JP2835396B2 - Reactive ultraviolet absorber composed of benzophenone compound and copolymer of benzophenone compound - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a benzophenone-based compound and a copolymer containing the compound in a polymer. More specifically, the present invention relates to a benzophenone-based compound having a carboxyl group, an ester group, an amide group, and a hydrazide group capable of reacting with a hydroxyl group, an epoxy group, and the like, and a copolymer composition containing the benzophenone-based compound. It is. The most effective application of these compounds is in the UV protection of polymeric and other organic materials.

2. Description of the Related Art Polymer materials used outdoors are exposed to daily sunlight, and indoors are exposed to fluorescent light. These sunlight and fluorescent light contain ultraviolet rays that are harmful to polymer materials of 200 to 400 nm, which excite the functional groups in the polymer and the remaining polymerization catalysts, and as a result, the photolysis reaction Occurs and deteriorates the polymer material.

Further, in a polymer material into which a dye or a pigment is kneaded, a problem of fading of the dye or the pigment occurs at the same time as the photodegradation of the polymer material. Furthermore, there is also a problem that the contents stored in a container or a packaging bag using a polymer material are deteriorated by ultraviolet rays.

In order to protect the polymer material from light in such a harmful area, an ultraviolet absorber is usually added to the polymer material. The UV absorber absorbs all or most of the light in the harmful area, converts that energy into harmless energy such as non-radiative transitions and emits it, protecting the polymer from photolytic reactions.

By the way, as a conventional ultraviolet absorber, a benzophenone-based or benzotriazole-based compound which is highly effective in suppressing or delaying photodecomposition of a polymer material or in preventing fading of a compounded dye or pigment is widely used. For benzophenones, 2,4-dihydroxybenzophenone, for benzotriazoles, 2- (2'-hydroxy-5 '
-Methylphenol benzotriazole is a representative of each.

However, since these are low-molecular compounds, they have poor compatibility with high-molecular materials, and bleed out from the high-molecular materials with time and are scattered or eluted into various media.
Photodegradation of the polymer material is gradually accelerated. Further, since the molding of the polymer material is performed at a high temperature, the kneaded ultraviolet absorber volatilizes or decomposes, so that the ultraviolet absorber often hardly remains in the final product.
Furthermore, elution into various media also raises sanitary problems when the polymeric material is used in food packs and beverage bottles.

In order to overcome these disadvantages, it has been attempted to increase the molecular weight of the ultraviolet absorber. For example, 2-hydroxy-4-long-chain alkoxybenzophenone has improved compatibility with a polymer material, and as a result, improved volatility and elution property. Examples of these are 2-hydroxy-4-
Octoxybenzophenone and 2-hydroxy-4-dodecyloxybenzophenone are commercially available. Also, the benzotriazole-based ultraviolet absorber has a high molecular weight, and alkyl and aralkyl-substituted 2- (2'-hydroxyphenyl) benzotriazoles are well known.

[Problems to be Solved by the Invention] These high-molecular-weight ultraviolet absorbers have improved volatility and dissolution after molding as compared with conventional low-molecular-weight ones, but still have poor heat resistance and have high polymer materials. However, there still remains a problem such as volatilization or decomposition of the ultraviolet absorbent during the high-temperature molding. At the present time, the addition of the ultraviolet absorber is extra in consideration of volatilization and decomposition during processing. In addition, even if the compatibility with the polymer material is improved, when it is used at a high concentration, the ultraviolet absorber also precipitates out and the transparent polymer material becomes opaque. Often, they bleed out and become dusty.

As a method for improving the drawbacks of the currently used ultraviolet absorbers including the low molecular weight ultraviolet absorbers and the high molecular weight type ultraviolet absorbers described above, it is conceivable to introduce an ultraviolet absorbing skeleton directly into the polymer chain. . That is, a reactive group is introduced into an ultraviolet absorber and incorporated into a polymer chain to prevent volatilization, elution or precipitation of the ultraviolet absorber. This compound is generally called a reactive ultraviolet absorber.

This research has been conducted in the past, and some proposals have been made. For example, in the case of the benzophenone system,
2039 and benzotriazoles are disclosed in JP-A-60-38411. However, there are many cases where the performance is worse than that of the conventional type, and at present, it is hardly commercially available. Also,
Most of these reactive ultraviolet absorbers have a reactive group having a double bond, and reactive ultraviolet absorbers that can be used for polyesters and the like are disclosed in JP-A-56-92914. Nothing is known other than '-dihydroxy-4-4'-di (β-hydroxyethoxy) benzophenone. However, since the reactive group is a hydroxyl group, the target polymer material is limited.

Means for Solving the Problems Accordingly, the present inventors have conducted intensive studies on the above-mentioned reactive ultraviolet absorber, and as a result, have developed a benzophenone-based compound which is general-purpose and excellent in performance, and an ultraviolet-absorbing polymer containing them. succeeded in.

That is, the present invention, polyesters, polyamides, polyurethanes that were not the target of conventional reactive ultraviolet absorbers,
An object of the present invention is to provide a novel ultraviolet absorbing compound having a reactive group capable of performing a condensation reaction and an addition reaction that can be introduced as one component of an epoxy resin. It is another object of the present invention to provide a polymer composition having improved ultraviolet absorbing properties derived from the novel ultraviolet absorbing compound.

The compound of the present invention is a benzophenone compound represented by the general formula [I].

However, in the formula (I), X: a group represented by a hydroxyl group or Q, Z: an atom or a group represented by hydrogen, a hydroxyl group, a methoxy group or Q, provided that at least one of X or Z is represented by Q It is a group to be performed.

Those selected from, but R ¹ is -OH, C ₁ -C straight or branched chain alkoxy group having ₄ or -NHNH ₂ from selected groups, straight-chain R ² is C ₁ -C ₄ Or a group selected from a branched chain alkylene group.

Y: hydrogen, hydroxyl, straight-chain or branched-chain alkyl residue, or an atom or a group selected from the group represented by Q of C ₁ -C _4.

R ³ and R ⁴ : groups selected from hydrogen and C _{1 to} C ₄ linear or branched alkyl residues.

h: any integer from 1 to 4, provided that X is different from 2 to 4.

l: any integer from 1 to 4, provided that Z is different from 2 to 4.

m: any integer not exceeding 4-l, provided that in the case of 2-3, R ³ may be different. n: any integer not exceeding 4-h, provided that R ⁴ may be different in the case of 2-3.

The compound represented by the general formula [I] is exemplified below.
For example, mono- or dicarboxylic acids of 2,4-dihydroxybenzophenone, 2-hydroxybenzophenone-4-oxyacetic acid, 2-hydroxybenzophenone-4-α-methyloxyacetic acid, 2-hydroxybenzophenone-4-
Oxypropionic acid, 2-hydroxybenzophenone-
4-hydroxybutyric acid, 2-hydroxybenzophenone-4-
Oxymalonic acid, 2,4,4'-trihydroxybenzophenone-carboxy-substituted product, 2,4,4'-trihydroxybenzophenone-mono or -dicarboxymethyl ether, 2,4,4'-trihydroxybenzophenone- mono,
Or -di (1-carboxy-1-methyl) methyl ether, 2,4,4'-trihydroxybenzophenone-mono,
Or -dicarboxypropyl ether, 2,4,4'-trihydroxybenzophenone-mono, or -dicarboxypropyl ether, 2,4,4'-trihydroxybenzophenone-mono, or -di (1,1'-bis Carboxy) methyl ether, 2,3,4-trihydroxy-5-carboxybenzophenone, 2,3,4-trihydroxybenzophenone-mono or -dicarboxymethyl ether, 2,3,
4-trihydroxybenzophenone-mono or -di (1-carboxy-1-methyl) methyl ether, 2,3,
4-trihydroxybenzophenone-mono or -dicarboxyethyl ether, 2,3,4-trihydroxybenzophenone-mono or -dicarboxypropyl ether, 2,3,4-trihydroxybenzophenone-mono or di (1 , 1-biscarboxy) methyl ether, 2,2 ′,
4,4'-tetrahydroxybenzophenone-mono,-
Di, -tri, or tetracarboxy derivatives, 2,2 ', 4,
4'-tetrahydroxybenzophenone-mono, -di,
Or -tricarboxymethyl ether, 2,2 ', 4,4'-
Tetrahydroxybenzophenone -mono, -di, or-
Tri (1-carboxy-1-methyl) methyl ether,
2,2 ', 4,4'-tetrahydroxybenzophenone-mono, -di or -tricarboxypropyl ether, 2,
2 ', 4,4'-tetrahydroxybenzophenone-mono,
-Di, or -tricarboxypropylethyl, 2,2 ', 4,
4'-tetrahydroxybenzophenone-mono, -di,
Or -tri (1,1-biscarboxy) methyl ether,
2,4-dihydroxy-4'-methoxy-3 ', 5'-bismethylbenzophenone-mono- or -dicarboxylic acid,
-Hydroxy-4'-methoxy-3 ', 5'-dimethylbenzophenone-4-oxyacetic acid, 2-hydroxy-4'
-Methoxy-3 ', 5'-dimethylbenzophenone-4-
α-methyloxyacetic acid, 2-hydroxy-4′-methoxy-3′-5′-dimethylbenzophenone-4-oxypropionic acid, 2-hydroxy-4′-methoxy-3 ′
-5'-dimethylbenzophenone-4-oxybutyric acid, 2
-Hydroxy-4'-methoxy-3 ', 5'-dimethylbenzophenone-4-oxymalonic acid, 2,5-dihydroxybenzophenone-mono or -dicarboxylic acid, 2-hydroxybenzophenone-5-oxyacetic acid, 2-hydroxy Benzophenone-5- (α-methyl) -oxyacetic acid, 2-hydroxybenzophenone-5-oxypropionic acid, 2-hydroxy-5-oxybutyric acid, 2-hydroxybenzophenone-5-oxymalonic acid, 2-hydroxybenzophenone-4 -Ethylenedioxyacetic acid, 2-
Hydroxybenzophenone-4- (β-methyl) -ethylenedioxyacetic acid, 2-hydroxybenzophenone-4
-Ethylenedioxypropionic acid, 2-hydroxybenzophenone-4-ethylenedioxybutyric acid, 2-hydroxybenzophenone-4-ethylenedioxymalonic acid, 2
-Hydroxy-3-carboxy-4- (β-hydroxyethoxy) benzophenone, and ester derivatives and hydrazide derivatives of the above compounds.

These novel benzophenones include benzophenones having at least two hydroxyl groups on one or both of the benzene rings, or a hydroxyl group at the 2-position of the benzene ring and an alkyl residue having a terminal hydroxyl group at the other substitution position. A general etherification reaction of a substituted benzophenone with a halogenated carboxylic acid or an ester thereof, a general esterification reaction of a benzophenone-carboxylic acid derivative obtained therefrom, and a general Kolbe It can be easily obtained by a Schmidt reaction, an oxidation reaction of a methyl group or the like, and a general hydrazide reaction from the above-mentioned ester derivative of a novel benzophenone.

The benzophenones of the present invention are reactive ultraviolet absorbers having a carboxyl group, an ester group, or a hydrazide group capable of reacting with a hydroxyl group, an epoxy group, an isocyanate group or the like, unlike the conventional addition type.

Accordingly, the novel benzophenones of the present invention can be used as one composition of a resin obtained by condensation polymerization or addition polymerization, such as polyester, polyamine, polyimine, polyacetal, polyhydrazide, polyurethane, epoxy resin, and the like, whereby The polymer material having improved light resistance and light resistance can be obtained.

For example, when the polymer is a polyester, the benzophenones of the present invention can be incorporated into the polyester chain as acid residues. If the benzophenones of the present invention used are monocarboxylic acids or monocarboxylic acid esters, they act on the terminal of the polymer and thus act as a so-called polymerization regulator. If the benzophenones are dicarboxylic acid derivatives, tricarboxylic acid derivatives, or esters thereof, they are incorporated into the polymer as intramolecular components. The concentration of these novel benzophenones is preferably from 0.001 to 30% by weight, especially from 0.002 to 10% by weight, based on the weight of the polymer.

The basic acids constituting the other acid portion of the polyester composition of the present invention are not particularly limited, for example, terephthalic acid,
Isophthalic acid, naphthalene-2,6-dicarboxylic acid, maleic acid, fumaric acid, adipic acid, sebacic acid, or their alkyl esters, or acid anhydrides such as maleic anhydride, fumaric anhydride, etc. More than one type of dibasic acid may be used.

The diol which is the partner of the condensation polymerization is not particularly limited, and examples thereof include ethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, and propylene glycol. Also in these cases, one or more diols can be combined.

Among these combinations, the benzophenones of the present invention are particularly preferably applied to a saturated polyester represented by polyethylene terephthalate resin and fiber (hereinafter referred to as PET resin, PET fiber and the like) and generally to anhydrous polyester. The field of unsaturated polyester resin coatings obtained by polycondensing maleic acid or fumaric acid with ethylene glycol.

PET resin is now in increasing demand for food containers such as soy sauce, sauces, sake, and juice, containers for cosmetics, and medical products. In particular, when PET resin is used for food containers, ultraviolet absorbers have been conventionally used to protect the contents from light degradation, but since these are low molecules, they are scattered or eluted by rain etc. However, there is a problem in that the content of the PET resin itself is protected for a long period of time, and there are not a few hygienic problems such as elution of the ultraviolet absorber into the content.

The PET resin composition having improved weather resistance or light resistance containing the benzophenones of the present invention as one component has improved scattering and dissolution of the ultraviolet absorber due to elution, and can impart light stability in the long term. .

In addition, PET fiber is extremely useful as a synthetic fiber having excellent strength and wear resistance, but the weather resistance of the present invention is improved.
PET fibers are effective in preventing long-term light degradation of the fibers themselves and long-term fading.

The coatings field is a field in which weather resistance is particularly required, and an ultraviolet absorber used in this field plays a role in preventing discoloration of a pigment and deterioration of a binder.

In the case of unsaturated polyester resin coatings as well, low molecular ultraviolet absorbers have been conventionally used, and it has been difficult to impart long-term light stability. The unsaturated polyester of the present invention containing benzophenones as one component has improved long-term light stability and is particularly suitable for the field where the paint is used outdoors.

Among the novel benzophenones of the present invention, a polyester in which a dicarboxylic acid derivative, a tricarboxylic acid derivative, or an esterified product thereof is present in an acid residue portion in an amount of 20% by weight or more is useful as a master batch type polymer type ultraviolet absorber. It is. These have a higher molecular weight than conventional high-molecular ultraviolet absorbers, 2-hydroxy-4-octoxybenzophenone and 2-hydroxy-4-dodecyloxybenzophenone, and have much higher scattering and elution properties than these. Be improved. In addition, since the molecular weight per unit in the polymer is smaller than that of 2-hydroxy-4-octoxybenzophenone or 2-hydroxy-4-dodecyloxybenzophenone, the density of the ultraviolet absorbing portion per unit weight increases, Since the same or higher ultraviolet absorbing ability can be obtained with a smaller amount than the conventional high molecular weight type ultraviolet absorbing agent, there is a cost advantage.

Further, the polyester containing the novel benzophenones of the present invention as a component can be used as a raw material for polyurethane. Polyurethane is one of polymer materials lacking in weather resistance, and causes yellowing due to ultraviolet rays or the like. For this reason, UV absorbers have been added in the past, but since these are low molecular types, there are still problems such as compatibility,
Scattering and elution from the resin occur.

This polyurethane is obtained by a urethane reaction between a polyisocyanate and a polyol.

Polyols are roughly classified into polyether-based and polyester-based polyols. The polyester of the present invention is extremely useful as a polyester-based polyol, and when the polyurethane composition derived from the polyester of the present invention is used, the weather resistance is greatly improved.

The polyisocyanate in the polyurethane composition having improved weather resistance is not particularly limited, and examples thereof include tolylene diisocyanate (TDI), 4,4'-diphenylenemethane diisocyanate (MDI), hexamethylene diisocyanate (HMDI), Range isocyanate (XDI),
Examples include hydrogenated diphenylmethane isocyanate (H ₁₂ MDI), hydrogenated tolylene diisocyanate (HTDI), and isophorone diisocyanate (IPDI).

As the polyol, a polyester composition containing the novel benzophenones of the present invention as a component may be used alone, or another common polyether-based polyol or polyester-based polyol may be used in combination.

The polyurethane composition containing the polyester composition of the present invention is suitable for application to a polyurethane paint and a sports surface.

Next, polyamide is an important synthetic fiber because it is light and has high tensile strength, abrasion strength and bending strength, but is also widely used for covering electric wires because of its excellent electrical insulation. However, the light resistance is extremely poor, and when exposed to sunlight for a long time, the strength decreases and yellowing occurs. For example, the phenomenon in which lace curtains, which are mainly made of nylon, quickly turn yellow is a sight that is often seen on a daily basis.

As described above, polyamide is a polymer material having poor light resistance, but up to now no ultraviolet absorber has been used because nylon has poor compatibility. The novel carboxylic acid derivatives of benzophenones of the present invention or their ester derivatives can be incorporated into the polyamide chain as acid residues. Of these new benzophenones,
The monocarboxylic acid derivative or its ester acts on a polyamide terminal as a polymerization regulator. When the benzophenones are a dicarboxylic acid derivative, a tricarboxylic acid derivative or an ester thereof, they are incorporated into the polymer as an intramolecular component. The concentration of these new benzophenones is from 0.001 to 30% by weight, based on the weight of the polymer, especially
It is desirable to contain 0.002 to 10% by weight.

The dibasic acids constituting the other acid portion of the polyamide composition of the present invention are not particularly limited, for example,
Examples thereof include adipic acid, sebacic acid and their alkyl-substituted products, and their esterified products. Further, one or more dibasic acids described above can be used. The diamine which is the partner of the polycondensation is not particularly limited, and includes, for example, hexamethylenediamine, dodecamethylenediamine, tetramethylenediamine, 1,4-diaminocyclohexane, p-phenylenediamine, m-phenylenediamine and the like.
Also in this case, one or more diamines may be combined.

Among the novel benzophenones of the present invention, a polyamide in which a dicarboxylic acid derivative, a tricarboxylic acid derivative, or an esterified product thereof is present in an acid residue portion in an amount of 20% by weight or more is useful as a master batch type polymer type ultraviolet absorber. It is. These are higher in molecular weight than conventional polymer-type UV absorbers and have better compatibility with polymer materials, so that their scattering and elution properties are improved compared to conventional polymer-type UV absorbers. Therefore, the stability of the polymer material to which it is added over time with respect to light is improved. This masterbatch type polymer type ultraviolet absorber is particularly useful when it is desired to use the ultraviolet absorber at a relatively high concentration without significantly changing the physical properties of the original base resin.

As described above, the novel benzophenones of the present invention open the way to the application of ultraviolet absorbers to polyamides for which ultraviolet absorbers have not been used so far. Polyamide fibers have recently come to be used in automobile seat covers, but they are also effective in preventing such fading.

Furthermore, the novel benzophenones of the present invention can react with an epoxy group or a hydroxyl group in an epoxy resin to pentant the hydroxybenzophenone skeleton in the epoxy resin molecular chain. In addition, if the novel benzophenones of the present invention are bifunctional or trifunctional, they act as a curing agent as well as an ultraviolet absorber.

Of the novel benzophenones of the present invention, those which are particularly suitable for reacting with epoxy resins are hydrazide derivatives. Currently, hydrazide compounds are latent one-part curing agents, and because of their high curing speed, many studies have been made recently.For example, aliphatic dihydrazides such as adipic hydrazide and azelaic dihydrazide,
Aromatic dihydrazides such as isophthalic dihydrazide are commercially available.

Among the novel benzophenone-hydrazide derivatives of the present invention, monohydrazide derivatives are extremely useful as one-part reactive ultraviolet absorbers, and dihydrazide derivatives and trihydrazide derivatives are extremely useful as one-part reactive ultraviolet absorbers and curing agents. .

The novel benzophenone-hydrazide derivative of the present invention can be easily obtained by reacting the novel benzophenone-carboxylate with hydrazine hydrate in a polar solvent.

The compounding amount of the benzophenones of the present invention is 0.001 to 1.5 equivalents as active hydrogen equivalents of the benzophenones per equivalent of epoxy group of the epoxy resin, preferably 0.002 to 1.0 equivalents for those having a monofunctional group, and bifunctional groups. If so, it is in the range of 0.002 to 1.2 equivalents.

The epoxy resin applied to the benzophenones of the present invention is a resin having one or more epoxy groups in one molecule, and includes various well-known epoxy resins. For example,
Examples include glycidyl ethers of polyhydric phenols, particularly glycidyl ethers of bisphenol A, glycidyl ethers of bisphenol F, and polyglycidyl ethers of phenol formaldehyde resin.

The benzophenones of the present invention may be used in combination with other curing agents. In particular, if the benzophenones of the present invention are monofunctional, a curing agent must be used. The curing agent is not particularly limited, and may be a known one. For example, a dihydrazide compound as described above, dicyandiamide,
Boron trifluoride-amine adduct, guanamines, melamine, amines, organic acids, acid anhydrides, and the like.

The compounding amount of these curing agents is 0.001 to 0.001 as active hydrogen equivalent of the curing agent with respect to 1 equivalent of epoxy group of the epoxy resin.
It is used in a range excluding the active hydrogen equivalent of the benzophenones of the present invention from 1.5 equivalents, preferably in a range excluding the active hydrogen equivalent of the benzophenones of the present invention from 0.002 to 1.2 equivalents. Further, the epoxy resin composition of the present invention may optionally contain a curing accelerator and a filler.

[Examples] Next, the present invention will be described in more detail with reference to Examples.
The present invention is not limited to these descriptions. still,
The molar extinction coefficient in the examples was calculated from the transmittance measured for each compound using an ultraviolet spectrophotometer (UV-3200: manufactured by Hitachi) using Lambert-Beer's law, that is, the following equation.

Here, ε: molar extinction coefficient C: molar concentration of sample solution l: cell length (cm) T: transmittance

 In Examples, “parts” indicates “parts by weight”.

Example 1 "Synthesis of methyl 2-hydroxybenzophenone-4-oxyacetate" 85.6 g (0.4 mol) of 2,4-dihydroxybenzophenone, 86.8 g (0.8 mol) of methyl monochloroacetate, 67.2 g (0.8 mol) of sodium hydrogen carbonate, 100.8 g of acetonitrile
(2.4 mol) is placed in a three-necked flask equipped with a stirrer and a Dimroth, and reacted at reflux temperature for 24 hours while stirring.

After completion of the reaction, the mixture is filtered while hot to remove inorganic salts, and the filtrate is allowed to stand as it is to precipitate light yellow needle-like crystals.
The needle crystals are collected by suction filtration and washed with a small amount of a 50/50 (V / V) solution of methanol / water to obtain a yield.
As a result, methyl 2-hydroxybenzophenone-4-oxyacetate (having a structural formula represented by the formula [II]) having a purity of 63% and a purity of 99% (HPLC analysis) was obtained.

This methyl 2-hydroxybenzophenone-4-oxyacetate had the maximum value of ultraviolet absorption at 325 nm and 285 nm, and the respective molar extinction coefficients were 9.08 × 10 ³ and 1.51 × 10 ⁴ .

Example 2 "Synthesis of 2-hydroxybenzophenone-4-oxyacetic acid" 20.8 g (0.52 mol) of sodium hydroxide and 100 ml of water are placed in a four-necked flask equipped with a Dim funnel, a stirrer, a dropping funnel and a thermometer, and stirred to dissolve sodium hydroxide. There, 57.2 g of methyl 2-hydroxybenzophenone-4-oxyacetate (formula II) obtained in Example 1
(0.2 mol) and reacted at 80 ° C. for 6 hours with stirring. After the reaction, when the pH in the previously prepared 50% aqueous sulfuric acid solution is slowly dropped until the pH becomes 1, yellow particles are precipitated. The mixture is further aged for 1 hour, cooled to room temperature, and the particles are collected by suction filtration. This particle
After sufficiently washing with water, the crystals were recrystallized from acetonitrile to obtain pale yellow needle crystals in a yield of 88.2%.

These crystals were found to have a purity of 99% of 2-hydroxybenzophenone-4-oxyacetic acid (having a structural formula represented by the formula [III]) by HPLC analysis. This crystal has 325n
m and 285 nm had the maximum value of ultraviolet absorption, and the molar extinction coefficients at that wavelength were 9.12 × 10 ³ and 1.49 × 10 ⁴ , respectively.

Next, various ester derivatives and carboxylic acid derivatives of benzophenones were obtained in the same manner as in Examples 1 and 2 (Examples 3 to 9). Table 1 shows the ultraviolet absorption characteristics of each carboxylic acid derivative. The ultraviolet absorption maximum wavelength of the ester derivative was not changed from that of the corresponding saponified product, that is, the carboxylic acid derivative, and the molar extinction coefficient was hardly changed.

Example 3 "Synthesis of diethyl 2-hydroxybenzophenone-4-oxymalonate and 2-hydroxybenzophenone-4-oxymalonic acid" Ester was used by using 2,4-dihydroxybenzophenone as benzophenones and ethyl bromomalonate as a reaction substrate, respectively. Light yellow needle crystals of diethyl 2-hydroxybenzophenone-4-oxymalonate as a derivative,
Obtained in a yield of 74% and a purity of 99%.

Further, as a saponified compound, 2-hydroxybenzophenone-4-oxymalonic acid was obtained as pale yellow needle-like crystals at a yield of 91%.
Obtained with a purity of 99%.

Example 4 "2-hydroxybenzophenone-4- (α-methyl)
-Synthesis of methyl oxyacetate and 2-hydroxybenzophenone-4- (α-methyl) -oxyacetic acid ”2,4-dihydroxybenzophenone as benzophenones, methyl 2-chloropropionate as a reaction substrate, and ester derivative 2 Pale yellow needle crystals of methyl-hydroxybenzophenone-4- (α-methyl) -oxyacetate were obtained at a yield of 58% and a purity of 98%.

In addition, pale yellow needle crystals of 2-hydroxybenzophenone-4- (α-methyl) -oxyacetic acid were obtained as a saponified product in a yield of 89% and a purity of 99%.

Example 5 "Synthesis of methyl 2-hydroxybenzophenone-4-oxyacetate and 2-hydroxybenzophenone-4-oxybutyric acid" Ester was used by using 2,4-dihydroxybenzophenone as benzophenones and ethyl 4-chlorobutyrate as a reaction substrate, respectively. Light yellow powder of methyl 2-hydroxybenzophenone-4-oxybutyrate as a derivative was obtained at a yield of 60%,
Obtained with a purity of 98%.

Further, as a saponified product, pale yellow needle crystals of 2-hydroxybenzophenone-4-oxybutyric acid were obtained with a yield of 90% and a purity of 99%.

Example 6 "Synthesis of methyl 2-hydroxybenzophenone-5-oxyacetate and 2-hydroxybenzophenone-5-oxyacetic acid" 2,5-dihydroxybenzophenone as benzophenones, methyl monochloroacetate as a reaction substrate, and ester derivatives Light yellow needle crystals of methyl 2-hydroxybenzophenone-5-oxyacetate were obtained in a yield of 68.
%, Purity 99%.

Further, as a saponified product, a light yellow needle-like crystal of 2-hydroxybenzophenone-5-oxyacetic acid was obtained at a yield of 85% and a purity of 85%.
Obtained at 99%.

Example 7 "2-hydroxybenzophenone-4'-methoxy-
Synthesis of methyl 3 ', 5'-dimethylbenzophenone-4-oxyacetate and 2-hydroxybenzophenone-4'-methoxy-3', 5'-dimethylbenzophenone-4-oxyacetic acid "2,5-dihydroxy- as benzophenones 4'-
Methoxy-3 ', 5'-dimethylbenzophenone, methyl monochloroacetate as a reaction substrate, and 2-hydroxybenzophenone-4'-methoxy-3', 5'-dimethylbenzophenone-4-oxyacetate yellow as an ester derivative A powder was obtained with a yield of 57% and a purity of 99%.

Further, as a saponified compound, 2-hydroxybenzophenone-4'-methoxy-3 ', 5'-dimethylbenzophenone-4-oxyacetic acid pale yellow needle-like crystals were obtained at a yield of 88% and a purity of 88%.
99% was obtained.

Example 8 "Synthesis of methyl 2-hydroxybenzophenone-4-ethylenedioxypropylene acid and 2-hydroxybenzophenone-4-ethylenedioxypropionic acid" 2-hydroxy-4-hydroxyethoxybenzophenone as benzophenones and 3 as a reaction substrate -Methyl chloropropionate was used, and pale yellow needle-like crystals of methyl 2-hydroxybenzophenone-4-ethylenedioxypropionate were obtained as ester derivatives in a yield of 82%.
Obtained with a purity of 99%.

Further, pale yellow needle crystals of 2-hydroxybenzophenone-4-ethylenedioxypropionic acid were obtained as a saponified derivative with a yield of 93% and a purity of 99%.

Example 9 "Synthesis of methyl 2,2 ', 4'-trihydroxybenzophenone-4-oxyacetate and 2,2', 4'-trihydroxybenzophenone-4-oxyacetic acid" 2,2 ', 4 as benzophenones , 4′-Tetrahydroxybenzophenone, methyl monochloroacetate as a reaction substrate, and yellow needle crystals of methyl 2,2 ′, 4′-trihydroxybenzophenone-4-oxyacetate as an ester derivative, 51% yield, Obtained with a purity of 99%.

Further, as a saponified product, pale yellow needle-like crystals of 2,2 ', 4'-trihydroxybenzophenone-4-oxyacetic acid were obtained in a yield of 94% and a purity of 99%.

Example 10 `` Methyl 2-hydroxybenzophenone-4,4'-dioxyacetate and 2-hydroxybenzophenone-4,4'-
Synthesis Of Dioxyacetic Acid " 92.0 g of 2,4,4'-trihydroxybenzophenone (0.4
Mol), methyl monoacetate 130.2 g (1.2 mol), sodium carbonate 63.6 g (0.6 mol), acetonitrile 100.0 g
(2.4 mol) is placed in a three-necked flask equipped with a stirrer and a Dimroth and allowed to react at reflux temperature for 30 hours with stirring.

After the completion of the reaction, the inorganic salts are removed by filtration under heating, and the filtrate is allowed to stand as it is to precipitate light yellow needle-like crystals.
The needle crystals are filtered by suction and collected by filtration, washed with a small amount of a 50/50 (V / V) solution of methanol / water, and dried. Thus, methyl 2-hydroxybenzophenone-4,4'-dioxyacetate (formula IV) with a yield of 54% and a purity of 99% (HPLC analysis)
was gotten.

This methyl 2-hydroxybenzophenone-4,4'-dioxyacetate has a maximum value of ultraviolet absorption at 330 nm and 290 nm, and its molar extinction coefficients are 1.03 × 10 ⁴ and 1.09 × 1.
0 was ⁴ .

Further, in the same manner as in Example 2, methyl 2-hydroxybenzophenone-4,4'-dioxyacetate was hydrolyzed,
Further, the product was recrystallized with acetic acid to give 2-hydroxybenzophenone-4,4'-dioxyacetic acid (formula [V]).
9% pure pale yellow needles were obtained. This pale yellow needle-shaped crystal has a maximum value of ultraviolet absorption at 330 nm and 290 nm,
The molar extinction coefficients were 1.01 × 10 ⁴ and 1.08 × 10 ⁴ , respectively.

Next, various ester derivatives and carboxylic acid derivatives of benzophenones were obtained in the same manner as in Example 10 (Examples 11 to 13). Table 2 shows the ultraviolet absorption characteristics of each carboxylic acid derivative. The maximum ultraviolet absorption wavelength of the ester derivative was not changed from that of the corresponding saponified product, that is, the carboxylic acid derivative, and the molar absorption coefficient was hardly changed.

Example 11 "Synthesis of methyl 2-hydroxybenzophenone-3,4-oxyacetate and 2-hydroxybenzophenone-3,4-oxyacetic acid" 2,3,4-trihydroxybenzophenone as benzophenones, methyl monochloroacetate as a reaction substrate Respectively, as a ester derivative methyl 2-hydroxybenzophenone-3,4-oxyacetate pale yellow needle-like crystals,
Obtained with a yield of 63% and a purity of 98%.

Further, as a saponified product, a light yellow needle-like crystal of 2-hydroxybenzophenone-3,4-oxyacetic acid was obtained at a yield of 85% and a purity of 9%.
Obtained at 9%.

Example 12 `` Synthesis of methyl 2,2'-dihydroxybenzophenone-4,4'-bisoxyacetate and 2,2'-dihydroxybenzophenone-4,4'-bisoxyacetic acid '' 2,2 ', 4,4 as benzophenones '-Tetrahydroxybenzophenone, methyl monochloroacetate as a reaction substrate, and light yellow particles of methyl 2,2'-dihydroxybenzophenone-4,4'-bisoxyacetate as an ester derivative were obtained at a yield of 45% and a purity of 98%. Obtained.

Further, a light yellow needle-like crystal of 2,2'-dihydroxybenzophenone-4,4'-bisoxyacetic acid as a saponified compound,
Obtained in 93% yield and 99% purity.

Example 13 “Methyl 2,2′-dihydroxybenzophenone-4,4′-bis (α-methyl) -oxyacetate and 2,2′-dihydroxybenzophenone-4,4′-bis (α-methyl)-
Synthesis of oxyacetic acid "2,2 ', 4,4'-tetrahydroxybenzophenone as benzophenones, methyl 2-chloropyrropionate as reaction substrate, and 2,2' as ester derivatives
-Yellow hydroxy needle crystals of -dihydroxybenzophenone-4,4'-bis (α-methyl) -oxyacetate were obtained in a yield of 55.
% 99%.

Further, as a saponified compound, pale yellow needle-like crystals of 2,2'-dihydroxybenzophenone-4,4'-bis (α-methyl) -oxyacetic acid were obtained in a yield of 90% and a purity of 99%.

Example 14 "Synthesis of 2-hydroxybenzophenone-2,4,4'-trioxyacetic acid" 56.0 g (1.4 mol) of sodium hydroxide and 300 ml of water are placed in a four-necked flask equipped with a Dim funnel, a stirrer, a dropping funnel, and a thermometer, and stirred to dissolve sodium hydroxide. There, 98.4 g (0.4 mol) of 2,2 ', 4,4'-tetrahydroxybenzophenone was added, and the mixture was stirred at 80 ° C.
The temperature is raised to dissolve 2,2 ', 4,4'-tetrahydroxybenzophenone. While keeping the temperature constant at 80 ° C., 160.4 g (1.3 mol) of sodium monochloroacetate dissolved in 100 ml of water is added dropwise over 1 hour, and the mixture is further reacted for 5 hours.

After the reaction, when a 50% aqueous sulfuric acid solution prepared in advance at 80 ° C. is slowly added dropwise until the pH in the system becomes 2, beige particles are precipitated. This is cooled to room temperature, the particles are collected by suction filtration, and the particles are sufficiently washed with water. Further, the particles were recrystallized from acetic acid, washed again with water and dried to obtain 114.2 g of white particles.

As a result of HPLC analysis, the particles were found to have 98% purity of 2-hydroxybenzophenone-2,4,4'-trioxyacetic acid (having a structural formula represented by the formula [VI]). In addition, this particle
It had the maximum value of ultraviolet absorption at 320 nm and 270 nm, and the molar extinction coefficients at each wavelength were 1.07 × 10 ⁴ and 7.00 × 10 ³ .

Example 15 "Synthesis of methyl 2-hydroxybenzophenone-2 ', 4,4'-trioxyacetate" The 2-hydroxybenzophenone-2 ', 4,4'-trioxyacetic acid (shown in Formula VI) obtained in Example 14 was placed in a four-necked flask equipped with a Dimroth, Dean-Stark separation tube, a thermometer, and a dropping funnel. 63.0 g (0.15 mol), 96.0 (3.0 mol) of methanol and 1.6 g (0.016 mol) of sulfuric acid are added, and the mixture is slowly reacted at reflux temperature for 12 hours with stirring.
During the reaction, methanol that comes out azeotropically with water is Dean =
Although captured by a Stark separation tube, the captured water methanol was replenished by a dropping funnel in a timely manner.

After the reaction was completed, excess methanol was removed by evaporation to obtain brass-colored particles as a residue. After sufficiently washing with water, and recrystallizing twice with ethyl acetate, 39.5 g of pale yellow particles were obtained. Was. As a result of HPLC analysis, the particles contained 98.2% of methyl 2-hydroxybenzophenone-2 ', 4,4'-trioxyacetate (the structural formula is represented by the formula [VII]).
It was of purity. Further, these particles had the maximum values of ultraviolet absorption at 320 nm and 270 nm, and the molar extinction coefficients at that wavelength were 1.05 × 10 ⁴ and 6.77 × 10 ³ , respectively.

Example 16 "Synthesis of 2-hydroxybenzophenone-4-oxyacetic acid hydrazide" Synthesis of 2-hydroxybenzophenone-4-oxyacetic acid hydrazide In a four-necked flask equipped with a Dim funnel, a stirrer, a thermometer, and a dropping funnel, methyl 2-hydroxybenzophenone-4-oxyacetate 57.2 obtained in Example 1 was added. 0.2 mol) and 150 ml of methanol, 12.5 g (0.25 mol) of hydrazine hydrate was added dropwise with stirring over 10 minutes, and then 60 ° C
For 3 hours.

After the completion of the reaction, the resulting pale yellow fine particles were collected by suction filtration, washed with methanol and dried, to give a yield of 85% of 98%.
% Purity (HPLC analysis) 2-hydroxybenzophenone
4-Oxyacetic acid hydrazide (Formula [VIII]) was obtained. The pale yellow fine particles have a maximum value of ultraviolet absorption at 325 nm and 285 nm, and the molar extinction coefficient at each wavelength is 9.07 × 1
0 ³ and 1.30 × 10 ⁴ .

Next, in the same manner as in Example 16, various benzophenone ester derivatives were reacted with hydrazine, whereby hydrazide compounds were obtained with high yield and high purity (Examples 17 to 20). Table 3 shows the ultraviolet absorption characteristics of each hydrazide compound.

Example 17 "Synthesis of 2-hydroxybenzophenone-4,4'-bisoxyacetic acid dihydrazide" 2-hydroxybenzophenone-4 as a reaction substrate,
Using methyl 4'-bisoxyacetate (Example 10: Formula [IV]) and adding 2.5-fold molar hydrazine hydrate,
The mixture was reacted at 60 ° C. for 6 hours in the same manner as in 6, to obtain a light yellow fine powder of 2-hydroxybenzophenone-4,4′-bisoxyacetic acid dihydrazide in a yield of 93% and a purity of 96%.

Example 18 "Synthesis of 2-hydroxybenzophenone-4-oxymalonic acid dihydrazide" 2-hydroxybenzophenone-4- as a reaction substrate
Using diethyl oxymalonate (Example 3),
Five-fold molar hydrazine hydrate was added and reacted at 60 ° C. for 6 hours in the same manner as in Example 16 to obtain light yellow fine particles of 2-hydroxybenzophenone-4-oxymalonic acid dihydrazide at a yield of 87% and a purity of 97%. %.

Example 19 "Synthesis of 2,2'-dihydroxybenzophenone-4,4'-bisoxyacetic acid dihydrazide 5 Using 2,2′-dihydroxybenzophenone-4,4′-bisoxyacetate methyl as a reaction substrate, 2.5-fold molar amount of hydrazine hydrate was added thereto, and the mixture was heated to 60 ° C. in the same manner as in Example 16.
The reaction was carried out for 6 hours to obtain light yellow fine particles of 2,2'-dihydroxybenzophenone-4,4'-bisoxyacetic acid dihydrazide in a yield of 96% and a purity of 98%.

Example 20 "Synthesis of 2-hydroxybenzophenone-2 ', 4,4'-trioxyacetic acid trihydrazide" 2-hydroxybenzophenone as a reaction substrate
Methyl 2 ', 4,4'-trioxyacetate (Example 15: Formula [VI
I]), to which was added a 4.5-fold molar amount of hydrazine hydrate, and reacted at 60 ° C. for 7 hours in the same manner as in Example 16 to give 2
-Hydroxybenzophenone-2 ', 4,4'-trioxyacetic acid trihydrazide fine powder was prepared in 82% yield and 96% pure.
%.

Example 21 `` Synthesis of 5,5′-dicarboxy-2,2 ′, 4,4′-tetrahydroxybenzophenone '' In a three-necked flask equipped with a Dimroth, stirrer and thermometer, 2,2 ', 4,4'-tetrahydroxybenzophenone 4
9.2 g (0.2 mol), 110 g (1.1 mol) of potassium hydrogen carbonate,
And 500 g of water, gradually heated in an oil bath for 4 hours, and further vigorously refluxed for 1 hour.

After the reaction, when the temperature of the system is adjusted to pH = 1 by adding hydrochloric acid while heating, yellow particles are precipitated. After cooling, the particles are further filtered by suction filtration, and the residue is sufficiently washed with water and dried. After drying, the particles were further recrystallized with acetic acid / water = 40/60 (V / V) to give a yield of 48% and a purity of 98% (HPLC analysis).
5'-Dicarboxy-2,2 ', 4,4'-tetrahydroxybenzophenone was obtained. This compound is 340 nm, 285 nm
Had a maximum value of ultraviolet absorption, and the molar extinction coefficients at that wavelength were 9.56 × 10 ³ and 1.01 × 10 ⁴ , respectively.

Example 22 "Synthesis of 3 ', 5'-dicarboxy-4'-methoxy-2,4-bishydroxybenzophenone" In a four-necked flask equipped with a Dimroth, a stirrer (including Airtight), a thermometer, and an oxygen inlet tube, 25 g (0.1 mol) of cobalt acetate (II value), a 30% hydrogen bromide-acetic acid solution 27
g (0.1 mol), acetic acid 500 ml, 4'-methoxy-3 ', 5'
136 g of dimethyl-2,4-bishydroxybenzophenone
(0.5 mol), heated to 90 ° C., and oxygen was passed at a rate of 600 ml / min with stirring, and the reaction was continued until the absorption of oxygen ceased.

After the reaction, 500 ml of water is added dropwise while heating, and the mixture is allowed to cool, whereby yellow needle-like crystals precipitate. This was collected by absorption filtration, and the residue was recrystallized again with a 40% aqueous acetic acid solution to give 98% (HPLC analysis) pure 3 ', 5'-dicarboxy-.
4'-Methoxy-2,4-bishydroxybenzophenone was obtained. This compound had the maximum value of ultraviolet absorption at 325 nm and 285 nm, and the molar extinction coefficients at that wavelength were 8.01 × 10 ³ and 1.34 × 10 ⁴ , respectively.

Example 23 "Synthesis of saturated polyester containing benzophenones of the present invention" In an autoclave, 166.0 g (1.0 mol) of terephthalic acid, 2,2'-dihydroxybenzophenone-4,4'-dioxy obtained in Example 12 1.1 g (0.003 mol) of acetic acid, 136.4 g (2.2 mol) of ethylene glycol, 0.05 g of germanium dioxide, and 0.05 g of sodium hydroxide were added, and the mixture was stirred at 230 ° C. for 1 hour and 250 ° C. for 1 hour while stirring at about 3 atm. time
The reaction was performed for 30 minutes. During the reaction, the produced water was distilled off azeotropically with ethylene glycol.

After the completion of the reaction, the reaction mixture is transferred to a polymerization reactor, and 0.05 g of antimony trioxide is added, followed by heating with stirring. Further reduce the pressure gradually and distill off ethylene glycol.
The reaction was performed at a final pressure of 0.3 Torr and 280 ° C. for 3 hours. After the reaction,
The obtained polymer was phenol / tetrachloroethane = 1 /
In 1 (wt / wt), it had an intrinsic viscosity of 0.62 dl / g.

Next, a part of this polymer was taken, melted and cast to obtain a transparent film having a thickness of 1 mm. For the remaining polymer, 0.02 parts of a dye (Sumiplast Blue GP: manufactured by Sumitomo Chemical Co., Ltd.) was melt-mixed with respect to the weight of the polymer, and cast to obtain a blue transparent film having a thickness of 1 mm. Was.

Example 24 "Synthesis of saturated polyester containing benzophenones of the present invention-Part 2" The 2-hydroxy compound obtained in Example 10 was placed in a polymerization reactor equipped with a vacuum stirrer, a nitrogen inlet tube, and a Liebig condenser. Benzophenone-4,4'-dioxyacetate methyl 37.4 g (0.1
Mol), 15.2 g (0.2 mol) of propylene glycol, 0.05 g of calcium acetate, and 0.05 g of antimony trioxide. The mixture is heated to 180 ° C. while stirring, and nitrogen gas is passed slowly.
The reaction is continued until the methanol generated by the reaction reaches a theoretical amount (about 2 hours). When the distillation of methanol is completed, the temperature is gradually raised and the pressure is reduced to 0.3 Torr. Then 2
The reaction was carried out at 50 ° C. for 3 hours, and cooled after the reaction to obtain a yellow polymer.

This polymer is phenol / tetrachloroethane = 1 /
It had an intrinsic viscosity of 0.55 dl / g in 1 (wt / wt).

Comparative Example 1 “Synthesis of saturated polyester for blank” The same operation as in Example 23 was performed using 332.0 g (2.0 mol) of terephthalic acid and 248.0 g (4.0 mol) of ethylene glycol to obtain a polymer. Next, 1/6 amount of this polymer was melted and cast to obtain a transparent film having a thickness of 1 mm.

Similarly, with respect to 100 parts of the polymer, 2- (5'-
A 1 mm thick transparent film containing 0.5 parts of methyl-2'-hydroxyphenyl) benzotriazole, and a 1 mm thick blue transparent film containing 0.02 parts of a dye (Sumiplast Blue GP) per 100 parts of the polymer. , This polymer 100
Parts, 0.02 parts of dye (Sumiplast Blue GP) and 2 parts
1 mm thick blue transparent films containing 0.5 part of-(5'-methyl-2'-hydroxyphenyl) benzotriazole were produced.

Example 25 "Production of a saturated polyester prepared by blending the polyester of the present invention by a master batch method" To 100 parts of the polyester obtained in Comparative Example 1, 0.62 part of the polyester of the present invention obtained in Example 24 was blended and cast. 1mm thick transparent film and Comparative Example 1
100 parts of the polyester obtained in the above, 0.62 parts of the polyester of the present invention obtained in Example 24, and 0.02 part of the dye (Sumiplast Blue GP) were blended to produce a 1 mm thick transparent blue film.

Example 26 "Synthesis of unsaturated polyester containing benzophenones of the present invention" 98 g (1 mol) of maleic anhydride, 2-hydroxybenzophenone-4-oxymalonic acid obtained in Example 3 1.
A polymer was obtained in the same manner as in Example 24, using 6 g (0.005 mol) and 136.4 g (2.2 mol) of ethylene glycol.
However, the reaction temperature in the esterification reaction was 170 ° C., and the reaction conditions in the polycondensation reaction were 180 ° C. and 0.3 Torr. The obtained polymer was phenol / tetrachloroethane = 1/1 (wt / w
In t) it had an intrinsic viscosity of 0.605 dl / g.

Next, the polymer is melted and cast to a thickness
A 1 mm transparent film was formed. In the same manner, a dye (Sumiplast Blue GP) is used for 100 parts of the polymer.
Was blended with 0.02 parts of a blue transparent film having a thickness of 1 mm.

Comparative Example 2 "Synthesis of Unsaturated Polyester for Blank" The same operation as in Example 26 was performed using 392.0 g (4.0 mol) of maleic anhydride and 496.0 g (8.0 mol) of ethylene glycol to obtain a polymer.

Take a part of this, melt and cast,
A transparent film having a thickness of 1 mm was obtained.

Similarly, with respect to 100 parts of the polymer, 2- (5'-
A 1 mm thick transparent film containing 0.5 parts of methyl-2'-hydroxyphenyl) benzotriazole and a 1 mm thick blue transparent film containing 0.02 parts of a dye (Sumiplast Blue GP) per 100 parts of the polymer. , This polymer 100
Then, a blue transparent film having a thickness of 1 mm was prepared by mixing 0.5 part of 2- (5'-methyl-2'-hydroxyphenyl) benzotriazole and 0.02 part of a dye (Sumiplast Blue GP).

Example 27 “Production of unsaturated polyester prepared by blending the polyester of the present invention by a master batch method” To 100 parts of the blank polymer obtained in Comparative Example 2,
A transparent film having a thickness of 1 mm containing 0.62 parts of the benzophenone-containing polyester of the present invention obtained in Example 24, and a dye (Sumiplast Blue G)
P) Blue transparent films having a thickness of 1 mm each containing 0.02 parts were produced.

Example 28 "Synthesis of polyamide containing benzophenones of the present invention" Adipic acid 146.02 g (1.0 mol) obtained in Example 12
1.1 g (0.003 mol) of 2,2'-dihydroxybenzophenone-4,4'-bisoxyacetic acid, hexamethylenediamine 12
1.8 g (1.05 mol) is added to 70 g of ion-exchanged water and stirred at room temperature until uniform. This is placed in an autoclave, and pressurization and release of pressure with nitrogen gas are repeated five times to replace air in the system with nitrogen gas. Thereafter, the autoclave is heated and reacted at a temperature of 210 ° C. and a pressure of 17 kg / cm ² for 4 hours.
When the pressure was increased, an operation of slightly opening the exhaust valve was performed so that the pressure became 17 kg / cm ² . During this operation, the internal temperature is further increased to 270 ° C., and after maintaining this temperature for 30 minutes even after normal pressure, the system is allowed to cool.

The resulting polymer had an intrinsic viscosity of 0.50 dl / g in m-cresol.

Next, the polymer is melted and cast to a thickness
A 1 mm transparent film was formed. In the same manner, a dye (Sumiplast Blue GP) 0.0
A 1 mm-thick blue transparent film containing 2 parts was prepared.

Comparative Example 3 "Synthesis of polyamide for blank" A polymer was obtained by performing the same operation as in Example 28 using 365.0 g (2.5 mol) of adipic acid and 290.0 g (2.5 mol) of hexamethylenediamine.

Next, a part of this was melted and cast to obtain a transparent film having a thickness of 1 mm.

Similarly, 2- (5 ') was added to 100 parts of the polymer.
-Methyl-2'-hydroxyphenyl) benzotriazole 0.5 part transparent film blended with 0.5 part, and 1 part thick blue transparent film blended with 0.02 part of dye (Sumiplast Blue GP) per 100 parts of this polymer And this polymer 1
Blue transparent films having a thickness of 1 mm were prepared by mixing 0.5 part of 2- (5'-methyl-2'-hydroxyphenyl) benzotriazole and 0.02 part of a dye (Sumiplast Blue GP) per 00 parts.

Example 29 "Synthesis of polyamide containing benzophenones of the present invention-Part 2, and production of polyamide prepared by blending the polyamide by a master batch method" 2-hydroxybenzophenone obtained in Example 10
A pale yellow polymer was obtained in the same manner as in Example 28 by using 34.6 g (0.1 mol) of 4,4'-dioxyacetic acid and 10.8 g (0.1 mol) of p-phenylenediamine. This polymer has m-
It had an intrinsic viscosity of 0.47 dl / g in cresol.

Next, with respect to 100 parts of the polymer obtained in Comparative Example 3, 0.62 parts of the polymer obtained above was melt-mixed and cast to obtain a transparent film having a thickness of 1 mm.

In the same manner, a blue transparent film having a thickness of 1 mm in which 0.62 part of the polymer obtained above and 0.02 part of the dye (Sumiplast Blue GP) were blended with 100 parts of the polymer obtained in Comparative Example 3 was prepared. Produced.

Example 30 "Synthesis of polyurethane containing benzophenones of the present invention" Methyl 2,2'-dihydroxybenzophenone-4,4'-bis (α-methyl) oxyacetate obtained in Example 13 35.
Using 0 g (0.08 mol), 87.0 g (0.5 mol) of dimethyl adipate, 106.0 g (1 mol) of diethylene glycol, 0.2 g of calcium acetate and 0.2 g of antimony trioxide,
A polyester having an average molecular weight of 5000 is obtained in the same manner as in 24.

Next, in a separable flask equipped with a stirrer, 100 parts of the polyester obtained above was reacted with theoretical N after the reaction.
Tolylene diisocyanate (TDI) is mixed and reacted so that the CO remaining amount becomes 3%, and finally the NCO remaining amount becomes 3.4%
Was obtained.

Further, 20 parts of dioctyl phthalate was mixed and stirred with 100 parts of the prepolymer, and the mixture was poured into a mold having a thickness of 1 mm, and left to stand for one week to be cured to obtain a polyurethane film.

Comparative Example 4 "Synthesis of polyurethane for blank" In Example 30, the same operation as in Example 30 was performed, except that the polyol was changed to a diol having a molecular weight of 2000, in which propylene glycol was added with 50% each of ethylene oxide and propylene oxide. Then, a polyurethane resin film for a blank in a weather resistance test was obtained.

Further, based on 100 parts of the urethane prepolymer for blank obtained above, 20 parts of dioctyl phthalate, 2-
0.5 part of (5'-methyl-2'-hydroxyphenyl) benzotriazole is kneaded and cured in the same manner to a thickness of 1 mm.
Was obtained.

Example 31 "Synthesis of Polyurethane Containing Benzophenones of the Present Invention-Part 2" 0.7 part of polyester obtained in Example 30, 69.3 parts of diol used in Comparative Example 1, and 50 parts each of glycerin containing ethylene oxide and propylene oxide. The theoretical NOC after the reaction was obtained using 30 parts of triol having a molecular weight of 2,000 added in%.
4,4'-diphenylenediisocyanate was blended so that the amount became 3%, and a urethane polymer having a residual NOC of 3.1% was finally obtained in the same manner as in Example 30.

Further, 20 parts of dioctyl phthalate was mixed and stirred with 100 parts of the urethane prepolymer, poured into a mold having a thickness of 1 mm, and allowed to stand for one week to cure, thereby obtaining a transparent polyurethane film.

Example 32 "Synthesis of Epoxy Resin Containing Benzophenones of the Present Invention" 100 parts of Asahi Epoxy Resin A, E, R330 (bisphenol A diglycidyl ether type liquid epoxy resin having an epoxy equivalent of 180 to 190: manufactured by Asahi Kasei Corporation) 2 obtained in Example 16
-Hydroxybenzophenone-4-oxyacetic acid hydrazide (5 parts) and adipic acid dihydrazide (25 parts) were mixed and stirred for 1 hour, defoamed, poured into a 1 mm thick mold, and cured in an oven at 160 ° C.

Example 33 "Synthesis of Epoxy Resin Containing Benzophenones of the Present Invention-Part 2" 100 parts of Asahi Epoxy Resin A, E, R330, 2,2'-dihydroxybenzophenone-4,4 obtained in Example 19 Using 25 parts of '-bisoxyacetic acid hydrazide, a cured product was obtained in the same manner as in Example 32.

Comparative Example 5 "Synthesis of epoxy resin for blank" For the blank test of the weather resistance test, the same operation was performed using 100 parts of Asahi epoxy resin A, E, R330 and 25 parts of adipic dihydrazide to obtain a cured product. .

Measurement—Weather Resistance Test— The films obtained in the above Examples and Comparative Examples were each subjected to a weather resistance test.

The test is carried out under the following conditions in accordance with the sunlight fastness test of JIS plastic building materials, and the color difference on the surface of the film is measured using a colorimetric color difference meter (Nippon Denshoku Industries Co., Ltd .: Z-1001DP type).
Was measured.

(Weather resistance test conditions) Model: Sunshine weather meter WEL-SUN-DC
(H) type (manufactured by Suga Test Instruments Co., Ltd.) Light source: carbon arc, continuous irradiation Spray circle: 18 minutes / 120 minutes Test tank temperature: 42 ° C Test tank humidity: 40% RH (Measurement results) Exposure time 100 hours, 200
The measurement was performed at the hour, the 2000 hour, and the 3000 hour, and the measurement results are shown in FIGS. 1 to 6. Note that ΔE in each drawing represents a color difference.

Among them, Fig. 1 shows a polyester dye blend, Fig. 2 shows a polyester dye not blended, Fig. 3 shows a polyamide dye blend, Fig. 4 shows a polyamide dye not blended, and Fig. 5 shows a polyurethane (no dye blended). 6) and FIG. 6 show the case of epoxy resin (without dye). In addition, when the dye is blended, the degree of yellowing of the resin itself is mainly shown when the dye is faded, and when the dye is not blended, the degree of yellowing is mainly shown.

As is clear from the figure, the resin incorporating the benzophenone-based compound of the present invention exhibits extremely excellent weather resistance.

[Effect of the Invention] The benzophenone-based compound of the present invention has a novel reactive ultraviolet absorption in which a carboxyl group, an ester group, an amide group, a hydrazide group, etc., which can react with a hydroxyl group, an epoxy group, an isocyanate group, etc., are introduced into the molecule. It has excellent ultraviolet absorption performance and exhibits a sufficient ultraviolet absorption effect even at low concentrations. In addition, it has versatility with many resins to be incorporated, and can be introduced as a component into many resins such as polyester, polyamide, polyurethane, and epoxy resins by a condensation reaction or an addition reaction. Further, a resin containing the benzophenone-based compound of the present invention as a component can be mixed with an ordinary resin in a masterbatch system to be molded.

On the other hand, the resin containing the benzophenone-based compound of the present invention as one component does not disappear due to scattering or elution of the ultraviolet absorber because the resin itself has ultraviolet absorption performance,
It has long term light stability and shows excellent weather resistance and light resistance.
In particular, it is a great feature that it is effective for a polyamide in which the ultraviolet absorber could not be mixed because of the poor compatibility with the conventional ultraviolet absorber. In addition, long-term prevention of light deterioration, prevention of discoloration, prevention of binder deterioration, long-term stability of contents when used in containers for polyester, polyurethane and other condensation reaction type and addition reaction type resins. To achieve.

Moreover, the incorporation of the benzophenone-based compound of the present invention can be carried out in the same manner as in the conventional condensation reaction and addition reaction, and is extremely significant because no special apparatus or technique is required.

[Brief description of the drawings]

The drawings are graphs showing the relationship between the exposure time and ΔE for the films of the examples and comparative examples. FIG. 1 shows a polyester dye blend, FIG. 2 shows a polyester dye unblended, and FIG.
The figure shows the case of blending a polyamide dye, FIG. 4 shows the case of a polyamide without a dye, FIG. 5 shows the case of a polyurethane (no dye), and FIG. 6 shows the case of an epoxy resin (no dye).

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C08G 63/66 C08G 63/66 63/68 63/68 // C07C 49/83 C07C 49/83 A (72) Inventor Takashi Ikeda Tsukasa 1516-1, Oda-cho, Ono-shi, Hyogo Pref.Inside Yatsuo Kogyo Co., Ltd. 165402 (JP, A) JP-A-62-129212 (JP, A) JP-A-62-30180 (JP, A) JP-A-61-200941 (JP, A) (58) Fields investigated (Int. ⁶ , DB name) C09K 3/00 C08G 63/18-63/68 C08G 59/40 C07C 49/83-49/84 CA (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] 1. A reactive ultraviolet absorber comprising a benzophenone compound represented by the general formula [I]. However, in the formula [I], X: a group represented by a hydroxyl group or Q, Z: an atom or a group represented by hydrogen, a hydroxyl group, a methoxy group or Q, wherein at least one of X or Z is represented by Q It is a group to be performed. Those selected from, but R ¹ is -OH, C ₁ -C straight or branched chain alkoxy group having ₄ or -NHNH ₂ from selected groups, straight-chain R ² is C ₁ -C ₄ Or a group selected from a branched chain alkylene group. Y: hydrogen, hydroxyl, straight-chain or branched-chain alkyl residue, or an atom or a group selected from the group represented by Q of C ₁ -C _4. R ³ and R ⁴ : groups selected from hydrogen and C _{1 to} C ₄ linear or branched alkyl residues. h: any integer from 1 to 4, provided that X is different from 2 to 4. l: any integer from 1 to 4, provided that Z is different from 2 to 4. m: any integer not exceeding 4-l, provided that in the case of 2-3, R ³ may be different. n: any integer not exceeding 4-h, provided that R ⁴ may be different in the case of 2-3. 2. A copolymer of a benzophenone compound comprising the compound [I] according to claim 1 as a polymerization component.