted at 80° C. for 16 hours with stirring.

After the reaction is complete, the contents are filtered and the filtrate is concentrated.

The obtained residue was recrystallized with methanol, and the recrystallized product was washed several times with methyl isobutyl ketone to obtain 2,2'-dihydroxy-4,4'-di(vinyloxycarbonylmethoxy) as pale yellow particles. Benzophenone (
The formula [■]) was obtained.

Furthermore, by concentrating the methyl isobutyl ketone solution and recrystallizing the residue with ethyl acetate, a white-yellow 2-hydroxy-2'4.4'-)li(vinyloxycarbonylmethoxy)benzophenone (formula [■]) was obtained. was gotten.

The former compound had ultraviolet absorption maxima at 330 nm and 294 nm, and the molar absorption coefficients at these wavelengths were 10561.10852, respectively. In addition, the latter compound has maximum ultraviolet absorption at 310 nm and 268 nm, and the molar extinction coefficient at these wavelengths is 1, respectively.
It was 4927.9048.

Example 9 Synthesis of 2-hydroxy-4-acryloxybenzophenone Table 2-A 4 equipped with a stirring device, Dimroth, dropping funnel, and temperature needle
In a Tulo flask, 32.0 g (0.15 mol) of 2,4-dihydroxybenzophenone, 12.0 g of pyridine.
(0.15 mol), methoquinone 0.1 g (0.8X l
O-3 mol) and 200 mt dried and distilled THF.
In addition, 13.6 g of acrylic acid chloride was added while stirring.
(0.15 mol) was added dropwise over 30 minutes, and after the addition, the reaction was carried out for 4 hours under THF reflux.

After the reaction, the solvent was distilled off and the residue was mixed with methanol/water = 20/8.
Recrystallize with a mixed solvent of 0 (v/v) to obtain pale yellow particles (
A compound of formula (Vl) was obtained. This compound is 325nm
It has a maximum wavelength of ultraviolet absorption at 285 nm,
The molar extinction coefficient was 9236.15515, respectively.

Examples 10 to 22 Table-2-B Table-2-C The compounds shown in Table-2 were obtained in the same manner as in Example 1.

Example 23 Synthesis of 2-hydroxy-4,4'-diacryloxybenzophenone
In a Tulo flask, 34.5 g (0.15 mol) of 2.4.4'-1-lyhydroxybenzophenone, 24 g of pyridine
．． 0g (0.30 mol), methoquinone 0゜2g (1,
6x10-3 mol), add 200d of dry and ruthless THF, and add 27.2g of acrylic acid chloride while stirring.
(0.30 mol) was added dropwise over 30 minutes at room temperature, then T
The reaction was carried out for 8 hours under HF reflux.

After the reaction, remove the solvent, wash the residue with water, and recrystallize it with cyclohexane to obtain the target product (compound of formula [■]).
I got it. This compound had maximum ultraviolet absorption values at 333 nm and 298 nm, and the molar absorption coefficients were 9818.10381, respectively.

Example 24 Synthesis of 2-hydroxy-4,4'-dimethacrylokidibenzophenone 2.4.4'-1-lyhydroxybenzophenone 34.5
g (0.15 mol), methacrylic acid chloride 31.
4g (0.30 mol), pyridine 24.0g (0°3
0 mol), methoquinone 0.2 g (1,6x 10'
The same operation as in Example 23 was performed using 3 mol) and THF 200d to obtain the target yellow particles (compound of formula [■]). This compound had maximum ultraviolet absorption at 333 nm and 298 nm. and the molar extinction coefficient at that wavelength was 9526.10062.

Example 25 Synthesis of 2.2'-dihydroxy-4,4'-bisacryloxybenzophenone and 2-hydroxy-244'-triacryloxybenzophenone 4 equipped with a stirrer, a Dimroth, a temperature needle, and a dropping funnel.
In a Tulo flask, 34.5 g (0.15 mol) of 2.2', 4.4' tetrahydroxybenzophenone, 40.0 g (0.5 mol) of pyridine, and 0.2 g of methoquinone.
(1,6XIO-3 mol), dried and distilled THF20
Add 0 m moxibustion and add acrylic acid chloride 22 while stirring.
．． 7 g (0.5 mol) was added dropwise over 1 hour, and THF was added after dropping.
The reaction is carried out under reflux for 8 hours.

After the reaction, the solvent was removed, and the residue was washed with water, dried once, and washed with methyl isobutyl ketone 200+*t. % Furthermore, by concentrating the methyl isobutyl ketone solution and recrystallizing the residual liquid with ethyl acetate, 2-hydroxy-2
,4,4'-1-reacryloxybenzophenone (formula [
X]) was obtained as white-yellow particles.

The former has ultraviolet absorption maximum values at 330 nm and 294 nm, and the molar extinction coefficient at those wavelengths is 11642.12303, respectively, and the latter has ultraviolet absorption maximum values at 310 nm and 268 nm. value, and the molar extinction coefficient at that wavelength is 19797
．． It was 10695.

Example 26 2.2'-dihydroxy-4,4'-bismethacryloxybenzophenone and 2-hydroxy-2,4,4'-
) Synthesis of remethacryloxybenzophenone 2.2', 4,4'-tetrahydro-bovine dibenzophenone 34.5 g (0.15 mol), pyridine 40.0 g (
0.5 mol), methoquinone 0.2 g (1,6xlQ-3
The same procedure as in Example 25 was carried out using 52.3 g (0.5 mol) of methacrylic acid chloride and 200 ml of dried and distilled THF.

Thereby, 2,2'-dihydroxy-4,4'-bismethacryloxybenzophenone (compound of formula (XI))
, and 2-hydroxy-2,4,4'-trimethacryloxybenzophenone (compound of formula (x■)) were obtained.

The former compound had maximum ultraviolet absorption at 3301 m and 294 nm, and the molar absorption coefficients at these wavelengths were 11790 and 12117, respectively. In addition, the latter compound has maximum ultraviolet absorption at 310 nm and 268 nm, and its molar absorption coefficient is 17367, respectively.
．． 9459-? Example 27 Synthesis of 2-hydroxy-4-[β-[methacryloxyethylcarbamoyloxy)ethoxy]benzophenone II Cl 38.7 g (0.15 mol) of 2-hydroxy-4-(β-hydroxy)benzophenone ), 0.2 g (3,OX 10-3 mol) of dibutyltin urilate, and 0.2 g (1,8xlO-3 mol) of P-hydroquinone are dissolved in 150 ml of dry, ruthless acetone without stirring. Methacryloxyethyl isocyanate 23.2g (
After 0 dropwise addition, the mixture was reacted for 3 hours under refluxing acetone.

After the reaction is complete, add acetone and dissolve the residue in acetonitrile/
By recrystallizing from a water=50150 (W/W) solution, yellow particles (compound of formula (X III)) were obtained. This compound had maximum ultraviolet absorption values at 325 nm and 286 nm, and the molar absorption coefficients at these wavelengths were 7929.12722, respectively.

Examples 28 to 38 In the same manner as in Example 27, the compounds shown in Table 3 were obtained.

Example 39 Synthesis of 2-hydroxy-4,4'-di(methacryloxyethylcarbamoyloxy)benzophenone 4 equipped with a stirring device, a Dimroth, a dropping funnel, and a thermometer.
In a Tulo flask, 34.5 g (0.15 mol) of 2,4.4'-1-lyhydroxybenzophenone, Table 3-A Table 3-B λ1: λmax 1/nw+ λ2: λ configuration χ2/r+Il Absorption characteristics The lower number is the molar absorption coefficient λ 1 : λ
-ax H/ns λ2: λw1ax 2 /ns The numbers on the bottom of the absorption characteristics are the molar absorption coefficient Table 3-C λ1: λmax 1 /na+ λ2: λmax 2 /nm The numbers on the bottom of the absorption characteristics are the number of molar absorbers Dibutyltin urirate 0.3 g (4,5x 1
0'mol), P-hydroquinone 0.4g (3,6xlO
-mol) in dry, grooveless acetone 150, and with stirring
46.4 g (0.3 mol) are added dropwise in 1 hour.

After the dropwise addition, the mixture was allowed to react for 5 hours under refluxing acetone. After the reaction is complete, remove the acetone and dissolve the residue in a small amount of methanol/water.
0150 (V/V) solution, yellow particles (formula (X
Compound IV) was obtained.

This compound had maximum ultraviolet absorption at 333 nm and 298 nm, and the molar extinction coefficient at each wavelength was 8247.9793. The compounds shown in Table 4 were obtained.

Example 43 Synthesis of 2-hydroxy-4-(β-(methacryloylethylcarbamoyloxy))ethoxybenzophenone homopolymer Example 27 was placed in a 4-turokolben equipped with a stirring device, a Dimroth, a nitrogen introduction tube, a thermometer, and a dropping funnel. 28.2 g (0.10 mol) of yellow particles obtained in
．． 2g (0.32 mol) was added to dissolve the yellow particles. This solution is degassed under a nitrogen stream and then heated to 70°C. Then, 0.05 g of abbisisobutyronitrile (hereinafter referred to as AIBN) was dissolved in a small amount of ethyl acetate and added dropwise from the dropping funnel, and reacted at 70° C. for 8 hours under a nitrogen atmosphere.

After the reaction, the contents were taken out, 50 g of ethyl acetate was added, and the solution was poured into methanol 2e to reprecipitate. The resulting yellow precipitate was collected by filtration and dried under reduced pressure for several days.

The average molecular weight of these yellow particles is 1.15 from GPC analysis.
X 105 and had a melting point of 72° C. according to DSC analysis. 1°5mg/10 of this polymer
The ultraviolet absorption spectrum in a 0 mj chloroform solution is shown in FIG. 1, and thermogravimetric analysis revealed that this polymer has a thermal decomposition point at 250°C.

Example 44 Synthesis of 2-Hydroxy-4-(β-methacryloxy)ethoxybenzophenone homopolymer The white particles obtained in Example 12 were placed in a 4-turbocolben equipped with a stirring device, a Dimroth, a nitrogen introduction tube, a temperature needle, and a dropping funnel. 28.8g
(0,10 mol), ethyl acetate 28.8 g (0,33
mol) to dissolve the white particles. After aerating this solution under a nitrogen stream, the temperature is raised to 70°C. Then, 0.05 g of AIBN was dissolved in a small amount of ethyl acetate and added dropwise from the dropping funnel, and reacted for 8 hours at 70° C. under a nitrogen atmosphere.

After the reaction, the contents were taken out, 50 g of ethyl acetate was added, and the solution was poured into methanol 21 to cause reprecipitation. The resulting white precipitate was collected by filtration and dried under reduced pressure for several days.

This white particle has an average molecular weight of 1.25 according to GPC analysis.
It was found to have a melting point of 77° C. by DSC analysis. 1.5 mg/l of this homopolymer
The ultraviolet absorption spectrum in a 00ml chloroform solution is shown in FIG. 1, and thermogravimetric analysis revealed that this polymer has a thermal decomposition point at 265°C.

Example 45 Synthesis of 2-Hydroxy-4-Acryloxybenzophenone Homopolymer 26.8 g of the white particles obtained in Example 9 were placed in a 4-turocolben equipped with a stirring device, a Dimroth, a nitrogen inlet tube, a temperature needle, and a dropping funnel. 0.1 mol), ethyl acetate 26.8
g (0.3 mol) and melt the white particles. This solution is aerated under a nitrogen stream and heated to 70°C.

Then, 0.05 g of AIBN was dissolved in a small amount of ethyl acetate and added dropwise from the dropping funnel, followed by reaction at 70° C. for 8 hours under a nitrogen atmosphere.

After the reaction, the contents were poured out, 50 g of ethyl acetate was added, and the solution was poured into methanol 21 to cause reprecipitation. The resulting white precipitate was collected by filtration and dried under reduced pressure for several days.

This white particle has an average molecular weight of 1.0I as determined by GPC analysis.
According to DSC analysis, it had a melting point of 104°C. 1.5mg/of this homopolymer
100mA! The ultraviolet absorption spectrum in a chloroform solution is shown in FIG. 1, and thermogravimetric analysis revealed that this polymer has a thermal decomposition point at 287°C.

Comparative Example 1 1.5 mg of a commercially available high molecular weight type ultraviolet absorber 2-hydroxy-4-octoxybenzophenone was dissolved in 100 ml of chloroform, and its ultraviolet absorption spectrum was measured using an ultraviolet spectrometer needle. The spectrum is shown in FIG.

Example 46 Synthesis of copolymer of 2-hydroxy-4-meccryloxybenzophenone and butyl acrylate pale yellow particles 14.1
g (0.05%), butyl acrylate 57.6 g
(0,45 mol), ethyl acetate 57.6 g (0,65
This solution was aerated under a nitrogen stream and heated to 70°C.
The temperature rises to Then, 0.05H AIBN was dissolved in a small amount of ethyl acetate and added dropwise from the dropping funnel, and reacted for 8 hours at 70° C. under a nitrogen atmosphere. 3 hours after reaction start f&A
IB No. 2g was added in the same manner as above.

After the reaction, the contents were taken out, 50 g of ethyl acetate was added, and the solution was poured into methanol 21 to cause reprecipitation.

The resulting white precipitate was collected by filtration and dried under reduced pressure for several days.

The average molecular weight of this particle is 6.90X1 from GPC analysis.
It was 05. Figure 2 shows 10mg/l of this polymer.
00m/ultraviolet absorption spectrum in chloroform solution.

Example 47 Synthesis of 2-hydroxy-4-(β-methacryloxy)ethoxybenzophenone-methyl methacrylate copolymer The procedure of Example 12 was carried out in a 4-turokolbene equipped with a stirring device, a Dimroth, a nitrogen introduction tube, a temperature needle, and a dropping funnel. 14.4 g (0.05 mol) of the obtained white particles, 45.0 g (0.45 mol) methyl methacrylate, and 45.0 g (0.45 mol) ethyl acetate.
0 g (0.51 mol) was added, the solution was aerated under a nitrogen stream, and the temperature was raised to 70°C. and 0.12 g Ar
BN is dissolved in a small amount of ethyl acetate and added dropwise from a dropping funnel, and reacted at 70° C. for 8 hours under a nitrogen atmosphere. Three hours after the start of the reaction, 0.2 g of AIBN was added in the same manner as above.

After the reaction, the contents were taken out, 50 g of ethyl acetate was added, and the solution was poured into 2 Il of methanol for reprecipitation. The resulting white precipitate was collected by filtration and dried under reduced pressure for several days.

The average molecular weight of this particle is 6.54X1 from GPC analysis.
It was 05. Figure 2 shows 10mg/1 of this polymer.
The ultraviolet absorption spectrum of a 00ml chloroform solution is shown.

Example 48 Synthesis of copolymer of 2.2',4-trihydroxy-4'-methacryloxybenzophenone and styrene 15.7 g (0.05 mol) of pale yellow particles obtained in step 20, styrene 47
．． 1g (0.45 mol), ethyl acetate 47.1g (0.
, 53 mol) and aerated this solution under a nitrogen stream,
Raise the temperature to 70°C. Then, 0.13 g of AIBN was dissolved in a small amount of ethyl acetate and added dropwise from the dropping funnel, followed by reaction at 70° C. for 8 hours under a nitrogen atmosphere.

After the reaction, 50 g of chloroform was added to the contents, and this solution was dropped into methanol 21 to cause reprecipitation.

The resulting white precipitate was collected by filtration and dried under reduced pressure for several days.

The average molecular weight of this particle was 4.82X by GPC analysis.
It was l 04. In Figure 2, 10 mg of this polymer
/100ml shows the ultraviolet absorption spectrum in a chloroform solution.

Example 49 (Weather resistance test) The polymers synthesized in Examples 46, 47, and 48 were coated on dyed polyester cloth, and the color change over time was observed in a weather meter. The test cloth was dyed under the following conditions: Fanix Brilliant Yellow
w 7G-5R (manufactured by Mitsubishi Chemical Industries, Ltd.) Cloth: Polyester processed yarn fabric Tropical dyeing conditions: Dye 4% acetic acid (90% product)
0.3cc Venerap HG (leveling agent) 0.5g/
1 bath ratio 1:20 Dyeing temperature 130°C Dyeing time 30 minutes A 10% by weight ethyl acetate solution of each of the polymers obtained in Examples 46, 47, and 48 was added to the above dyed fabric in a 40 μm thick layer.
It was applied using an applicator and dried at 105° C. for 1 hour, and then used as a test cloth.

The test cloth prepared as described above was subjected to a weather resistance test under the following conditions, and the degree of fading of the dye was visually determined.

・Weather resistance test conditions Model used: Suga Test Instruments Sunshine Weather Meter L-5UN-DCII model Exposure conditions: Light source
Continuous irradiation spray cycle (rainfall/period) 18/120 minutes Temperature 65°C Humidity 70% R1+ The measurement results are shown in Table-5.

As can be seen from Table 5, the polymer of the present invention exhibits excellent weather resistance.

Comparative Example 2 Polymethyl methacrylate resin (Elvacite 20
09: 20g (manufactured by DuPont), 207g (2,
35 mol) of ethyl acetate, and this solution was dissolved in 40 μm
It was applied to the test cloth dyed in Example 49 using an applicator and dried at 105° C. for 1 hour. A dye weathering test was conducted on this test cloth according to Example 49.

The measurement results are shown in Table 5.

Example 50 (Elution test) (Sample preparation) Polymethyl methacrylate resin (Elvacite 20
09: DuPont) was melted at 150°C, 20g of the homopolymer of Example 43 (containing 15% by weight) was added thereto, and after sufficiently kneading, it was poured into a mold of 3.4 m.
It was molded into a sheet with a thickness of m (sample 43). In the same manner, sheets were formed using the homopolymers of Examples 44 and 45 (Samples 44 and 45).

For the copolymers of Examples 46, 47, and 48, 112 g of each was melted at 150°C and poured into a mold.
Formed into a 4 mm thick sheet (sample 46.47.4
8).

(Measurement) 500m7 each of water, ethanol, and hexane in a 500me-Kolben equipped with a Dimroth! 5011III+×50mm each sheet above.
The pieces cut into widths were immersed, heated to 50°C, and left for 500 hours.

After leaving it for a while, add 1 9m7 of each liquid! The degree of ultraviolet absorption at 330 nm was determined as ○ (transmittance 100-91%) and △ (transmittance 9).
0 to 60%), × (transmittance less than 60%). The measurement results are shown in Table-6.

Table 6 Comparative Example 3 Polymethyl methacrylate resin (Elvacite 20
09: DuPont) 112g was melted at 150°C, and 2-hydroxy-4-methoxybenzophenone 2
Add 0g and mix well, then pour into the mold 3.4
It was molded into a sheet with a thickness of mm. Table 6 shows the results of a dissolution test conducted in the same manner as in Example 50.

As can be seen from Table 6, the polymer of the present invention exhibits excellent elution resistance.

[Effects of the Invention] As can be seen from the above examples, the polymer of the benzophenone compound of the present invention has superior ultraviolet absorbing ability compared to conventional ultraviolet absorbers. In addition, it has a high thermal decomposition temperature, excellent weather resistance and elution resistance, and can maintain a stable UV absorption effect for a long period of time, making it an extremely excellent UV absorber. It can be widely used as a polymer. .

Furthermore, the benzophenone monomer of the present invention can be easily polymerized alone or with various vinyl monomers to form a polymer.

[Brief explanation of the drawing]

FIG. 1 is an ultraviolet absorption spectrum diagram of the homopolymer according to the present invention and a comparative example material, and FIG. 2 is an ultraviolet absorption spectrum diagram of the copolymer of the present invention.

Claims (1)

[Claims] 1. A benzophenone compound represented by the general formula [I]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [I] However, in the formula [I], R: hydrogen or methyl group A: R^1-X-R^2, R^1-X, X-R^2 or A group selected from , straight chain or branched chain alkyl residues of C_1 to C_1_0, or atoms or groups R^ selected from the group consisting of groups represented by ▲ mathematical formulas, chemical formulas, tables, etc. ▼ in formula [I] 3: Hydrogen or a linear or branched chain alkyl residue of C_1 to C_1_0 n: An integer of 1 to 3, however, in the case of 2 to 3, R^3 may be different. 2. A homopolymer of the compound [I] according to claim 1. 3. A copolymer of the compound [I] according to claim 1 and a vinyl monomer.