JP2537907B2 - Synthetic resin composition containing stabilized halogen - Google Patents

Description

TECHNICAL FIELD The present invention relates to a synthetic resin composition containing a stabilized halogen. More specifically, it relates to a synthetic resin composition containing a stabilized halogen having improved light resistance and heat resistance, which is obtained by adding a mixed product of a compound having a piperidine group and perchloric acid.

The present invention has been made to a synthetic resin composition containing halogen. The “halogen-containing synthetic resin composition” described in the present invention is composed of one kind or a combination of two or more kinds selected from halogen resins, non-halogen resins and halogen-based flame retardants.

The halogen resin means a synthetic resin containing halogen in a polymer such as vinyl chloride resin and vinylidene chloride resin. On the other hand, the term “non-halogen resin” as used herein means a synthetic resin such as polyethylene or ABS resin which does not contain halogen in the polymer.

The halogen-based flame retardant refers to a flame retardant containing halogen itself, such as a halogen-containing phosphate ester.

A combination of one or more selected from halogen resins, non-halogen resins and halogen-based flame retardants, in which the halogen is always contained in the resin composition in some form, as shown in the following table. As a representative example, there are five types.

Form 1 is only a halogen resin Form 2 is a combination of halogen resin and non-halogen resin Form 3 is a combination of halogen resin and halogen-based flame retardant Form 4 is a combination of halogen resin, non-halogen resin and halogen-based flame retardant Form 5 is A “halogen-containing synthetic resin composition”, to which the present invention is applied, is a combination of a non-halogen resin and a halogen-based flame retardant. A resin composition.

(Prior art and problems) Generally, molded products of synthetic resins such as polyvinyl chloride, polyethylene, and ABC resin are used for long-term outdoor use.
It is known that the mechanical strength is lowered and the color is changed under the influence of ultraviolet rays of sunlight, heat rays, and the like. In order to prevent these phenomena, various UV stabilizers such as benzophenone-based, benzotriazole-based, benzoate-based, piperidine-based and the like are used. Among these UV stabilizers, compounds having a piperidine group, so-called hindered amine type UV stabilizers are widely used in synthetic resins because they have excellent UV stabilizing performance, and development and application studies are also vigorous. Has been done.

However, when the compound having a piperidine group itself is blended alone as an ultraviolet stabilizer, and the halogen is contained in the resin composition in any form, the stabilizing effect of the ultraviolet stabilizer is significantly reduced. Or, it is known that the molded product causes remarkable coloring. In other words, in the "halogen-containing synthetic resin composition", the compound having a piperidine group cannot be an ultraviolet stabilizer by itself.

(Means for Solving Problems) The inventors of the present invention overcome obstacles such as reduction of the stabilizing effect of the ultraviolet stabilizer, which is considered to be caused by halogen in the compound having a piperidine group, and coloring of a molded product. Therefore, as a result of repeated intensive studies, it was found that a compound having a piperidine group is not used alone but a mixed product of it and perchloric acid is added, and a remarkable improving effect on light and thermal stability is found. The present invention has been completed.

The mixed product of the compound having a piperidine group and perchloric acid used in the present invention is considered to be a compound having the following general formula in the molecule.

In the formula, R ₁ , R ₂ , R ₃ and R ₄ are hydrogen atoms or hydrocarbon groups, R ₅
Is a hydrogen atom, a hydroxy group, an alkyl group or an acyl group,
X and Y are hydrogen atoms or groups containing O and N, and n is 0.01 to 1.

These mixed products can be prepared by mixing a compound having a piperidine group in a solvent such as alcohol or directly with an aqueous solution of perchloric acid. The molar ratio of perchloric acid to piperidine group 1 is 0.01.
The range from 1 to 1 is particularly preferred. The amount of perchloric acid used can be calculated from the molecular weight of the compound having a piperidine group.

Further, as the amount of perchloric acid used approaches from 0.01 to 1, the PH of the mixed product approaches from basic to neutral. 1
In the above case, the pH of the mixed product becomes acidic, and the effect of the acid becomes too strong, which is not preferable. In this way, the amount of perchloric acid used can be determined based on the change in PH of the mixed product. When the molecular weight of the compound having a piperidine group is unknown, the addition amount of perchloric acid can be determined by PH.

The compound having a piperidine group used in the present invention includes 2,2,6,6-tetramethyl-4-piperidyl benzoate, N-hydroxyethyl-2,2,6,6-tetramethyl-
4-piperidinol bis (3,5-di-t-butyl-4-
Hydroxyphenyl propionate), bis (2,2,6,6
-Tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2 -N-butyl-2- (3,5-di-t-butyl-
4-hydroxypentyl) malonate, tris (2,2,6,
6-tetramethyl-4-piperidyl) nitrilotriacetate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, N-hydroxyethyl-2, 2,6,6-tetramethyl-
4-piperidinol / dimethyl succinate condensate, bis (9-aza-8,8,10,10-tetramethyl-3-ethyl-
1,5-Dioxaspiro [5.5] -3-undecylmethyloxycarbonyloxy) -4,4'-isopropylidene biscyclohexane, bis (9-aza-8,8,10,10-tetramethyl-3-hydroxymethyl) -1,5-dioxaspiro [5,5] -3-undecylmethyl) ether, cyanuric chloride / t-octylamine / bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane condensate, Poly [6-morpholino-1,3,5-triazine-2,4diyl]
[(2,2,6,6-Tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-
Piperidylimino)], [2-[(2,2,6,6-tetramethyl-4-piperidyl) imino] 2-butyryl [(2,2,
6,6-Tetramethyl-4-piperidyl] imino] and the like.

The halogen resin referred to in the present invention is, for example, polyvinyl chloride, polyvinyl bromide, polyvinyl fluoride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene,
Brominated polyethylene, chlorinated rubber, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride −
Vinylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride terpolymer, vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorine Propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylic acid ester copolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride-methacrylic acid ester copolymer, Examples thereof include vinyl chloride-acrylonitrile copolymers and vinyl chloride-urethane copolymers.

Examples of the non-halogen resin referred to in the present invention include polyolefin resins such as polyethylene, polypropylene, polybutylene, and polyisobutylene, vinyl acetate, vinyl propionate, vinyl benzoate, acrylic acid, methacrylic acid, acrylic acid ester, and methacrylic acid polymerizable. Polymer of vinyl monomer, or polystyrene, AS, styrene resin such as ABS, polyester resin such as polyethylene terephthalate, polybutylene terephthalate, polyamide resin, polyacrylonitrile resin, polymethacryl resin, polycarbonate resin, polyacetal resin, polyacetic acid Vinyl resin, polyurethane resin, epoxy resin, urea resin, melamine resin, phenol resin, etc.,
Included are copolymers and polymer blends between these non-halogen resins.

The halogen-based flame retardant referred to in the present invention includes halogen-containing phosphate ester, aliphatic chloride, aliphatic bromide, aromatic chloride, aromatic bromide, and the like, and the compound includes trischloroethyl phosphate and tris (dichloro). Propyl)
Phosphate, trischloropropyl phosphate, tris-dichloropropyl / chloropropyl phosphate, bischloropropyl / dichloropropyl phosphate, bischloropropyl / chloroethyl phosphate,
Bischloroethyl dichloropropyl phosphate, tris (dibromopropyl) phosphate, tris (bromochloropropyl) phosphate, acetylene tetrabromide,
Ethane dibromide tetrachloride, ethane tetrabromide, butane tetrabromide, acetic acid dibromide, ethyl pentabromide, tetrabromide benzene, pentabromide benzene, hexabromide, pentabromide-cyclohexane chloride, hexa Ethane chloride, methane diiodide, ammonium bromide,
Brominated polyphenyl, chlorinated polyphenyl, perchloropentacyclodecane, 1,2-dibromo-3-chloropropane, 1,2,3-tribromopropane, hexabromocyclododecane, chlorinated diphenyl, chlorotetrabromoethane, Tetrabromobisphenol A, tetrabromophthalic anhydride, hexabromocyclododecane, bis (bromoethyl ether) tetrabromobisphenol A, tetrachlorophthalic anhydride, chlorendic acid, chlorentic acid, chlorinated paraffin, tribromopolystyrene, decabromodiene Phenoxyethane and the like.

In the stabilized halogen-containing synthetic resin composition of the present invention, the addition amount of the mixed product of the present invention is 100 parts by weight of the total amount of the halogen resin and / or the non-halogen resin.
It is 0.01 to 10 parts by weight. If the added amount of the mixed product is 0.01 parts by weight or less, the improvement effect is poor, and if it is 10 parts by weight or more, the addition effect cannot be expected to increase due to the increased amount, and the economic effect decreases.

(Scope of application of the invention) In the practice of the present invention, one or more conventional additives for halogen resins and non-halogen resins are added together with the mixed product of the present invention, depending on the type of synthetic resin. When used together, an excellent synergistic effect may be sometimes obtained.

Examples of such additives include metal salts of organic acids, metal oxides, hydroxides, basic inorganic acid salts, hydrotalcite compounds, organic phosphite compounds, metal organic metal phosphates, polyols, Examples thereof include nitrogen-containing non-metal compounds, antioxidants, light stabilizers, β-diketone compounds, epoxy compounds, and organic tin compounds.

Among these conventional additives, the metal salts of organic acids and the organic phosphite compounds were able to be recognized to have a further improving effect with the composition of the present invention. Such metal salts of organic acids include salts of Li, Na, K, Mg, Ca, Sr, Ba, Cd, Pb and Sn.

As the organic acid residue, there are the following carboxylic acid or phenol residues. Examples of carboxylic acids include formic acid,
Acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, 2-ethylhexoic acid, tridecanoic acid, capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, 12-hydroxystearic acid , Oleic acid, linoleic acid, linoleic acid, thioglycolic acid, mercaptopropionic acid, lauryl mercaptopropionic acid, benzoic acid, para-t-butylbenzoic acid, dimethylbenzoic acid, aminobenzoic acid, salicylic acid, aminoacetic acid, glutamic acid, shu Acids, glutaric acid, succinic acid, malonic acid, adipic acid, phthalic acid, fumaric acid, maleic acid, malic acid, citric acid, tartaric acid, thiodipropionic acid, trimellitic acid, pyromellitic acid, and mellitic acid. .

Examples of phenols include phenol, nonylphenol, t-butylphenol, octylphenol,
Examples include isoamylphenol, cresol and xylenol.

Examples of organic phosphite compounds include isooctyl phosphite, distearyl phosphite, triisodecyl phosphite, triisooctyl phosphite, trilauryl phosphite, tristearyl phosphite,
Tridipropylene glycol phosphite, diphenyl phosphite, triisononyl phenyl phosphite,
Triphenyl phosphite, diphenyl isodecyl phosphite, diphenyl isooctyl phosphite, phenyl diisooctyl phosphite, diisodecyl pentaerythritol-diphosphite, tetraphenyl dipropylene glycol diphosphite, polydipropylene glycol phenyl phosphite, trilauryl trithiophos Fight, trisnonylphenylphosphite,
Distearyl pentaerythritol-diphosphite,
Bis (2,4-di-t-butylphenyl) -pentaerythritol diphosphite, dilauryl phosphite, ditridecyl phosphite, ethylhexyl diphenyl phosphite, phenyl neopentylene glycol phosphite, peptakistripropylene glycol phosphite , Diphenyldidecyl (2,2,4-trimethyl-1,3-
Pentadiol) -diphosphite, diisooctyloctylphenyl phosphite, poly-4,4'-isopropylidene diphenol neodol 25 alcohol phosphite and the like.

Further, if necessary, antimony trioxide, a flame retardant aid such as an inorganic borate, a plasticizer, a lubricant, a pigment, a foaming agent, a filler,
Antistatic agents, heavy metal deactivators, nucleating agents, processing aids and the like can be added.

(Preparation of Piperidine Compound and Mixed Product of the Present Application) Prior to presenting actual measurement data according to the examples, types of piperidine compound used (a to f) and mixed products (A to F) prepared using the same. Are summarized in a list. As an example, the preparation of A and E will be described.

When bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate is used alone, the abbreviation is a.

Using this, a mixed product A was prepared according to the following procedure.

Preparation of A 481 g of bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate was dissolved in 200 g of methanol, and 334 g of a 60% perchloric acid aqueous solution was added dropwise with stirring (perchloric acid 100
200g in%). After completion of dropping, stirring was continued for 1 hour and the solvent was distilled off to obtain a white powder product (A) having a melting point of 140 to 150 ° C.

Similarly, using a compound e having a piperidine group, E
Was prepared.

Preparation of E Cyanuric chloride / t-octylamino / bis (2,2,6,6-
While stirring 250 g of the tetramethyl-4-piperidylamino) hexane condensate, 100 g of a 20% aqueous perchloric acid solution was added dropwise (20 g in terms of 100% perchloric acid), and the stirring was continued for about 1 hour after the completion of the addition. It was dried under reduced pressure to obtain a white powder (E) having a melting point of 135 to 160 ° C.

Hereinafter, the mixed product of the present application and the piperidine compound are collectively referred to as a test formulation. The test formulations of Tables 1-5 are used in this sense.

(Example) Example 1 In order to see the effect of the present invention, a test sheet having a thickness of 0.5 mm was prepared by a kneading roll using the following compounds. A gear aging tester was used to examine the coloring property at 180 ° C. for 15 minutes and 30 minutes, and the coloring degree was visually determined. Further, deterioration due to light was measured using a sunshine weather meter. The degree of deterioration was expressed as the residual elongation percentage after 400 hours, and the degree of coloring of the test piece was visually observed at the same time and the color tone was also shown. The closer the residual elongation rate is to 100%, the smaller the deterioration due to light. Further, for comparison, the same test was conducted on a compound having a piperidine group before preparation with perchloric acid, and the results are shown in Table 1. The abbreviation of the above-mentioned list of test compounds was used for the notation of test compound.

Blended polyvinyl chloride 100 parts by weight (halogen resin) DOP 40 〃 Epoxidized soybean oil 1.0 〃 TiO ₂ 1.0 〃 Ba-nonylphenate 0.8 parts by weight Zn-stearate 0.2 〃 Test compound Mixture products (A, B, D) Or E) 0.2〃 piperidine compound (a, d or e) 0.2〃 Example 2 A sheet for a test piece having a thickness of 0.5 mm was prepared by pressing the following composition after kneading, and using a sunshine weather meter,
The time until light embrittlement (light resistance) was measured. Further, the degree of coloring at 500 hours was measured. The results are shown in Table 2.

Blended polyethylene 100 parts by weight (non-halogen resin) Perchlorocyclopentadecane 15 〃 (Halogen flame retardant) Ca stearate 1.0 〃 Pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) ) Propionate 0.2 〃 Distearyl thiodipropionate 0.1 〃 Test mixture Mixed product (C or F) 0.2 〃 Piperidine compound (c or f) 0.2 〃 Example 3 The following composition was kneaded and then pressed to form a test sheet having a thickness of 0.5 mm, and the time until embrittlement (light resistance) was measured using a fade odometer. The results are shown in Table 3.

Blend polypropylene 100 parts (halogen resin) Tribromopolystyrene 10 (halogen flame retardant) Ca stearate 0.3 Pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate 0.2 Test blend Products Mixed product (A, D or E) 0.3 Piperidine compound (a or e) 0.3 Example 4 The following mixture was kneaded and pressed to form a sheet having a thickness of 2 mm, and the residual tensile strength after 500 hours of weather meter measurement was measured. For comparison, the same test was carried out for the case of the piperidine compound, and the results are also shown in Table 4.

Blended ABS resin 100 parts by weight (non-halogen resin) Tetrabromide bisphenol A 9 〃 (Halogen flame retardant) 4,4'-Butylidene bis (3-methyl-6-t-butylphenol) 0.1 〃 Test blend Mixed product ( C, D or F) 0.2〃 piperidine compound (c or f) 0.2〃 Example 5 In order to examine the effect when an organic phosphite compound is used in combination, a test sheet having a thickness of 0.5 mm is prepared with a kneading roll at 180 ° C. using the following formulation example, and a 1000 sheet is obtained with a sunshine weather meter. The residual elongation and the degree of coloring after the lapse of time were measured. The results are shown in Table 5.

Blended polyvinyl chloride 70 parts by weight (halogen resin) ABS resin 30〃 (non-halogen resin) Trisdibromopropyl phosphate 0.2 (halogen flame retardant) DOP 30〃 calcium carbonate 10〃 Ba-stearate 1.0〃 Zn-octoate 0.5〃 ST -210 ^* 1 0.5〃 Compounded product C 0.3〃 Organic phosphite compound Table 5 * 1 Dipentaerythritol dibasic acid partial ester
Made by Ajinomoto Co., Inc. (Effects of the Invention) The mixed product of the present application is added to the synthetic resin composition containing halogen consisting of one or more kinds selected from halogen resins, non-halogen resins and halogen-based flame retardants, only the compound having a piperidine group. It is clear from each of the Examples that the stabilizing effect is greater than the addition of.

Example 1 is a case where the synthetic resin composition containing halogen is a halogen resin alone. The effect of the mixed product is remarkable by comparing the groups of Experiment Nos. 1 to 4 with the groups of 5 to 6.

In Examples 2, 3, and 4, the halogen in the synthetic resin composition containing halogen is derived from the halogen-based flame retardant contained therein. All resins are non-halogen resins.

The stability comparison criteria are the light resistance and the degree of coloring of the sunshine weather meter in Example 2, the light resistance of the fadeometer in Example 3, and the tensile residual ratio in Example 4. The invention with mixed products in each case is superior to the control.

Example 5 is a little different and shows that the effect of the mixed product is promoted by the addition of the organic phosphite compound, ie the synergistic effect is significant.

The synergistic effect is different depending on the addition amount of the organic phosphite compound, but it is clear that the positive effect is observed in any case.

From the above examples, it is proved that the mixed product of the compound having a piperidine group of the present invention and perchloric acid contributes to the improvement of light resistance and heat resistance.

Claims (1)

(57) [Claims] 1. A compound having a piperidine group and perchloric acid for a synthetic resin composition containing halogen, which is composed of one or more selected from halogen resins, non-halogen resins and halogen-based flame retardants. A synthetic resin composition containing stabilized halogen, characterized in that the mixed product of (1) is added.