JPH0794655B2 - UV stabilizer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention relates to a novel compound which is compounded with various organic substances and exhibits an excellent ultraviolet absorbing ability.

[Conventional Technology and Problems Thereof] As a UV stabilizer (UV absorber) for synthetic polymer substances, conventionally known are salicylic acid ester-based compounds, benzotriazole-based compounds, hydroxybenzophenone-based compounds, and the like. With the exception of very few conventional UV stabilizers [eg 2-hydroxy-4- (2-hydroxy-3-methacrylyloxy) propoxybenzophenone], most of them are solid at room temperature and generally Used in powder form.
Therefore, when compounding a conventional ultraviolet stabilizer with a plastic or the like, there is a problem that dust generated during weighing or blending pollutes the work environment.

Therefore, the present invention proposes a UV stabilizer containing a novel compound as an active ingredient, which is liquid at room temperature and exhibits a performance comparable to or superior to that of the conventional UV stabilizers.

[Means for Solving Problems] The novel compound of the present invention is represented by the following general formula.

In the formula, R ₁ represents a hydrogen atom or a hydroxy group, R ₂ and R ₃ represent a hydrogen atom, a halogen, a carboxy group, an amino group, an alkyl group having 1 to 6 carbon atoms, an aryl group, an alkoxy group having 2 to 7 carbon atoms. A carbonyl group, an alkoxy group having 1 to 18 carbon atoms, an alkylamino group having 1 to 3 carbon atoms or a dialkylamino group having 1 to 3 carbon atoms, Y ₁ , Y ₂ , Z ₁ and Z ₂ are hydrogen atoms, Or an -OCnH ₂ nO _m R ₆ (where the R ₄ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ₅ is an alkyl group having 2 to 12 carbon atoms, R ₆ is from 1 to 12 carbon atoms N is 2
3 and m are 2 to 4, but Y ₁ and Z ₁ are not both hydrogen atoms).

The novel compound which is liquid at room temperature according to the present invention is at the 4-position and / or the 4'-position of 2-hydroxybenzophenone, Or it is important to have a -OCnH ₂ nO _m R _6. Therefore, in synthesizing the compound of the present invention, 2-hydroxybenzophenone or a derivative thereof having a hydroxy group at the 4-position and / or the 4'-position is used as a starting material. For example, 2,4-dihydroxybenzophenone or
Using 2,2 ', 4,4'-tetrahydrobenzophenone as a starting material, the method for producing the compound of the present invention will be described. The starting material, benzophenone, is dissolved in an appropriate organic solvent, and alkali carbonate, caustic soda, In the presence of caustic potash or the like, an unsaturated lower aliphatic hydrocarbon halide having an alkoxy group is reacted at 50 to 80 ° C. By this, the hydroxy group in the para position with respect to the carbonyl group of benzophenone, Or -OCnH ₂ nO _m so selectively substituted in R _6, after removing the organic solvent from the reaction mixture, separation and recovery with appropriate means, by purification, can be obtained the desired compound is liquid at room temperature .

Even when benzophenone having a substituent other than the para-position with respect to the carbonyl group of benzophenone is used as a starting material, the compound of the present invention can be produced by the method described above in principle.

The compound of the present invention, which is liquid at room temperature, is effective as an ultraviolet stabilizer for various polymer substances or organic compounds,
Examples of polymeric substances that can be protected from ultraviolet rays by the compounds of the present invention are as follows.

Olefin-based homopolymers and copolymers; Styrene-based homopolymers and copolymers; Halogen-containing polymers such as polyvinyl chloride; Homopolymers and copolymers of α, β-unsaturated acids or derivatives thereof; Unsaturated alcohols and amines or acyl derivatives thereof Or polymers obtained from acetals; homopolymers and copolymers of cyclic ethers; polyacetals; polyphenyl oxides and polyphenyl sulfides; polyethers having hydroxy end groups, polyesters and polybutadienes as one component, and aliphatic or aromatic polyisocyanates Polyurethanes and their precursors (polyisocyanates, polyols and their prepolymers) produced as the other component; diamines and dicarboxylic acids and / or aminocarboxylic acids or the corresponding laths. Homopolyamides and copolyamides obtained from lactams; Polyureas, polyimides and polyamideimides; Polyesters obtained from dicarboxylic acids and diols and / or hydroxycarboxylic acids or corresponding lactones; Polycarbonates; Polysulfones and polyethersulfones; And crosslinked polymers obtained by using phenol, urea and melamine as the other components; dry and non-drying alkyd resins; unsaturated polyesters obtained from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and vinyl compounds as crosslinking agents Resins and flame retardant halogen-containing modified products; Substituted acrylic acid esters; Alkyd resins, polyester resins and acrylates crosslinked with melamine resins, urea resins, polyisocyanates or epoxy resins Fats; polyepoxides; natural polymers; aqueous emulsion or the like of natural or synthetic rubber.

The UV stabilizer of the present invention, like the conventionally known UV stabilizers or UV absorbers, has the effect of preventing the photodegradation of the various polymeric substances themselves exemplified above, for example, a packaging material for polymeric substances. Also, it is effective in preventing the deterioration of the contents when the above condition occurs or preventing the fading of the adhesive having poor light resistance.
The method of use is also the same as that of the conventionally known ultraviolet stabilizer or ultraviolet absorber, and it is possible to employ kneading into a molding material or surface coating onto a molded product. In particular, since the UV stabilizer of the present invention is liquid at room temperature, it is suitable as a stabilizer when stabilizing a polymer substance or other organic compound that is liquid at room temperature, and when kneaded into a molding material. Even when it is applied to the surface of a molded product such as a film, the workability is excellent.

The amount of the ultraviolet stabilizer of the present invention to be used varies depending on the kind of the target polymer substance and its application, but generally about 0.01 to 5% by weight, preferably about 0.05 to about 5 to about 100 to be stabilized.
2% by weight, particularly preferably 0.1 to 1% by weight is added. In this case, the UV stabilizer of the present invention includes, for example, phenolic antioxidants, wetting agents, raw materials, colorants, dyes, other UV absorbers, light stabilizers such as hindered amines,
It does not prevent the combined use with various additives such as metal deactivators and fillers such as talc.

[Examples] Example 1 To a 300 ml four-necked Kolben flask, 21.4 g (0.1 mol) of 2,4-dihydroxybenzophenone, 150 ml of acetone, and 4.4 g (0.11 mol) of caustic soda were added and heated to 50 ° C. 2-ethoxyethylene chloride 11.4g (0.105mol)
Was added dropwise at the same temperature for 4 hours. Next, after reacting at 55 ° C. for one day under stirring, acetone was distilled off, and 50 ml of warm water was added to the residual reaction product to dissolve the produced inorganic substance and the like, and the produced oily substance was fractionated.

This oily substance is washed several times with warm water, dehydrated under reduced pressure, and then subjected to vacuum distillation to obtain 225 to 227 ° C.
A compound of the present invention which is a pale yellow oily substance at / 6 mmHg, 2-
Hydroxy-4- (2'-ethoxyethoxy) benzophenone was obtained. Yield 21.1g, yield 78%, viscosity 490cps (25
C).

Example 2 In a 300 ml four-necked Kolben flask, 2,2 ', 4,4'-tetrahydroxybenzophenone 24,6 g (0.1 mol), methyl ethyl ketone 150 ml, potassium carbonate 29.0 g (0.2 mol), 2-
Charge 32.2 g (0.20 mol) of ethoxyethylene bromide and 150 ml of methyl ethyl ketone and heat to 70-75 ° C for 16
Reacted for hours. Then, methyl ethyl ketone was distilled off, and 100 ml of warm water was added to the remaining reaction product to dissolve the produced inorganic substance and the like, and the produced oily substance was separated.

This oily substance is washed with warm water several times, dehydrated under reduced pressure, and then subjected to vacuum distillation to obtain 205 to 209 ° C.
A compound of the present invention that exhibits a pale yellow oily state at / 2 mmHg, 2,
2'-Dihydroxy-4,4'-di (2'-ethoxyethoxy) benzophenone was obtained. Yield 20.7g, yield 65%, viscosity 520cps (25 ° C).

Example 3 By repeating exactly the same operation as in Example 2 except that 2-butoxyethylene bromide was used in place of 2-ethoxyethylene bromide, the compound of the present invention which was in the form of a pale yellow oil, 2-hydroxy- 4- (Butoxyethoxy) benzophenone was obtained. Yield 74%, viscosity 51
5cps (25 ℃).

Example 4 Instead of 2-ethoxyethylene bromide, 2- (2
-Methoxyethoxy) ethylene bromide was used, except that the same operation as in Example 2 was repeated,
The compound of the present invention, which is in the form of a pale yellow oil, 2,2'-dihydroxy-4,4'-di [2- (2-methoxyethoxy)
Ethoxy] benzophenone was obtained.

Yield 48%, viscosity 490cps (25 ℃).

Example 5 The compound obtained in Example 1 was dissolved in acetone to give 0.15 g /
A solution of 1 was prepared. To 31.6 parts by weight of this solution, 40 parts by weight of polypropylene powder which has not been substantially stabilized is added, and acetone which is 1.5 times the volume of the solution is further mixed to form a homogeneous slurry. It was distilled off by an evaporator to obtain a dry powder.

Place 14g of this dry powder in a 6x6x0.015 inch mold,
The mold and mica plate were heated in the press under contact pressure for 5 minutes. Then, a pressure of 2700 kg / cm ² was applied for 1 minute and then cooled, then the pressure was raised to 10800 kg / cm ² at 150 ° C., then cooled and taken out of the press at 50 ° C. to obtain a sample sheet.

Sample sheets having different compounded compounds were prepared in exactly the same manner as described above except that the compounds obtained in Examples 2 to 4 were used in place of the compound obtained in Example 1.

Next, in the light irradiation device in which 28 solar lamps and black light lamps are alternately arranged in a circular row, each of the above sample sheets is stored, and each sample sheet is uniformly irradiated with light while each sample is sampled. The time until it was bent at 180 degrees and broken was measured periodically.

For comparison, the same test was performed for the blank test and the case where a known ultraviolet stabilizer was used. The results are shown in Table 1.

The results shown in the above table show that the compounds of the present invention exhibit a far superior photostabilizing effect as compared with known ultraviolet stabilizers.

Claims (1)

[Claims] 1. A UV stabilizer containing a 2-hydroxybenzophenone derivative represented by the following general formula as an active ingredient. [In the formula, R ₁ represents a hydrogen atom or a hydroxy group, and R ₂ , R ₃
Is a hydrogen atom, halogen, carboxy group, amino group, alkyl group having 1 to 6 carbon atoms, aryl group, alkoxycarbonyl group having 2 to 7 carbon atoms, alkoxy group having 1 to 18 carbon atoms,
Shows an alkylamino group having 1 to 3 carbon atoms or a dialkylamino group having 1 to 3 carbon atoms, Y ₁ , Y ₂ , Z ₁ and Z ₂ are hydrogen atoms, Or -OCnH ₂ nO _m indicating the R ₆ a (R ₄ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ₅ is an alkyl group having 2 to 12 carbon atoms, R ₆ is an alkyl group having 1 to 12 carbon atoms , N is an integer of 2 to 3, and m is an integer of 2 to 4, provided that Y ₁ and Z ₁ are not both hydrogen atoms. ]