JPH0359936B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is characterized in that a combination of at least two or more organic metal salt compounds, an organic phosphite compound, and an aluminum sulfate compound are added to polyvinyl chloride, and the polyvinyl chloride has improved printability. This invention relates to a resin composition. The stabilized resin composition consisting of polyvinyl chloride resin, stabilizers and other additives has excellent physical, chemical and mechanical properties, and by adding plasticizers and increasing or decreasing them, It is extremely useful in providing molded products that can fully meet the demands of a wide variety of markets. These molded products are often used as packaging films, sheets, containers, etc., and are also printed with various types of printing. However, processing aids such as plasticizers, stabilizers, pigments or lubricants are added to such polyvinyl chloride resins.
The resin composition containing other additives may be susceptible to temperature changes and/or temperature effects, especially under harsh conditions such as hot and humid times or severe cold periods, when the molded product is left after heat processing. BACKGROUND ART A phenomenon in which powdery or oily substances are discharged or oozed out on the surface of a molded article, that is, blooming or bleeding occurs. For this reason, the molded article before printing suffers from deterioration in printability due to the above-mentioned phenomenon, and more specifically, defects such as color shading, unprinted areas, and printing misalignment. In addition, problems such as peeling of the printing or transfer to other parts due to the above-mentioned phenomenon occur in the molded product after printing, and there is a drawback that the commercial value of the molded product is significantly reduced. Conventionally, methods to solve such technical problems include using only phthalate ester plasticizers as additives, without using secondary plasticizers that have migration properties, and methods to prevent blooming or bleeding. Various solutions have been investigated, including methods of combining several stabilizers with relatively small amounts, methods of combining stabilizing aids, and methods of reducing the amount of processing aids such as lubricants. However, the effect of improving printability by these methods is not sufficient. There has been a desire for such a resin composition that exhibits better effects. The inventors of the present invention have conducted various studies to solve these technical problems, and have found that various additives added to polyvinyl chloride resin are molded due to changes in temperature or humidity after being subjected to thermoforming processing. The present inventors have discovered a polyvinyl chloride resin composition that exhibits no blooming or bleeding phenomena caused by migration to the surface of an article, and therefore has extremely excellent printability, leading to the present invention. That is, the present invention provides polyvinyl chloride resin with (a) lithium, sodium, potassium, magnesium,
Calcium, strontium, barium, zinc,
At least two or more organic metal salt compounds of tin or cerium, (b) an organic phosphite compound, and (c) the following general formula XAl(SO ₄ ) ₂ .nH ₂ O or Al ₂ (SO ₄ ) ₃・nH ₂ O (1) (wherein, X represents sodium, potassium or ammonium, and n represents a number of 0, 12 and 18). This is a polyvinyl chloride resin composition with improved printability. The metals constituting the organometallic salt compound used in the present invention include lithium, sodium, potassium, magnesium, calcium, strontium, barium, zinc, tin, and cerium, and the organic residues constituting the compound include carboxylic acids and phenols. It is a residue such as a class. Examples of carboxylic acids include saturated aliphatic or unsaturated aliphatic monocarboxylic acids and dicarboxylic acids having 4 to 22 carbon atoms, and carbocyclic carboxylic acids having 7 to 16 carbon atoms, such as hexanoic acid, octanoic acid, 2-ethylhexylic acid, and decane. acids, isodecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, myristoleic acid, palmitoleic acid, oleic acid, ricinoleic acid, ricinoleic acid, isooleic acid, isostearic acid, 12-hydroxystearic acid and succinic acid. , glutaric acid, adipic acid, pimelic acid, superric acid, azelaic acid, sebacic acid, isocrotonic acid, as well as benzoic acid, toluic acid, xylic acid, ethylbenzoic acid,
Examples include p-tert-butylbenzoic acid, p-octylbenzoic acid, phthalic acid, isophthalic acid, terephthalic acid, cinnamic acid, salicylic acid, and mixed acids of these carboxylic acids. In addition, examples of phenols include phenol, cresol, p-tert-butylphenol,
Examples include p-tert-octylphenol, nonylphenol, dinonylphenol, decylphenol, dodecylphenol, and xylenol. Therefore, the organometallic salt compound bound to such an organic residue may be an acidic salt or a neutral salt, and may also be a basic or overbased salt in which more than a chemical equivalent of the metal is bound to the compound. good. In addition, tin compounds are typified by alkyltin compounds, such as dimethyltin bis(isooctylthioglycolic acid ester).
salt, dibutyltin dilaurate, dibutyltin maleate polymer, dibutyltin bis(maleic acid monoester) salt, dibutyltin bis(isooctylthioglycolic acid ester) salt, dioctyltin maleate polymer, dioctyltin bis(isooctylthio) Examples include glycolic acid ester) salt or dioctyltinthiopropionate. These organometallic salt compounds, when used in the present invention, include zinc salts and other metal salts such as lithium, sodium, potassium, magnesium, calcium,
Combination with strontium, barium or cerium salt is more preferable from the viewpoint of synergistic effect, and the amount added is 0.1 to 100 parts by weight of polyvinyl chloride resin.
5 parts by weight, preferably 0.5 to 3 parts by weight. Examples of the organic phosphite compound used in the present invention include trialkyl phosphites, triaryl phosphites, trialkyl phosphites, alkylaryl phosphites, bisphenol A phosphites, and phosphites made of polyhydric alcohols. Examples of compounds include triisooctylphosphite, triisodecylphosphite, tristridecylphosphite, triphenylphosphite, tricylylphosphite, tribenzylphosphite, trisnonylphenylphosphite, diphenylisooctylphosphite, Diphenylisodecylphosphite, diphenyltridecylphosphite, 4,
4'-Isopropyldenediphenylalkyl ( _C12
~ _C15 ) Phosphite, hydrogenated 4,4'-isopropylidene diphenyl phosphite, 2-tert-butyl-α(3-tert-butyl-4-hydroxyphenyl) p-cumenylbis(p-nonylphenyl) phosphite, Distearyl pentaerythritol diphosphite, tris(4-oxy-
3,5-di-tert-butylphenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, heptakis(dipropylene glycol) triphosphite, poly(dipropylene glycol) phenyl phosphite, etc. , acid phosphites of the above organic phosphites in which one or two of the organic residues such as alkyl, aryl or aralkyl are substituted with hydrogen atoms, such as diphenyl acid phosphite, diisodecyl acyl, etc. Compounds such as dophosphite, phenyl isooctyl acid phosphite, phenyl isodecyl acid phosphite, dibenzyl acid phosphite, and dinonylphenyl acid phosphite can be mentioned. At least one or two or more of these organic phosphite compounds are used, and the amount added depends on the polyvinyl chloride resin.
0.001 to 3 parts by weight per 100 parts by weight, preferably
It is 0.03 to 1.5 parts by weight. Examples of the aluminum sulfate compound represented by the general formula (1) used in the present invention include potassium aluminum sulfate dodecahydrate, potassium aluminum sulfate anhydrate, sodium aluminum sulfate dodecahydrate, sodium aluminum sulfate anhydrate, and aluminum sulfate. They are ammonium dodecahydrate, aluminum sulfate ammonium anhydrate, aluminum sulfate hexahydrate, and aluminum sulfate anhydrate. The amount of these aluminum sulfate compounds added is 0.01 to 2 parts by weight per 100 parts by weight of polyvinyl chloride resin.
Part by weight, preferably 0.1 to 1 part by weight. As described above, the polyvinyl chloride resin composition of the present invention has a combination of the above-mentioned (a) to (c) added as an essential component, and the resin composition is It has excellent effects not only in stabilization but also in printability. In the present invention, the following stabilizers or stabilizing aids, such as β-diketone compounds, antioxidants, organic phosphates, etc. are added to the three components (a) to (c) for the purpose of the present invention. They can be used together as long as they do not inhibit. Examples of β-diketone compounds include compounds such as benzoylacetone, dibenzoylmethane, tribenzoylmethane, palmitoylbenzoylmethane, stearoylbenzoylmethane, anisoylbenzoylmethane, dianisoylmethane, dihydroacetic acid, and the above β-diketones and zinc. Examples include metal complex salts combined with metals such as barium and calcium. Also, hindered phenols which are antioxidants, such as alkylated phenols, alkylated phenol esters, alkylene or alkylidene bisphenols, polyalkylated phenols, and compounds such as sulfur-containing alkanes alkyl esters and piperidine compounds. Examples include butylated hydroxytoluene, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 4,4'-thiobis(6-tert-butyl-
m-cresol), tetrakis [methylene-3-
(3,5,-di-tert-butyl-4-hydroxyphenyl)propionate] methane, dilaurylthiodipropionate, distearylthiodipropionate and 2,2,6,6-tetramethylpiperidine- Examples include 4-ol ester. Examples of organic phosphate compounds include polyoxyethylene (5-55) nonyl phenyl ether phosphate, polyoxyethylene (4-10) tridecyl ether phosphate, diisooctyl phosphonate,
These include diphenylphosphonate, phenylisodecylphosphonate, diphenylisodecylphosphonate, tris(nonylphenyl)phosphonate, and the like. Examples of epoxy compounds include epoxidized unsaturated fats and oils such as epoxidized soybean oil and epoxidized linseed oil, alkylated epoxy stearates such as butyl or octyl, epoxidized unsaturated fatty acid esters, epoxycyclohexane derivatives, and epichlorohydrin. , epoxy resin which is a polycondensate with 2'-isopropylidene diphenyl, and polyhydric alcohol compounds such as pentaerythritol, dipentaerythritol, mannitol, sorbitol or these alcohols and aliphatic polycarboxylic acids, Ester compounds with amino acids. β, a nitrogen-containing compound
-Aminocrotonic acid alkyl ester salts and tris(hydroxyethyl)isocyanurate.
In addition, benzophenone such as 2-hydroxy-4-methoxybenzophenone, which is a light stabilizer,
These include benzotriazole compounds such as (2'-hydroxy-5-methylphenyl)benzotriazole, benzoate compounds, salicylate compounds, and cyanoacrylate compounds. These stabilizers or stabilizing aids can be appropriately used as thermal stability, weather resistance, processing aids, etc. depending on the purpose of use. The polyvinyl chloride resin in the present invention may include not only polyvinyl chloride alone, but also copolymers of this resin and the following. For example, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-vinylidene chloride copolymer , vinyl chloride-urethane copolymer, vinyl chloride and chlorinated ethylene, chlorinated propylene,
Copolymers with polybutene etc., blend products of vinyl chloride and styrene-maleic anhydride terpolymer, acrolinitrile-butadiene-styrene copolymer etc. and polyvinyl chloride resin, block or graft copolymers, etc. I can give it to you. The resin composition of the present invention can be molded over a wide range from soft to soft by increasing or decreasing the amount of plasticizers, such as phthalate esters, aliphatic dibasic acid esters, and polyester plasticizers, depending on the purpose of the molded product. In addition, fillers, pigments, antistatic agents, antifogging agents,
A flame retardant, a fungicide, a crosslinking agent, a foaming agent, etc. can be used in combination. Next, the present invention will be specifically explained based on Examples. Furthermore, the present invention is not limited to these Examples in any way. Example 1 In order to examine the thermal stability and printability of a polyvinyl chloride resin composition prepared by adding a combination of stabilizer components (a) to (c) of the present invention, the following formulation was heated to 180°C. Knead for 5 minutes using a kneading roll to obtain a thickness.
A uniform sheet of 0.3 mm was made. Compounded polyvinyl chloride resin TK800 (Note-1)
100 parts by weight M B S B-31 (Note-2) 10 Dioctyl phthalate 6 Epoxidized soybean oil 4 Barium stearate 0.6 Barium nonylphenol 0.6 Zinc 2-ethylhexylate 0.2 Zinc stearate 0.3 Diphenyl Isodecyl phosphite 0.8 Dibenzoylmethane 0.1 Additives (Table 1) 0.3 Note 1 Polyvinyl chloride resin manufactured by Shin-Etsu Chemical Note 2 Methacrylic ester-butadiene manufactured by Kanegabuchi Chemical - Styrene copolymer resin test 1 A 20 x 40 mm test piece was made from the above uniform sheet and placed in a gear oven aging tester heated to a constant temperature for a certain period of time to determine the initial degree of coloring due to thermal deterioration and black decomposition. Thermal stabilization effects such as time were tested. The results are shown in Table 1. Test 2 A 100 x 200 mm test piece was made from the above uniform sheet and placed in a closed constant temperature and humidity chamber set at a temperature of 60°C and a humidity of 80% for a certain number of days, and subjected to forced blooming and/or forced bleeding tests. I went. Next, the original sheet and the sheet after the test (forced blooming, etc.) were printed using a small rotogravure printing machine and a printing roll (diameter 100 x length 140 mm) (manufactured by Hatsuzawa Iron Works Co., Ltd.) to test printability. . In addition, regarding the evaluation of the printability of the printed sheet, a peeling test of the printing ink (Note 3) was conducted using cellophane tape. The degree of ink peeling was evaluated using the following numerical values. 5: Not peeled off at all 4: Slightly peeled off 3: 50% peeled off 2: Most of it peeled off 1: Almost all of it peeled off In addition, a so-called printing adhesive test was conducted on the printed sheets. The degree of printing adhesion was evaluated using the following numerical values. A: Good printing B: Fair C: Slightly bad D: Not printing at all These results are shown in Table 1. Note-3 White ink manufactured by Tokushu Shikiryo Kogyo Co., Ltd. HiCorp S

[Table] As is clear from the test results in Table 1 above, the molded articles of the polyvinyl chloride resin compositions formed by combining the stabilizer components (a) to (c) of the present invention are superior to those of the comparative examples. It turned out to be extremely good. Also,
Test conditions for the forced blooming or forced bleeding test in Test 2 above, i.e. 60°C
When left at ×80% for one day, this corresponds to 80 to 10 days when left in a natural environment. Therefore, days 3, 7, 15, and 30 of the test correspond to 1 month, 2 months, 5 months, and about 1 year, respectively, if left in the natural environment. In addition, in the evaluation of the printing adhesive test, "well printed" in A means that the markings such as letters were printed extremely clearly without any color shading of the printing ink. And D, “Not printed at all”
This is a phenomenon in which the printing ink is repelled without forming characters after printing. Example 2 A sheet was prepared using the following polyvinyl chloride resin composition under the same conditions as in Example 1. In addition, Example 1
The test was conducted under the same test conditions and method (Tests 1 and 2). The results are shown in Table 2. Compounded polyvinyl chloride resin (TK1000) 100 parts by weight dioctyl phthalate 38 Epoxidized soybean oil 2 Titanium oxide (rutile type) 10 Barium stearate 0.5 Overbased barium dodecyl phenolate carbonate complex 0.5 2-ethylhexylic acid Zinc 0.3〃 Zinc stearate 0.3〃 4,4'-isopropylidene diphenylalkyl (C ₁₂ - C ₁₅ ) phosphite 0.5〃 Dibenzoylmethane 0.1〃 Additives (Table 2) 0.3〃

[Table] Example 3 This example contains, in addition to the stabilizer components (a) to (c) of the present invention, other known stabilizer components, lubricants, fillers, secondary softeners, etc., for comparison. A sheet was prepared under the same conditions as in Example 1 using a polyvinyl chloride resin composition that also contained a component that inhibited printability. Further, tests were conducted under the same test conditions and methods as in Example 1 (Tests 1 and 2). The results are shown in Table 3. Compounded polyvinyl chloride resin (TK800) 100 parts by weight Dioctyl phthalate 10 Epoxidized soybean oil 3 Barium stearate 0.5 Barium nonylphenol 0.5 Zinc 2-ethylhexylate 0.3 Zinc stearate 0.3 Poly(dipropylene glycol) Phenyl phosphite 0.8 Potassium aluminum sulfate dodecahydrate 0.3 Additive (Table 3)

【table】

Claims (1)

[Scope of Claims] 1. A polyvinyl chloride resin containing (a) at least two or more organometallic salt compounds of lithium, sodium, potassium, magnesium, calcium, strontium, barium, zinc, tin, or cerium, and (b) _An organic phosphite compound _and ( _c ) _the following _{general formula :} 1. A polyvinyl chloride resin composition with improved printability, characterized in that it is made by adding ammonium in combination with at least one of the aluminum sulfate compounds represented by (n represents the number of 0.12 and 18).