JPS61192778A - Water-soluble ultraviolet absorber - Google Patents

Abstract

PURPOSE:To provide the titled absorber having excellent dispersion and transparency and capable of being added to a cationic electrodeposition paint because of its high water solubility, which is low in volatility and exhibits the effect by adding a small amount of it, by using a 2-hydroxybenzophenone compound as a starting material. CONSTITUTION:The substituent C1 and/or the substituent C2 of a 2- hydroxybenzophenone compound of the formula I (wherein A and B are each H, a halogen, an alkyl or an alkoxy; Y is H or OH; C1 and C2 are each groups of the formula II or III, etc.; and Q1 and Q2 are each a 1C or 5C or lower alkylene) are reacted with an amino compound of the formula IV or V (wherein Q3 is an alkylene and Q4-Q5 are each an alkyl). The terminal amino group or tertiary amine of the obtained compound is reacted with an alkyl halide of the formula Q6X (wherein Q6 is CH3, etc.; and X is a halogen) to obtain a water-soluble benzophenone ultraviolet absorber of the formula VI [wherein Z1 and/or Z2 are a quaternary ammonium salt of the formula VII or VIII (wherein R1 is a direct bond or an alkylene; R2 is an alkylene; and R3-R5 are each an alkyl)].

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a water-soluble ultraviolet absorber, which can be added to various organic materials such as paints, cosmetics, and dyes to impart ultraviolet absorption ability. Ru.

[Prior Art] Generally, organic compounds are degraded by ultraviolet rays contained in sunlight, causing problems such as discoloration and decreased strength. In order to solve this problem, ultraviolet absorbers are conventionally added to paints, cosmetics, resin films, etc. to protect the materials to which they are added or the skin, foods, etc. covered by them from ultraviolet rays. A wide variety of such ultraviolet absorbers have been developed, including benzotriazole-based, benzophenone-based, and cyanoacrylate-based UV absorbers, and various types are selected and used depending on the use, purpose, etc.

[Problems to be Solved by the Invention] The conventional ultraviolet absorbers described above are generally oil-soluble and cannot be incorporated into water-soluble paints, cosmetics, etc. Furthermore, benzophenone-based ultraviolet absorbers with anionic groups have been developed, but none with cationic groups have yet been developed.

For this reason, there have been no benzophenone-based ultraviolet absorbers that can be added to cationic electrodeposition paints.

Conventional UV absorbers also have compatibility with additive materials,
Many have small molecular weights in consideration of their ultraviolet absorption ability.

Such ultraviolet absorbers sometimes sublimate and volatilize due to heating during baking of paint films, molding of resins, etc., or gradually volatilize over time, resulting in a decrease in effectiveness. To solve these problems, a method of reacting the additive material and the ultraviolet absorber is known. However, this method requires complicated reaction control, compounding methods, etc., and is applicable only to specific materials, making it difficult to apply it widely. Another method is to increase the molecular weight of the ultraviolet absorber, but there is generally a problem that increasing the molecular weight lowers the ultraviolet absorbing ability.

The present invention was made in view of the above-mentioned problems, and it is an object of the present invention to provide an ultraviolet absorber that is water-soluble, can be added to cationic electrodeposition paints, and is difficult to volatilize.

[Means for solving the problems] The water-soluble ultraviolet absorber of the present invention has the general formula (I) (wherein A
and B are selected from a hydrogen atom, a halogen atom, an alkyl group, and an alkoxy group, and Y represents a hydrogen atom or a hydroxyl group, respectively),
At least one of t is a quaternary ammonium salt.

The active ingredient of the present invention is a novel benzophenone compound represented by the general formula (I), which is extremely effective as an ultraviolet absorber for protecting organic substances from the harmful effects of ultraviolet light.

In the compound represented by the general formula (,T) of the present invention,
A and B represent substituents on the benzene ring, and may be any of a hydrogen atom, a halogen atom, an alkyl group, and an alkoxy group. Here, halogen atoms are chlorine, fluorine,
Each element of bromine and iodine can be used. Further, the number of carbon atoms of the alkyl group and alkoxy group is not limited, but it is particularly desirable to use a methyl group or a methoxy group having one carbon number.

In this way, the molecular weight of compound (I) becomes small and the ultraviolet absorption ability increases. Note that A and 8 may be the same substituent or different substituents.

Y also represents a substituent on the benzene ring like A and B above, but
It is a substituent present at the 2- or 2-position of formula (I), and either a hydrogen atom or a hydroxyl group can be used.

Zt and Zt similarly represent substituents on the benzene ring, but the feature of the present invention is that at least one end of Zt and Zt is a quaternary ammonium salt. In addition, when only one is made into a quaternary ammonium salt, the other means a hydrogen atom.

Here, a quaternary ammonium salt is an ammonium salt represented by the general formula NHaX, where X is an acid group, a hydroxyl group, etc., and N(
R) 4X. This quaternary ammonium salt N (R)
4 X dissociates like N (R) a ''+X- and has good water solubility.

In the compound (I>) of the present invention, at least one of Zt and Zt has -R+-000-R2-N" (R3, R4, R5).
X-1 -RI -Co0-R2-N" (R3, R4, R5
)・X-1 -R+ -Co-NH-Rt-N" (R3, R4
, R5) ・X″″, -R1-803-NH-R1-N” (R3, R4,
Quaternary ammonium salts such as Rs).X- can be used. Here, R+ represents a direct bond or alkylene, and one end is bonded to the carbon of the benzene ring of the benzophenone compound. This R1 has 1 to 5 carbon atoms, considering the reactivity during synthesis, ultraviolet absorption performance, water solubility, etc.
Alkylene or a direct bond with zero carbon atoms is preferable. Similarly, R2 is alkylene,
For the same reason, it is desirable to select one having less than 4 carbon atoms. R3, R4 and R5 are alkyl groups. This alkyl group is also preferably one having a small number of carbon atoms for the same reason as above, and a methyl group having one carbon number is particularly desirable. Further, the halogen atom of X can be selected from iodine, bromine, chlorine, and the like. Note that even when both Zl and Zt are quaternary ammonium salts, ZI and 72 do not necessarily have to be the same substituent.

The raw materials and manufacturing method for obtaining the ultraviolet absorbent of the present invention will be described below.

In producing the water-soluble ultraviolet absorber of the present invention, for example, a 2-hydroxybenzophenone compound represented by the general formula ([) having ultraviolet absorbing ability can be used as a starting compound.

Here, A and B can be freely selected from hydrogen atoms, halogen atoms, alkyl groups, and alkoxy groups. Note that among these alkyl groups and alkoxy groups, it is desirable to use those containing 1 carbon number.

In the compound of formula (IF), Y may be either a hydrogen atom or a hydroxyl group. Moreover, at least one or both of C1 and C2 is -Q + -OH, -Qz-C
It can be freely selected from OOH, -Qz GOX, and -Qt 503Na. Note that here, X is a halogen atom. Further, QI and Qt are alkylene, and QI preferably has 1 carbon number or a direct bond, and C2 preferably has 5 or less carbon atoms.

At least one group of CI and Ox in the compound of formula (If) above is, for example, HtN-C3-NHt.

HO-C3-N (C4, Qs), HOOC-C3
-N (Qa, Qs), X0C-C3-N (C
4, Qs), etc. Note that here, X is a halogen atom, C3 is alkylene, C
4, C5 is an alkyl group. And C3 has 4 carbons
As for the smaller C4 and C5, it is desirable to use a methyl group having one carbon number.

According to the above, at least one of C1 and C2 of the compound of formula (IF) has a terminal of -N H2 or -N (C
4, C5). Then, by reacting this terminal amino group or tertiary amine with an alkyl halide (Q@X), a quaternary ammonium salt can be obtained. Note that here, X is a halogen atom. Further, from the viewpoint of reactivity, 06 is preferably a methyl group having one carbon.

A typical example of this is methyl iodide.

In order to apply the ultraviolet absorber of the present invention containing the compound of general formula (I) as an active ingredient to organic substances, conventionally known general methods can be used as they are. The compound (I) of the present invention can generally be used for all organic polymeric materials, but especially for fully synthetic polymers such as addition polymers, especially for polymers of compounds having ethylenic double bonds, such as polymers. Vinyl chloride, polyvinylidene chloride, styrene polymers, diene polymers and copolymers thereof, polyethylene, polypropylene, polyacrylic compounds, especially polymethyl methacrylate or polyacrylonitrile, and also condensation polymers such as polyethylene glycol terephthalate Q- or polyamides, such as polybrolactam, or mixed polymers, such as addition copolymers of olefins and unsaturated polyesters, such as polyester resins, such as styrene or methyl methacrylate, as well as natural polymers or their synthesis. Modified products such as cellulose, cellulose ester,
It has excellent effects on cellulose ether and protein.

The most distinctive feature of the present invention is that the end group of the ultraviolet absorber is a cationic quaternary ammonium salt. As a result, a water-soluble ultraviolet absorber can be obtained while maintaining the ultraviolet absorption performance of the benzophenone moiety. Therefore, it can be added to water-dispersible or water-soluble organic materials. It also becomes possible to add it to cationic W paints, which was previously difficult.

The surfaces of inorganic and organic pigments, fillers, etc. that are electrolyzed into paints and the like are often hydrophilic. Since the ultraviolet absorber of the present invention is ionic, it easily adsorbs onto the surfaces of these pigments and fillers. That is, it is adsorbed with the hydrophilic group (quaternary ammonium salt part) facing inside and the lipophilic group (benzophenone part) facing outside.

Therefore, pigments and fillers become lipophilic, which has the great effect of improving dispersibility in solvent-based paints, inks, etc., and reducing volatility. Therefore, the ultraviolet absorber of the present invention can be bonded to the pigment, filler, etc. by adsorbing the ultraviolet absorber of the present invention to the pigment, filler, etc. in advance and drying the water. By blending these pigments, fillers, etc. into solvent-based paints, paints with excellent ultraviolet absorption ability can be obtained, and since the ultraviolet absorbers are combined with the pigments, fillers, etc., they have excellent thermal stability and volatilization. This makes it possible to maintain its effectiveness for a long time.

[Function] The compound of general formula (I) of the present invention obtained by top filling is
At least one of C+ and Ct of the compound of formula (IF) is reacted with an amino compound, and the terminal thereof is converted into a quaternary ammonium salt.

Therefore, the basic skeleton of the molecule remains unchanged and the ultraviolet absorbing ability of the compound of formula (I) is maintained. Furthermore, the terminal is cationic and ionic due to the quaternary ammonium salt, making it water-soluble.

The obtained ultraviolet absorber has the excellent property of efficiently absorbing light with a wavelength of 290 to 380 + -, which degrades or destroys organic substances, but hardly absorbing light with a wavelength of 400 + - or more. Therefore, it has a strong protection effect from ultraviolet rays and has very little coloring. Therefore, by adding 0.01 to 10% by weight, preferably 0.1 to 1% by weight, to an organic material such as paint, the organic material itself or the organic substance covered by the organic material can be protected from ultraviolet rays. can be protected.

[Effects of the Invention] The water-soluble ultraviolet absorber of the present invention can be used in most organic materials in the same manner as in the past.

A very small amount is sufficient, and even if a large amount is added, transparency will not be impaired. Furthermore, since it has the characteristic of being water-soluble, it can be used in water-soluble paints, cosmetics, water-based dyes, etc., and has a wider range of uses than ever before. For example, since the terminal is cationic, it can be added to cationic electrodeposition paints. Furthermore, when adsorbed onto paints and fillers, the effects of the present invention are tremendous, such as the ability to obtain pigments and fillers with no volatilization of the ultraviolet absorber and good dispersibility and ultraviolet absorbing ability.

[Example] This will be explained in detail below using examples.

(First Example) 0.1 mol of 2,4-dihydroxybenzophenone and 0.1 mol of 2-7minoacetic acid chloride were heated in pyridine in the presence of sodium hydroxide at 100°C for 6 hours with stirring. .

Pyridine was distilled under reduced pressure from the resulting reaction solution, and the residue was washed with water and dried. Then, add 0.3 methyl iodide to this residue.
mol and heated in a pressure vessel at 120°C for 10 hours to carry out the reaction of formula (IV'), resulting in the following formula (A
The compound (A) obtained from the quaternary ammonium salt of
As shown in the U■ spectrum in Figure 1, from 290 nm to 3
It is a good ultraviolet absorber with excellent ability to absorb light with a wavelength in the ultraviolet region of 80 nm. .

(Second Example) First example using 0.1 mole of 2.2',4.4-tetrahydroxybenzophenone, 02 mole of 2-aminoacetic acid chloride, and 0.6 mole of methyl iodide as raw materials. A compound of the following formula (B) was obtained by reacting in the same manner as above.

Compound (B) is also a water-soluble ultraviolet absorber having good ultraviolet absorption ability as shown in FIG.

(Third Example) 2.2'-dihydroxy-4,4'-dimethoxy-5,
0.1 mol of sodium 5'-disulfonate and 0.2 mol of N-dimethyl-1,3-propyldiamine were reacted by heating at 150°C for 5 hours in the presence of concentrated sulfuric acid. 0.2 mol of methyl bromide was added to the obtained reaction product, and 1
After heating at 00° C. for 15 hours, compound (C) has good ultraviolet absorption ability as shown in FIG.

(Test Example 1) 0.5g of the compound (A) obtained above, 1.0Q
, 2.0Q1 Compounds (B) and (C) were treated as 1. Og
Each sample was dissolved in 100 CG of water. At this time, the solution was all transparent and homogeneous, containing compounds (A), (B), and (C).
) showed good water solubility.

Next, 50 g of anatase titanium oxide was added to the obtained solution, and water was evaporated while stirring. Then, the entire amount of each titanium oxide obtained was added to a solvent-type amino alkyd paint 200Q with a non-volatile content of 60%, and dispersed in a ball mill for 12 hours to obtain a white paint. At the same time, compounds (A>, (B)
, and titanium oxide to which (C) was not added was similarly dispersed to obtain a white paint of Comparative Example 1.

Each paint was diluted with a mixed solvent consisting of an aromatic hydrocarbon solvent and an alcohol solvent, applied to a steel plate by air spray to an average dry film thickness of 40 μm, and then baked and dried at 140°C for 20 minutes. A test piece was prepared.

Each test piece was exposed to 11 m outdoors for one month, and the gloss values (60° gloss) at that time are shown in Table 1. Note that the gloss value of each test piece before exposure was between 95 and 100.

From Table 1, the paints to which the compounds (A>, (B), and (C) were added have much higher gloss values than the paint of Comparative Example 1. As the value increases, the gloss value also increases.

Here, a high gloss value means that there is little decrease in gloss due to exposure, that is, there is little deterioration due to ultraviolet rays. This is compound (A), <8), (C
) is clearly due to the ultraviolet absorption effect.

(Test Example 2) Compounds (A), (B), and (C) were each taken in the same amount as in Test Example 1, and added together with anatase titanium oxide 50Q to a cationic electrodeposition paint 150Q with a non-volatile content of 50%, and processed in a ball mill. Each white paint was obtained by dispersing for 12 hours. Each white paint was cationically electrodeposited onto a steel plate to an average film thickness of 3 μm, and baked and dried at 170° C. for 30 minutes to prepare test pieces. In addition, a white paint of Comparative Example 2 was also prepared by similarly dispersing titanium oxide without adding compounds (A), (B), and (C).

Each test piece was exposed in the same manner as in Test Example 1, and the gloss was measured in the same manner and the results are shown in Table 2. Note that the gloss value of each test piece before exposure was between 90 and 100.

From Table 2, the test pieces to which compounds (A>, (8), and (C) were added had clearly higher values than Comparative Example 2. Also, as the amount of compound (A> added) increased, the gloss value also increased. These results indicate that compounds (A), (B), and (C
) is clearly due to the ultraviolet absorption effect.

[Brief explanation of the drawing]

Figure 1 shows compounds (A), (B:, (C) synthesized in Examples.
) is a graph showing the ultraviolet absorption spectrum of

Claims (2)

[Claims] (1) General formula ▲ Numerical formulas, chemical formulas, tables, etc. ), and Z_
A benzophenone-based water-soluble ultraviolet absorber, characterized in that at least one of 1 and Z_2 is a quaternary ammonium salt. (2) Quaternary ammonium salt is -R_1-OCO-R_2-N^+(R_3, R_4,
R_5)・X^-, -R_1-COO-R_2-N^+(R_3, R_4,
R_5)・X^-, -R_1-CO-NH-R_2-N^+(R_3, R_
4, R_5)・X^- and -R_1-SO_3-NH-R_2-N^+(R_3,
Claim 1 selected from the following: Water-soluble ultraviolet absorber as described.