JPH0317864B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a stabilized polyvinyl chloride resin composition. More specifically, it has excellent coloring resistance and weather resistance, roll surface sticking phenomenon (plate-out phenomenon), high temperature heat resistance, low temperature heat resistance (heat storage ability), additive blowing phenomenon (blooming phenomenon), and urethane adhesion ( The present invention relates to a polyvinyl chloride resin composition with improved adhesion to PVC resin in contact with urethane. [Prior Art] It is well known that polyvinyl chloride resins become colored due to external energy such as heating during molding or photodegradation, mainly ultraviolet rays, after they are made into processed products, and cannot be used as excellent products. In order to improve these drawbacks, various stabilizers have been proposed and put into practical use. As is well known, the performance required of stabilizers for polyvinyl chloride resins is wide-ranging in addition to the above-mentioned heat and light performance. Conventionally used stabilizers have various characteristics as their effects, and no stabilizer has been obtained that fully satisfies all of them. Even though relatively excellent stabilizers have been put into practical use, stabilizers with even better effects are required in order to obtain superior products. For example, organotin stabilizers have very good stabilizing effects. In particular, organotin mercapto stabilizers are very effective stabilizers with excellent heat resistance and initial coloring effects, but they have a strong peculiar odor and can be said to pose problems in the working environment. Furthermore, organic acid salts of alkaline earth metals generally have excellent heat resistance, but are poor in initial coloring properties. For this reason, for example, when obtaining a colored product, it not only takes time to delicately match the colors, but also changes depending on the processing temperature and time, making it difficult to obtain the desired uniform colored product. There is. Therefore, if an attempt is made to obtain the desired initial coloring by adding an organic acid salt of zinc to supplement this, the thermal stability and transparency will decrease, causing anxiety in thermal processing. Furthermore, as a conventional technique, compositions using a specific metal salt of a halogen oxyacid in combination with other stabilizers have been proposed (Japanese Patent Publication No. 47925/1983, Japanese Patent Publication No. 57-47925).
47926, Special Publication No. 57-47927, Special Publication No. 57-57056)
According to experiments conducted by the present inventors, these methods are not comprehensively sufficient as measures for stabilizing polyvinyl chloride resins. [Problem to be solved by the invention and means for solving the problem] As a result of various studies in view of these circumstances, the present inventor has added dehydroacetic acid, perchloric acid, and a metal selected from calcium, magnesium, barium, and zinc to polyvinyl chloride resin. By making the polyvinyl chloride resin composition characterized by blending one or more kinds of complex salts with , it has excellent high-temperature heat resistance, low-temperature heat resistance, coloring resistance, etc., and also has plate-out, The inventors have discovered that a composition with significantly improved blooming phenomenon can be obtained, leading to the present invention. The total amount of one or more of the perchlorine metal complex salts of dehydroacetic acid used in the present invention is based on 100 parts by weight of the polyvinyl chloride resin.
0.01 to 5 parts by weight can be used. Preferably, 0.05 to 3 parts by weight are used. [Resin to be stabilized] The polyvinyl chloride resin to be stabilized in the present invention includes polyvinyl chloride and vinyl chloride as components, and copolymers with monomers that can be copolymerized with the polyvinyl chloride, graft polymers, and block polymers. Polymers and polymer blends containing these as main components. [Other additive stabilizers that can be used in combination] In the present invention, the following stabilizers can be included as necessary. That is, acidic, neutral, basic group a, group a b
It is an organic acid salt of group B, and organic acids used in these include 2-ethylhexoic acid, octylic acid, isooctylic acid, lauric acid, oleic acid,
Higher fatty acids such as palmitic acid, isopalmitic acid, phenylstearic acid, stearic acid, isostearic acid, hydroxystearic acid, ricinoleic acid, caproic acid, myristic acid, neoacid, or maleic acid, malonic acid, sebacic acid, azelain Acid, dibasic acid such as adipic acid, phthalic acid, cyclohexanedicarboxylic acid, straight chain or side chain having 1 to 18 carbon atoms, substituted or unsubstituted saturated or unsaturated alcohol, alkoxy alcohol or having a total number of carbon atoms of 5 to 18 Substituted or unsubstituted aliphatic mono- or dicarboxylic acids such as semiesters with hydroxy compounds of cycloalkyl, arylalkyl, aryl, alkylaryl, benzoic acid, methylbenzoic acid, t-butylbenzoic acid, cinnamic acid, salicylic acid , rosin acid, octylphenol, nonylphenol, t-butylphenol, naphthenic acid, pyrrolidonecarboxylic acid, acetoacetate and condensates thereof, benzoylacetone, dibenzoylmethane, stearoylbenzoylmethane, and the like. Other stabilizers, such as organotin compounds, may also be used in combination. Examples include mono- or dialkyltin fatty acid salts or aromatic acid salts, mono- or dialkyltin maleates and polymer salts, mono- or dialkyltin maleic acid alkyl ester salts, mono- or dialkyltin mercaptocarboxylic acid salts and polymer salts, mono- or dialkyltin Tin mercaptocarboxylic acid alkyl ester salt, mono- or dialkyltin mercaptocarboxylic acid alkyl ester salt, mono- or disulfide salt, mono- or dialkyltin mercaptocarboxylic acid alkyl ester oxide salt, mono- or dialkyltin mercaptide mercaptoate ester salt, mono- or dialkyltin Examples include fatty acid alkyl mercaptide mono- or disulfide, and tin compounds described in JP-A-51-44149. (Here, the alkyl of alkyltin has 1 to 1 carbon atoms.
Showing 12. ) Furthermore, organic non-metallic stabilizers may also be used in combination as long as they do not impede the purpose. These organic nonmetallic stabilizers include, for example, 2-phenylindole, diphenylthiourea, cetyl and stearyl β-aminocrotonic acid esters, 1,3 and 1,4-butanediol bisβ-aminocrotonic acid esters, thiodiethylene glycol bis β - nitrogen-containing compounds such as aminocrotonic acid esters, isocyanuric acid and its derivatives such as tris(2-hydroxyethyl) cyanurate, pentaerythritol,
Polyhydric alcohols such as glycerin, diethylene glycol, dipentaerythritol, mannitol, and sorbitol, carboxylic acids such as benzoic acid, methylbenzoic acid, glycolic acid, maleic acid, cinnamic acid, p-tert-butylbenzoic acid, crotonic acid, and acetate. Acetate ester and its condensate, boric acid ester, thiodiglycolic acid ester, malonic acid mono- or diester, didodecyl-1,4-dihydro-2,6-dimethyl-3,5-pyridinedicarboxylate, benzoylacetone, dibenzoyl Examples include β-diketones such as methane, stearoylbenzoylmethane, dehydroacetic acid, and acetylacetone. [Other additives] Antioxidants may be used in the composition of the present invention, if necessary. These antioxidants include phenolic antioxidants including phenol derivatives such as hindered phenols, poly(alkylphenols) bonded via alkylene or alkylidene, and poly(alkylphenols) bonded via sulfur. There are sulfur compounds such as alkanoic acids and their alkyl esters, such as laurylstearyl thiodipropionate and diraryl thiodipropionate, and triphenylphosphite, tridecylphosphite, monophenyldidecylphosphite, Tricresyl phosphite, trisnonylphenyl phosphite,
Triscyclohexyl phenyl phosphite, tris phenyl phenyl phosphite, tris(dipropylene glycol) phosphite, tris(ethoxyethoxyethyl) phosphite, tris[4,4-butylidenebis(2-t-butyl-
5-methylphenol)] phosphite diphenyl phosphite, mono-2-ethylhexyl phosphite, tetra(tridecyl)-4,4-isopropylidene diphenyl diphosphite, tetra(phenyl) dipropylene glycyl diphosphite, heptakis (nonylphenyl)tetrakis(bisphenol A)pentaphosphite, heptakis(nonylphenyl)tetrakis(bisphenol A)pentaphosphite, heptakis(dipropylene glycol)triphosphite,
Bis (neopentyl glycol) dipropylene glycol diphosphite, tetrakis (butoxyethoxyethyl) ethylene glycol diphosphite, bis (cyclohexyl phenyl) bis (phenylethyl) 1,4-dibutanediol diphosphite, didecyl potassium phosphite , zinc di(octyl phosphite), calcium butoxyethoxyethyl phosphate, barium dilauryl stearate phosphite, tricresyl phosphate, trioctyl phosphate, tris(butoxyethyl) phosphate, xylenyl diphenyl phosphate, mono Lauryl phosphate, lauryloxypolyethoxyphosphate, di-t-butyl phenoxypolyethoxyphosphate, oleyloxypolyethoxydilauryl phosphate, other distearyl pentaerythritol diphosphite, didecyl pentaerythritol diphosphite, spiro-type phosphites such as diphenylpentaerythritol didecylphosphite, cage-type phosphites and tris(laurylthio)phosphites,
Tetrakis(mercaptooctyl)1,6-dimethylmercaptohexylene diphosphite, pentakis(dodecylmercapto)bis(1,6-hexylene dimercapto)triphosphite, 0,
There are phosphites and phosphates such as 0-diisopropylthiol phosphate and zinc dibutyl dithiophosphite. Weather resistance (light) by adding a UV absorber to the present invention
Since they can improve properties, they are used alone or in combination as appropriate depending on the purpose of use. These include benzophenones, benzotriazoles, salicylates,
These include cyanoacrylates, hindered amines, metal chelates, especially nickel and chromium salts. Also, phthalate ester plasticizers, other ester plasticizers, polyester plasticizers, phosphate ester plasticizers, chlorine plasticizers, other plasticizers, and epoxy compounds such as epoxidized soybean oil, epoxidized Epoxidized vegetable oils such as linseed oil, butyl epoxy stearate, octyl epoxy stearate, 2-ethylhexyl tall oil fatty acid ester, epoxy stearyl epoxy stearate, epoxidized tetrahydrophthalic acid octyl ester, epoxidized distearyl cyclohexanedicarboxylate. Epoxy compounds such as epoxidized esters such as epoxy resins and epoxy resins such as polycondensates of 4,4-isopropylidenephenol and epichlorohydrin may also be used in combination as necessary. Other metal oxides, hydroxides, chlorides, sulfides, carbonates, sulfates, sulfites, phosphates, phosphites, etc. of metals from groups of the periodic table, as required.
hypophosphites, chlorates, perchlorates, borates,
Inorganic metal compounds such as silicates may also be used. Examples include calcium carbonate, calcium oxide,
Calcium hydroxide, zinc oxide, zinc chloride, zinc hydroxide, zinc carbonate, zinc sulfide, zinc phosphite, zinc borate, barium perchlorate, magnesium oxide, magnesium hydroxide, magnesium carbonate, aluminum oxide, aluminum hydroxide, Synthetic zeolites such as alumina, sodium silicate, aluminum silicate, magnesium silicate, calcium silicate, A-type, Silicate metal salts such as metal-substituted zeolites substituted with group or group metal ions, activated clay, bentonite, talc, monazite powder, Oya stone powder, clay, red iron, kaolin,
Dioxide, hydrotalcite, anhydrous hydrotalcite, asbestos, antimony trioxide, barium hydroxide, barium carbonate, lithium hydroxide,
These include sodium hydroxide, potassium hydroxide, barium sulfate, etc. In addition, fluorescent agents, anti-fungal agents, plate-out inhibitors, anti-fog agents, cross-linking agents, surfactants, reinforcing agents, processing aids, mold release agents, and clay reducing agents are added to the polyvinyl chloride resin of the present invention. composition. [Synthesis Example] Next, a synthesis example of the product of the present invention will be shown. Synthesis example 1 500g of methanol and
Add 5g dimethyl sulfoxide (DMS).
After adding 74.1g of calcium hydroxide and stirring well,
Gradually add 168.1 g of dehydroacetic acid while maintaining the temperature at 40°C. After the addition is complete, the reaction is carried out at 40°C for about 1 hour while stirring. Next, add 201.0 g of perchloric acid, which had been adjusted to a 50% aqueous solution, using a dropping funnel for 40 minutes.
Drop the mixture over approximately 30 minutes while keeping the temperature below ℃. After the dropwise addition is complete, the reaction is continued at 60°C for 1 hour while stirring. The solvent and water are distilled off from the reaction solution using an evaporator under conditions of 60°C x 15mmHg. The obtained powder of calcium perchlorate dehydroacetate is washed with acetone and ether and dried. Yield 301.6g, yield
98.4%. Synthesis example 2 500g of methanol and
Add 5g dimethyl sulfoxide (DMS).
After adding 40.3g of magnesium oxide and stirring well,
Gradually add 168.1 g of dehydroacetic acid while keeping the temperature at 40°C. After the addition is complete, the reaction is continued at 40°C for 1 hour with stirring. Next, 201.0 g of perchloric acid, which had been previously adjusted to a 50% aqueous solution, was added dropwise over about 30 minutes using a dropping funnel while keeping the temperature below 40°C. After the dropwise addition is complete, the reaction is continued at 60°C for 1 hour while stirring. The solvent and water are distilled off from the reaction solution using an evaporator under conditions of 60°C x 15mmHg. The obtained powder of dehydroacetic acid magnesium perchlorate is washed with acetone and ether. Yield 286.2g, yield 98.4%. Synthesis Example 3 171.4 g of barium hydroxide is added to 500 g of ethanol in a 2000 c.c. four-necked flask and stirred well, and then 168.1 g of dehydroacetic acid is gradually added while maintaining the temperature at 40°C. After the addition is complete, the reaction is continued at 40°C for about 1 hour while stirring. Next, 201.0 g of perchloric acid, which had been previously adjusted to a 50% aqueous solution, was added dropwise over about 30 minutes using a dropping funnel while keeping the temperature below 40°C. After the dropwise addition is complete, the reaction is continued at 60°C for 1 hour while stirring.
The solvent and water are distilled off from the reaction solution using an evaporator under conditions of 60°C x 15mmHg. The obtained powder of dehydroacetic acid magnesium perchlorate is washed with acetone and ether. Yield 397.4g, yield 98.4%. Synthesis Example 4 Add 500 g of ethanol and 81.4 g of zinc oxide to a 2000 c.c. four-necked flask and stir well, then gradually add 168.1 g of dehydroacetic acid while maintaining the temperature at 40°C. After the addition is complete, the reaction is continued at 40°C for 1 hour with stirring. Next, 201.0 g of perchloric acid, which had been adjusted to a 50% aqueous solution in advance, was added dropwise using a dropping funnel over a period of about 30 minutes while keeping the temperature below 40°C. After the dropwise addition is complete, the reaction is continued at 60°C for 1 hour while stirring. The solvent and water are distilled off from the reaction solution using an evaporator under conditions of 60°C x 15mmHg. The obtained powder of dehydroacetic acid zinc perchlorate is washed with acetone and ether. Yield: 324.0 g, Yield: 97.6% [Example] Next, the stabilizing effect of the polyvinyl chloride resin according to the present invention will be shown by Examples and Synthesis Examples. In the following examples, initial colorability, heat resistance, plate-out, bloom, urethane adhesion, and weather resistance test results were evaluated using the following symbols, indicating the stages.
The heat resistance test is the time to black in the gear oven test, the initial coloring property is after 5 minutes, and the heat aging property is 400%.
Shows the degree of coloring after time. Bloom is a press sheet

[Table] After soaking in tap water for 24 hours and air drying, the blooming state was compared. Weather resistance evaluation shows the state of deterioration after 500 hours using a weather meter. Example 1 The additives shown in Table 1 were dry blended to the following basic formulation and kneaded for 10 minutes with two rolls at 175°C to make a sheet. This sheet was tested in a gear oven at 175°C. Also from this sheet 175
A press sheet was produced under the conditions of ℃ and 100 kg/cm ² .
Table 1 shows the heat resistance, initial coloration, bloom, and plate-out condition on the roll surface during kneading. (In the table, invention: invention example, ratio or comparison: comparative example, urethane adhesion: foamed urethane and soft PVC
Represents adhesion with. ) Basic blend polyvinyl chloride resin 100 parts by weight Dioctyl phthalate 50 〃 Epoxidized soybean oil 0.4 〃 Calcium stearate 0.5 〃 Zinc stearate 0.5 〃 Didecyl monophenyl phosphite 0.5 〃

[Table] Example 2 The additives shown in Table 2 were dry-blended to the following basic formulation and kneaded using two rolls at 175°C for 10 minutes to prepare a sheet. At this time, plate-out properties were evaluated. The sheet was tested in a gear oven at 185℃ to evaluate its heat resistance.
The heat storage property was evaluated after 400 hours in a gear oven. In addition, the sheet was pressed at 175° C. and 100 kg/cm ² and evaluated for initial colorability. These results are shown in Table 2. Basic blend polyvinyl chloride resin 100 parts by weight MBS 10 〃 Processing aid 1 〃 Epoxidized soybean oil 3 〃 Calcium stearate 0.5 〃 Zinc stearate 0.5 〃 Trisnonylphenyl phosphite 0.5 〃 Dioctyltin bis(octylthioglycolate) 0.5 〃

【table】

Claims (1)

[Claims] 1. A polyvinyl chloride resin characterized by blending one or more complex salts of dehydroacetic acid and perchloric acid with a metal selected from calcium, magnesium, barium, and zinc into a polyvinyl chloride resin. Composition.