JP3500669B2 - 1-Naphthoic acid ester and its use as stabilizer - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel 1-naphthoic acid ester and its use as a stabilizer for organic materials.

[0002]

2. Description of the Related Art Organic materials such as thermoplastic resins, thermosetting resins, natural or synthetic rubbers, mineral oils, lubricating oils, adhesives and paints are deteriorated by the action of light, and physical properties such as strength, elasticity and viscosity are deteriorated. Further, it is known that it causes discoloration or other poor appearance and cannot be used for a long period of time. Therefore, conventionally, various stabilizers have been used alone or in combination.

[0003]

However, the conventional stabilizers are not yet sufficiently satisfactory in the stabilizing effect, and there has been a demand for a stabilizer having a further excellent effect.

An object of the present invention is to provide a compound having an excellent stabilizing effect on the photodegradation of organic materials.

Another object of the invention is to use such compounds to stabilize organic materials, especially those which are susceptible to degradation by light.

[0006]

The present inventors have conducted research to develop a compound capable of imparting excellent stability against photodegradation of organic materials. As a result, 1-of the specific structure
It was found that naphthoic acid ester has an excellent effect, and the present invention has been completed.

That is, the present invention relates to 1-naphthoic acid 4-
Benzoyl-3-hydroxyphenyl is provided. This compound is represented by the following formula, and may be hereinafter simply referred to as 1-naphthoic acid ester.

[0008]

The above-mentioned 1-naphthoic acid ester is effective for stabilizing an organic material, particularly for stabilizing an organic material having a property of being deteriorated by light. Therefore, the present invention also provides a stabilizer for an organic material containing the 1-naphthoic acid ester as an active ingredient, a method for stabilizing an organic material by blending the 1-naphthoic acid ester with a stabilizing effective amount in the organic material, and Provides an organic material composition comprising an organic material containing the 1-naphthoic acid ester.

The 1-naphthoic acid ester of the present invention can be produced by utilizing a known ester synthesis reaction.
For example, it can be produced by an esterification reaction using 1-naphthoic acid or an acid halide thereof and 2,4-dihydroxybenzophenone. When using free 1-naphthoic acid, it is preferable to react in the presence of a halogenating agent such as thionyl chloride, phosphorus trichloride and phosphorus pentachloride. In this case also, the reaction proceeds via an acid halide. It is presumed to do.

This reaction is preferably carried out in the presence of a solvent. As the solvent which can be used, aromatic hydrocarbons such as toluene, benzene and xylene, and aliphatic hydrocarbons such as n-hexane and n-heptane are used. Ethers such as diethyl ether, tetrahydrofuran, chloroform,
Examples thereof include carbon tetrachloride and halogenated hydrocarbons such as monochlorobenzene. In this reaction, 1-naphthoic acid or an acid halide thereof and 2,4-dihydroxybenzophenone are preferably used in an approximately equimolar amount, or 1-naphthoic acid or an acid halide thereof is used in a slight excess molar amount, for example, 2, It is preferable to use 1-naphthoic acid or its acid halide in an amount of about 1 to 1.2 mol per mol of 4-dihydroxybenzophenone. In this reaction, pyridine, triethylamine, N, N
-A base such as a tertiary amine such as dimethylaniline may coexist. This reaction usually proceeds under atmospheric pressure, but may be performed under pressure. Further, this reaction may be carried out in the air, but normally, it is preferably carried out in an atmosphere of an inert gas such as nitrogen gas. After completion of the reaction, the solvent is removed, and the desired 1-naphthoic acid ester can be isolated by purifying by a suitable means, if necessary.

The 1-naphthoic acid ester of the present invention is effective for stabilizing organic materials such as synthetic resins, natural or synthetic rubbers, paints, waxes and oils which have the property of being deteriorated by light as described above. It is valid. The organic material that can be stabilized by the present invention,
For example, the following may be mentioned, and each of them may be stabilized alone or a mixture of two or more may be stabilized, but of course, the organic materials are not limited to these.

(1) Polyethylene, for example, high density polyethylene (HD-PE), low density polyethylene (LD-P)
E), linear low density polyethylene, (2) polypropylene, (3) methylpentene polymer, (4) EEA (ethylene / ethyl acrylate copolymer) resin, (5) ethylene / vinyl acetate copolymer resin, (6 ) Polystyrenes such as polystyrene, poly (p-methylstyrene), poly (α-
Methylstyrene), (7) AS (acrylonitrile-styrene copolymerization) resin, (8) ABS (acrylonitrile-butadiene-styrene copolymerization) resin, (9) AAS (special acrylic rubber-acrylonitrile-styrene copolymerization) resin, ( 10) ACS (acrylonitrile / chlorinated polyethylene / styrene copolymer) resin, (11) chlorinated polyethylene,
Polychloroprene, chlorinated rubber, (12) polyvinyl chloride, polyvinylidene chloride, (13) methacrylic resin, (14)
Ethylene / vinyl alcohol copolymer resin, (15) fluororesin,

(16) Polyacetal, (17) Polyphenylene ether resin and polyphenylene sulfide resin, (18) Polyurethane, (19) Polyamide, (20) Polyethylene terephthalate, Polybutylene terephthalate, (21) Polycarbonate, (22) Polyacrylate,
(23) Polysulfone, polyether ether ketone, polyether sulfone, (24) aromatic polyester resin,
(25) Epoxy resin, (26) Diallyl phthalate prepolymer, (27) Silicone resin, (28) Unsaturated polyester resin, (29) Acrylic modified benzoguanamine resin, (30)
Benzoguanamine / melamine resin, (31) urea resin,

(32) polybutadiene, (33) 1,2-polybutadiene, (34) polyisoprene, (35) styrene / butadiene copolymer, (36) butadiene / acrylonitrile copolymer, (37) ethylene / propylene copolymer Polymer, (3
8) Silicone rubber, (39) Epichlorohydrin rubber, (4
0) Acrylic rubber, (41) Natural rubber,

(42) Chlorine rubber paint, (43) Polyester resin paint, (44) Urethane resin paint, (45) Epoxy resin paint, (46) Acrylic resin paint, (47) Vinyl resin paint,
(48) Amino alkyd resin paints, (49) Alkyd resin paints, (50) Nitrocellulose resin paints, (51) Oil paints,
(52) Wax, (53) Lubricating oil.

The stabilizer of the present invention containing 1-naphthoic acid ester as an active ingredient is mixed in a stabilizing effective amount with respect to an organic material, and the preferable addition amount naturally varies depending on the kind of the target organic material. However, usually, 1-naphthoic acid ester is added in an amount of 0.01 to 5 with respect to 100 parts by weight of the organic material.
It is preferably used in the range of about parts by weight. If the amount of 1-naphthoic acid ester is less than 0.01 part by weight, the stabilizing effect is not always sufficient, and even if it exceeds 5 parts by weight, the effect corresponding to it cannot be obtained and the effect is economical. Will be at a disadvantage.

The organic material composition containing 1-naphthoic acid ester according to the present invention may further contain other additives, such as phenol-based antioxidants, amine-based antioxidants, sulfur-based antioxidants and phosphorus, if necessary. It may contain a system antioxidant, an ultraviolet absorber, a hindered amine light stabilizer, a lubricant, a plasticizer, a flame retardant, a nucleating agent, a metal deactivator, an antistatic agent, a pigment, an inorganic filler and the like. These additives can be added at the same time as the 1-naphthoic acid ester, or can be added at another stage.

In blending the organic material with the 1-naphthoic acid ester of the present invention, or any other additive optionally used in addition thereto, any known method and apparatus for obtaining a homogeneous mixture should be used. You can For example, when the organic material is a solid polymer, 1-
The naphthoic acid ester or further optional additives can be dry blended directly into the solid polymer, or the 1-naphthoic acid ester or further optional additives can be incorporated into the solid polymer in the form of a masterbatch. it can. When the organic material is a synthetic polymer, in addition to the polymer solution during or immediately after the polymerization,
The 1-naphthoic acid ester or further optional additives can also be incorporated in the form of solutions or dispersions. On the other hand, when the organic material is a liquid such as oil, 1-naphthoic acid ester or further any additive can be directly added and dissolved, or 1-naphthoic acid ester or further any additive can be added. It can also be added in the state of being dissolved or suspended in a liquid medium.

[0020]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. The parts in the examples are based on weight unless otherwise specified. First, a synthesis example of 1-naphthoic acid ester according to the present invention will be shown.

Example 1 0.86 g of 1-naphthoic acid was placed in a flask, and 3 cm ³ of thionyl chloride was added dropwise thereto at room temperature, and then 5 cm ^{3 of} toluene was added.
Was added and dissolved. A solution prepared by dissolving 1.03 g of 2,4-dihydroxybenzophenone in 15 cm ³ of toluene was added to this at 10 ° C. for 10 minutes under a nitrogen atmosphere. This mixed solution was kept for 2 hours and then washed with water, and the solvent was distilled off from the organic layer under reduced pressure. The residue was separated and purified by a silica-packed column using toluene as a mobile phase to obtain 0.91 g of 4-benzoyl-3-hydroxyphenyl 1-naphthoate as a pale yellow solid.

Melting point: 135-137 ° C. Mass spectrometry (MS): m / z 368 (M ⁺ ).

An example of a polypropylene stabilization test using the 1-naphthoic acid ester (referred to as LS-1) obtained in Example 1 is shown below.

Example 2 << Compound >> Unstabilized polypropylene 100 parts Calcium stearate 0.05 parts Phenolic antioxidant ^{* 1} 0.05 parts Phosphorus antioxidant ^{* 2} 0.05 parts LS-10 or 0 .2 copies

^{* 1} Tetrakis [methylene-3- (3,5
-Di-t-butyl-4-hydrocyphenyl) propionate] methane ^{* 2} tris (2,4-di-t-butylphenyl) phosphite

Each compound having the above composition was melt-kneaded at 230 ° C. with a 4-inch φ electric heating roll, and the obtained melt-kneaded product was molded at 250 ° C. by a press molding machine to give a sheet having a thickness of 1 mm. A test piece having a length of 40 mm and a width of 60 mm was punched out from this sheet. This test piece was put in a sunshine weather ohm meter, carbon arc was used as a light source, and light was irradiated under the conditions of a black panel temperature of 83 ° C. and a rain spray cycle of 18 minutes / 120 minutes, and a crack was generated on the light irradiation surface of the test piece. Was measured. It means that the longer the time until cracking occurs, the better the weather resistance. The results are shown in Table 1.

[0027]

[Table 1]

[0028]

INDUSTRIAL APPLICABILITY The 4-benzoyl-3-hydroxyphenyl 1-naphthoate of the present invention is effective for preventing deterioration of various organic materials such as thermoplastic resins, especially by light. Therefore, the organic material containing the 1-naphthoic acid ester, for example, a synthetic resin is a high-quality product because it is stable against photodegradation during use.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Norman Sidney Allen England, Lancashire, Bolton B L1 3NR, Halliwell, 16 Maplewood Gardens (72) Inventor Michel Edge England, Lancashire, Bolton B L1 3NR, Halliwell , 16 Maplewood Gardens (56) Reference JP-A-2-22222 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) CA (STN) CAOLD (STN) REGISTRY (STN)

Claims (4)

(57) [Claims] 1. 4-Benzoyl-3-hydroxyphenyl 1-naphthoate. 2. A stabilizer for organic materials, which comprises 4-benzoyl-3-hydroxyphenyl 1-naphthoate as an active ingredient. 3. A method for stabilizing an organic material, which comprises adding 4-benzoyl-3-hydroxyphenyl 1-naphthoate to the organic material in a stabilizing effective amount. 4. An organic material composition comprising an organic material containing 4-benzoyl-3-hydroxyphenyl 1-naphthoate.