JP7261790B2 - Vinyl chloride resin composition for waterproof sheet and waterproof sheet - Google Patents

Description

TECHNICAL FIELD The present invention relates to a vinyl chloride resin composition for a waterproof sheet (hereinafter also simply referred to as a "resin composition") and a waterproof sheet. The present invention relates to a vinyl chloride resin composition for a waterproof sheet from which a sheet is obtained, and to a waterproof sheet.

Waterproof sheets used for waterproofing roofs such as flat roofs generally use a vinyl chloride-based resin composition for waterproof sheets comprising a vinyl chloride-based resin, a plasticizer, a filler, and the like. In recent years, as houses are required to have high durability, waterproof sheets are also required to have high durability (weather resistance).

Under such circumstances, waterproof sheets made of various vinyl chloride resin compositions have been proposed. For example, in Patent Document 1, a soft polyvinyl chloride resin-based waterproof sheet composed of polyvinyl chloride resin, a plasticizer, glycine zinc, an organic phosphate ester, and chlorinated titanium oxide is disclosed, and in Patent Document 2, basic zinc phosphate is used. Alternatively, vinyl chloride resin compositions for waterproof sheets using basic zinc phosphite have been proposed.

JP-A-5-306343 Japanese Unexamined Patent Application Publication No. 2006-1963

However, the waterproof sheet proposed in Patent Document 1 was not necessarily sufficient in terms of weather resistance. Moreover, the waterproof sheet proposed in Patent Document 2 is still unsatisfactory in long-term weather resistance, so-called durability.

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a vinyl chloride resin composition for a waterproof sheet and a waterproof sheet that can provide a waterproof sheet excellent in heat stability, heat color resistance, weather resistance and durability.

As a result of intensive studies to solve the above problems, the present inventors have found that a predetermined amount of basic zinc phosphite, a hindered amine light stabilizer, and a plasticizer are added to a vinyl chloride resin. Therefore, the inventors have found that the above problems can be solved, and have completed the present invention.

で表され、Ｒ^１は、炭素原子数１～３０のアルキル基であるピペリジル基を有するヒンダードアミン系光安定剤であることを特徴とするものである。 That is, the vinyl chloride resin composition for a waterproof sheet of the present invention contains, with respect to 100 parts by mass of the vinyl chloride resin,
(A) as a component, the following general formula (1),
_{xZnO.ZnPHO3.yH2O (} 1)
0.01 to 10.0 parts by mass of basic zinc phosphite, where x is a number from 0.1 to 20, and y is 0 or a positive number,
(B) as a component, 0.01 to 10.0 parts by mass of a hindered amine light stabilizer;
30 to 100 parts by mass of a plasticizer as the component (C),
contains,
The component (B) is represented by the following general formula (2),

wherein R ¹ is a hindered amine light stabilizer having a piperidyl group which is an alkyl group having 1 to 30 carbon atoms.

The waterproof sheet of the present invention is characterized by being obtained from the vinyl chloride resin composition of the present invention.

According to the present invention, it is possible to provide a vinyl chloride-based resin composition for a waterproof sheet and a waterproof sheet from which a waterproof sheet having excellent thermal stability, heat color resistance, weather resistance and durability can be obtained.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described in detail.
The vinyl chloride resin used in the vinyl chloride resin composition for waterproof sheets of the present invention is not particularly limited to polymerization methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. Vinyl, chlorinated polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, chloride vinyl-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-chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride-methacrylic acid ester copolymer vinyl chloride-based resins such as coalescence, vinyl chloride-acrylonitrile copolymers, vinyl chloride-various vinyl ether copolymers, and blends thereof or other chlorine-free synthetic resins, such as acrylonitrile-styrene copolymers, Acrylonitrile-butadiene-styrene copolymers, ethylene-vinyl acetate copolymers, ethylene-ethyl (meth)acrylate copolymers, blends with polyesters, block copolymers, graft copolymers and the like can be mentioned. . These vinyl chloride resins may be a mixture of two or more, or may be a mixture with other synthetic resins. The vinyl chloride resin used is preferably polyvinyl chloride from the viewpoints of heat stability, heat color resistance, weather resistance and durability.

The resin composition of the present invention contains basic zinc phosphite represented by the following general formula (1) as component (A).
_{xZnO.ZnPHO3.yH2O (} 1)

Here, x in the general formula (1) represents 0.1 to 20, preferably 0.3 to 10, more preferably 0.3 to 10 in terms of thermal stability, heat color resistance, weather resistance and durability. 1 to 5. If x is less than 0.1 or exceeds 20, the effect of improving weather resistance is insufficient. again. y represents 0 or a positive integer.

The basic zinc phosphite according to the resin composition of the present invention has a composition represented by the above general formula (1), and its production method is not particularly limited. and zinc orthophosphite, or those obtained by the reaction of zinc oxide and phosphorous acid, such as the method described in JP-A-50-50297.

The average particle diameter of the basic zinc phosphite is not particularly limited, but is preferably 100 μm or less, more preferably 10 μm or less. By using particles having an average particle size within the above range, higher effects can be exhibited in terms of thermal stability, resistance to heat coloration, weather resistance and durability.

The content of the component (A) in the resin composition of the present invention is 0.01 to 10.0 parts by mass with respect to 100 parts by mass of the vinyl chloride resin. From the viewpoint of properties and durability, the amount is preferably 0.01 to 5.0 parts by mass, more preferably 0.05 to 2.0 parts by mass. If the amount of component (A) is less than 0.01 parts by mass, the above effect is hardly observed, while if it exceeds 10 parts by mass, not only is there no effect of increasing the amount, but the thermal stability is lowered. . In addition, in the resin composition of this invention, (A) component may be used individually by 1 type, and may use 2 or more types together.

In the resin composition of the present invention, together with the basic zinc phosphite, metals other than zinc, such as alkali metals such as lithium, sodium and potassium, alkaline earth metals such as magnesium, calcium and barium, and aluminum A basic phosphite such as In that case, a mixture with basic zinc phosphite or a complex salt of zinc and other metals can also be used. However, when a basic phosphite of a metal other than zinc is used together, the content of the metal other than zinc should preferably not exceed 50% by mass of the total metal content.

Moreover, the resin composition of this invention contains a hindered amine light stabilizer as a (B) component. Such a hindered amine light stabilizer may be a conventionally known hindered amine light stabilizer, and is not particularly limited. For example, 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6-tetramethyl-4- piperidyl benzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1-octoxy-2, 2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, tetrakis(1, 2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, bis(2,2,6,6-tetramethyl-4-piperidyl) bis(tridecyl) -1,2,3,4-butanetetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) bis(tridecyl)-1,2,3,4-butanetetracarboxylate , bis(1,2,2,6,6-pentamethyl-4-piperidyl)-2-butyl-2-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, 1,2,2,6 , 6-tetramethyl-4-piperidyl methacrylate, poly[{6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl}{(2,2 ,6,6-tetramethyl-4-piperidyl)imino}hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl)imino}], 1,2,3,4-butanecarboxylic acid/2 ,2-bis(hydroxymethyl)-1,3-propanediol/3-hydroxy-2,2-dimethylpropanal/1,2,2,6,6-pentamethyl-4-piperidinyl ester polycondensate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) decanedioate/methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate mixture, 2,2,6,6 -tetramethyl-4-piperidyl methacrylate, 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol/diethyl succinate polycondensate, 1,6-bis(2,2, 6,6-tetramethyl-4-piperidylamino)hexane/dibromoethane polycondensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane/2,4-dichloro- 6-morpholino-s-triazine polycondensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane/2,4-dichloro-6-tert-octylamino-s- Triazine polycondensate, 1,5,8,12-tetrakis[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)-s-triazine- 6-yl]-1,5,8,12-tetraazadodecane, 1,5,8,12-tetrakis[2,4-bis(N-butyl-N-(1,2,2,6,6- pentamethyl-4-piperidyl)amino)-s-triazin-6-yl]-1,5,8,12-tetraazadodecane, 1,6,11-tris[2,4-bis(N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl)amino)-s-triazin-6-ylamino]undecane, 1,6,11-tris[2,4-bis(N-butyl-N-( 1,2,2,6,6-pentamethyl-4-piperidyl)amino)-s-triazin-6-ylamino]undecane, 3,9-bis[1,1-dimethyl-2-{tris(2,2, 6,6-tetramethyl-4-piperidyloxycarbonyl)butylcarbonyloxy}ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, 3,9-bis[1,1-dimethyl- 2-{tris(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)butylcarbonyloxy}ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, bis( 1-undecyloxy-2,2,6,6-tetramethylpiperidin-4-yl)carbonate, 2,2,6,6-tetramethyl-4-piperidylhexadecanoate, 2,2,6,6 -tetramethyl-4-piperidyl octadecanoate and the like.

Further, the hindered amine light stabilizer of the component (B) is a hindered amine light stabilizer having a piperidyl group represented by the following general formula (2) from the viewpoint of heat stability, heat color resistance, weather resistance and durability. is preferred.

ここで、一般式（２）中、Ｒ^１は、炭素原子数１～３０のアルキル基を表す。

Here, in general formula (2), R ¹ represents an alkyl group having 1 to 30 carbon atoms.

Examples of the alkyl group having 1 to 30 carbon atoms which R ¹ in the general formula (2) can take include a linear alkyl group and a branched alkyl group. Linear alkyl groups include, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, Pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, henicosyl group, docosyl group, tricosyl group, tetracosyl group, pentacosyl group, hexacosyl group, heptacosyl group, octacosyl group, nonacosyl group, triacontyl group, and the like. Examples of branched alkyl groups include groups obtained by substituting one or more of the above linear alkyl groups with alkyl groups having 1 to 9 carbon atoms.

Examples of the hindered amine light stabilizer having a group represented by the general formula (2) include bis(1-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis(1-undecyl). oxy-2,2,6,6-tetramethylpiperidin-4-yl)carbonate and the like.

In the resin composition of the present invention, the component (B) is 0.01 to 10.0 parts by mass with respect to 100 parts by mass of the vinyl chloride resin. From the viewpoint of properties, the amount is preferably 0.02 to 5.0 parts by mass, more preferably 0.05 to 2.0 parts by mass. In addition, in the resin composition of this invention, (B) may be used individually by 1 type, and may use 2 or more types together.

Moreover, the resin composition of this invention contains a plasticizer as (C)component. Such a plasticizer is not particularly limited, and any plasticizer commonly used for vinyl chloride resins can be used. For example, phthalate plasticizers such as dibutyl phthalate, butylhexyl phthalate, diheptyl phthalate, dioctyl phthalate, di-2-ethylhexyl phthalate, diisononyl phthalate, diisodecyl phthalate, diundecyl phthalate, dilauryl phthalate, ditridecyl phthalate, dicyclohexyl phthalate, dioctyl terephthalate, etc. Adipate plasticizers such as dioctyl adipate, diisononyl adipate, diisodecyl adipate, and di(butyldiglycol) adipate; triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tri(isopropylphenyl) phosphate, triethyl phosphate, tributyl Phosphate-based plasticizers such as phosphate, trioctyl phosphate, tri(butoxyethyl) phosphate, and octyldiphenyl phosphate; polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, and 1,3-propylene glycol , 1,3-butanediol, 1,4-butanediol, 1,5-hexanediol, 1,6-hexanediol, neopentyl glycol, etc., and dibasic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, Polyester-based plasticizers using acids, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, etc., optionally using monohydric alcohol and/or monocarboxylic acid as a stopper. In addition, tetrahydrophthalic acid plasticizer, azelaic acid plasticizer, sebacic acid plasticizer, stearic acid plasticizer, citric acid plasticizer, trimellitic acid plasticizer, pyromellitic acid plasticizer, biphenylene poly Carboxylic acid-based plasticizers and the like are included. Among these plasticizers, phthalic acid ester plasticizers obtained from phthalic acid and alcohols having 8 to 13 carbon atoms, particularly alcohols having 9 to 11 carbon atoms, especially diisononyl phthalate and diundecyl phthalate should be used. However, it is preferable because a waterproof sheet having particularly excellent weather resistance can be obtained.

The content of component (C) in the resin composition of the present invention is 30 to 100 parts by mass, preferably 40 to 80 parts by mass, more preferably 45 to 100 parts by mass, based on 100 parts by mass of the vinyl chloride resin. It is in the range of 70 parts by mass. In addition, in the resin composition of this invention, (C)component may be used individually by 1 type, and may use 2 or more types together.

The resin composition of the present invention may further contain a filler. Examples of fillers used in the resin composition of the present invention include calcium carbonate (heavy, light, precipitated), gypsum, titanium oxide, barium sulfate, alumina, hydrocalumite, sodium silicate, and aluminum silicate. , magnesium silicate, calcium silicate, zeolite, silica, diatomaceous earth, activated clay, talc, mica, clay, red iron oxide, asbestos, graphite, carbon black, etc., but the use of calcium carbonate or clay in particular reduces vinyl chloride It is preferable because it has little adverse effect on the weather resistance of the system resin.

When the filler is used, the content thereof is preferably 5 to 100 parts by mass, more preferably 8 to 60 parts by mass, and even more preferably 10 to 60 parts by mass with respect to 100 parts by mass of the vinyl chloride resin.

Furthermore, it is preferable to add an organic acid zinc salt to the resin composition of the present invention because it can suppress the coloring of the product. Organic acid zinc salts include zinc salts of carboxylic acids or phenols. Here, examples of the carboxylic acid include caproic acid, caprylic acid, pelargonic acid, 2-ethylhexylic acid, capric acid, neodecanoic acid, undecylenic acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, 12 - hydroxystearic acid, chlorostearic acid, 12-ketostearic acid, phenylstearic acid, ricinoleic acid, linoleic acid, linoleic acid, oleic acid, arachidic acid, behenic acid, erucic acid, brassic acid and similar acids, and tallow fatty acids, Mixtures of the above naturally occurring carboxylic acids such as coconut oil fatty acid, tung oil fatty acid, soybean oil fatty acid and cottonseed oil fatty acid, benzoic acid, p-tert-butylbenzoic acid, ethylbenzoic acid, isopropylbenzoic acid, toluic acid, xylyl acid . The organic acid zinc salt may be a normal salt, an acid salt, a basic salt, an overbased complex, or the like.

The amount of the zinc salt of the organic acid is preferably 0.001 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, per 100 parts by mass of the vinyl chloride resin. One or two or more organic acid zinc salts may be used.

In addition, the resin composition of the present invention may contain an organic acid salt of a metal other than zinc. Ca, Mg, Ba, Sr, Cd, Al) salts and the like.

Examples of the carboxylic acids, organic phosphoric acids and phenols include those exemplified above. The organic acid salt may be a normal salt, an acid salt, a basic salt, an overbased complex, or the like. Among the above organic acid salts, calcium salts and barium salts are preferred, and organic acid barium salts are particularly preferred. Moreover, it is preferable to use an organic acid zinc salt and an organic acid barium salt together.

The amount of the organic acid salt of a metal other than zinc is preferably 0.001 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, per 100 parts by mass of the vinyl chloride resin.

In addition, the resin composition of the present invention may further contain various additives that are usually used as additives for vinyl chloride resins, such as hydrotalcite compounds, β-diketone compounds, organic phosphite compounds, phenolic Alternatively, a sulfur-based antioxidant, an epoxy compound, a polyol compound, an ultraviolet absorber, or the like may be blended.

As the hydrotalcite compound, a double salt compound composed of magnesium and aluminum, or zinc, magnesium and aluminum represented by the following general formula (3) is preferably used. good too.

ここで、式（３）中、ｘ１、ｘ２およびｙ１は各々下記式、０≦ｘ２／ｘ１＜１０、２≦ｘ１＋ｘ２＜２０、０≦ｙ１≦２で表される条件を満足する数を示し、ｍは０または任意の整数を示す。

Here, in formula (3), x1, x2 and y1 are numbers satisfying the conditions represented by the following formulas: 0 ≤ x2/x1 < 10, 2 ≤ x1 + x2 < 20, 0 ≤ y1 ≤ 2, m represents 0 or any integer.

The above hydrotalcite compound may be a natural product or a synthetic product. Methods for synthesizing synthetic products include JP-B-46-2280, JP-B-50-30039, JP-B-51-29129, JP-B-3-36839, JP-A-61-174270, Known methods described in JP-A-2001-164042, JP-A-2002-53722, etc. can be exemplified. In addition, in the present invention, the above hydrotalcite compound can be used without being limited by its crystal structure, crystal particle size, and the like.

In addition, the surface of the hydrotalcite compound may be treated with a higher fatty acid such as stearic acid, a higher fatty acid metal salt such as an alkali metal oleate, an organic sulfonate metal salt such as an alkali metal dodecylbenzenesulfonate, Those coated with higher fatty acid amide, higher fatty acid ester, wax, or the like can also be used. These hydrotalcite compounds may be used singly or in combination of two or more.

Examples of the β-diketone compounds include acetylacetone, triacetylmethane, 2,4,6-heptatrione, butanoylacetylmethane, lauroylacetylmethane, palmitoylacetylmethane, stearoylacetylmethane, phenylacetylacetylmethane, dicyclohexylcarbonylmethane. , benzoylformylmethane, benzoylacetylmethane, dibenzoylmethane, stearoylbenzoylmethane, octylbenzoylmethane, bis(4-octylbenzoyl)methane, benzoyldiacetylmethane, 4-methoxybenzoylbenzoylmethane, bis(4-carboxymethylbenzoyl) Methane, 2-carboxymethylbenzoylacetyloctylmethane, dehydroacetic acid, cyclohexane-1,3-dione, methyl 3,6-dimethyl-2,4-dioxycyclohexane-1carboxylate, 2-acetylcyclohexanone, dimedone, 2- benzoylcyclohexane and the like. Metal salts of these β-diketone compounds can also be used, and examples of metal species capable of providing β-diketone metal salts include alkali metals such as lithium, sodium and potassium; magnesium, calcium, strontium and barium. alkaline earth metals such as zinc, aluminum, tin, and alkyltin. These β-diketone compounds may be used singly or in combination of two or more.

Examples of the organic phosphite compounds include triphenylphosphite, tris(2,4-di-tert-butylphenyl)phosphite, tris(nonylphenyl)phosphite, tris(dinonylphenyl)phosphite, tris(mono , dimixed nonylphenyl)phosphite, diphenylacid phosphite, 2,2′-methylenebis(4,6-di-tert-butylphenyl)octylphosphite, diphenyldecylphosphite, phenyldiisodecylphosphite, tributylphosphite, tri (2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, dibutyl acid phosphite, dilauryl acid phosphite, trilauryl trithiophosphite, bis(neopentylglycol) 1,4-cyclohexanedimethyldiphosphite Phyto, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, Phenyl-4,4'-isopropylidenediphenol pentaerythritol diphosphite, tetra(C12-C15 mixed alkyl)-4,4'-isopropylidenediphenyl diphosphite, hydrogenated 4,4'-isopropylidenedi Phenol polyphosphite, bis(octylphenyl)・bis[4,4′-n-butylidenebis(2-tert-butyl-5-methylphenol)]・1,6-hexanediol・diphosphite, tetratridecyl・4, 4'-butylidenebis(2-tert-butyl-5-methylphenol) diphosphite, hexa(tridecyl) 1,1,3-tris(2-methyl-5-tert-butyl-4-hydroxyphenyl)butane triphosphite , 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2-butyl-2-ethylpropanediol/2,4,6-tri-tert-butylphenol monophosphite and the like. . These organic phosphite compounds may be used singly or in combination of two or more.

Examples of the phenolic antioxidant include 2,6-di-tert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-di-tert-butyl-4- hydroxyphenyl)propionate, distearyl (3,5-di-tert-butyl-4-hydroxybenzyl)phosphonate, thiodiethylenebis[(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 4,4' - thiobis(6-tert-butyl-m-cresol), 2-octylthio-4,6-di(3,5-di-tert-butyl-4-hydroxyphenoxy)-s-triazine, 2,2'-methylenebis( 4-methyl-6-tert-butylphenol), bis[3,3-bis(4-hydroxy-3-tert-butylphenyl)butyric acid] glycol ester, 4,4'-butylidenebis(6-tert-butyl- m-cresol), 2,2′-ethylidenebis(4,6-di-tert-butylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, bis[ 2-tert-butyl-4-methyl-6-(2-hydroxy-3-tert-butyl-5-methylbenzyl)phenyl]terephthalate, 1,3,5-tris(2,6-dimethyl-3-hydroxy- 4-tert-butylbenzyl) isocyanurate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris(3,5-di-tert-butyl) Butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,3,5-tris[(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxyethyl]isocyanurate, tetrakis[methylene -3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, 2-tert-butyl-4-methyl-6-(2-acryloyloxy-3-tert-butyl-5-methylbenzyl ) phenol, 3,9-bis[1,1-dimethyl-2-hydroxyethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane-bis[β-(3-tert-butyl- 4-hydroxy-5-butylphenyl)propionate], triethylene glycol bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate] and the like. These phenol-based antioxidants may be used singly or in combination of two or more.

Examples of the sulfur-based antioxidants include dilauryl, dimyristyl, myristylstearyl, and distearyl esters of thiodipropionic acid such as dialkylthiodipropionates, and pentaerythritol tetra(β-dodecylmercaptopropionate). Examples include β-alkylmercaptopropionate esters of polyols. These sulfur-based antioxidants may be used singly or in combination of two or more.

Examples of the epoxy compound include epoxidized animal and vegetable oils such as epoxidized soybean oil, epoxidized linseed oil, epoxidized tung oil, epoxidized fish oil, epoxidized beef tallow oil, epoxidized castor oil, and epoxidized safflower oil; Methyl stearate, -butyl, -2-ethylhexyl, -stearyl ester, epoxidized polybutadiene, tris(epoxypropyl) isocyanurate, epoxidized tall oil fatty acid ester, epoxidized linseed oil fatty acid ester, bisphenol A diglycidyl ether, vinylcyclohexene Epoxy compounds such as diepoxide, dicyclohexene diepoxide, 3,4-epoxycyclohexylmethylepoxycyclohexane carboxylate, and the like. In addition, when using an epoxy compound that is also used as a plasticizer, such as epoxidized soybean oil, 100 parts by mass together with the component (C) in order to prevent a decrease in the rigidity of the waterproof sheet. Do not use more than These epoxy compounds may be used individually by 1 type, and may use 2 or more types together.

Examples of the polyol compound include trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentalythritol, polypentaerythritol, stearic acid half ester of pentaerythritol or dipentaerythritol, bis(dipentaerythritol) adipate, and glycerin. , tris(2-hydroxyethyl) isocyanurate and the like. These polyol compounds may be used singly or in combination of two or more.

Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 5,5′-methylenebis(2-hydroxy-4-methoxybenzophenone ) and other 2-hydroxybenzophenones; 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-3, 5-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5 -dicumylphenyl)benzotriazole, 2,2′-methylenebis(4-tert-octyl-6-benzotriazolyl)phenol, 2-(2-hydroxy-3-tert-butyl-5-carboxyphenyl)benzotriazole 2-(2-hydroxyphenyl)benzotriazoles such as polyethylene glycol esters of; benzoates such as ,4-di-tert-amylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate; 2-ethyl-2'- Substituted oxanilides such as ethoxyoxanilide and 2-ethoxy-4'-dodecyloxanilide; ethyl-α-cyano-β,β-diphenylacrylate, methyl-2-cyano-3-methyl-3-(p- cyanoacrylates such as methoxyphenyl)acrylate; 2-(2-hydroxy-4-octoxyphenyl)-4,6-bis(2,4-di-tert-butylphenyl)-s-triazine, 2-(2- hydroxy-4-methoxyphenyl)-4,6-diphenyl-s-triazine, 2-(2-hydroxy-4-propoxy-5-methylphenyl)-4,6-bis(2,4-ditert-butylphenyl) )-s-triazine and other triaryltriazines. These ultraviolet absorbers may be used singly or in combination of two or more.

Moreover, the resin composition of the present invention may contain a stabilizing aid that is usually used for vinyl chloride resins. Examples of such stabilizing aids include diphenylthiourea, anilinodithiotriazine, melamine, benzoic acid, cinnamic acid, p-tert-butylbenzoic acid, silicic anhydride, silicates, zeolites, perchlorates, and the like. is mentioned.

In addition, the resin composition of the present invention may optionally contain additives normally used for vinyl chloride resins, such as cross-linking agents, antistatic agents, foaming agents, anti-fogging agents, plate-out inhibitors, and surface treatment. agents, lubricants, flame retardants, antifogging agents, fluorescent agents, antifungal agents, bactericides, metal deactivators, release agents, pigments, processing aids, antioxidants, light stabilizers, etc. .

In addition, the resin composition of the present invention is not particularly limited in the processing method of the vinyl chloride resin, for example, calendar processing, roll processing, extrusion molding processing, melt casting method, pressure molding processing, powder molding, etc. It can be used preferably.

The resin composition of the present invention is preferably used for waterproof sheets, building materials and the like. Specifically, it can be preferably used for waterproof sheets used on roofs such as flat roofs, roofing sheets, waterproof sheets for swimming pools, waterproof sheets for civil engineering work, waterproof sheets for impermeable water, reservoirs, irrigation channels, etc.

EXAMPLES The vinyl chloride resin composition for waterproof sheets of the present invention will be described in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited to these.

[Example 1, Reference Examples 1 to 3, Comparative Examples 1 to 3]
Calendering was performed at 175° C., 30 rpm, and 5 minutes using the formulation below to prepare a sheet having a thickness of 0.7 mm. The obtained sheet was placed in a gear oven at 190° C. and the blackening time (minutes) was measured as a <thermal stability test>. Table 1 shows the results.

Also, the above 0.7 mm thick sheets were laminated together and pressed at 180° C. for 5 minutes or 30 minutes to prepare 1 mm thick press sheets. Using the obtained sheet, a heat color resistance test and a weather resistance test were conducted by the following methods. These results are shown in Table 1.

<Heat-resistant coloring test>
A yellowness index (Y.I value) was measured for a 1 mm thick sheet pressed at 180° C. for 5 minutes and a 1 mm thick sheet pressed at 180° C. for 30 minutes. It can be said that the smaller the value of the yellowness index is, the less coloration is and the better the heat-resistant coloration resistance is.

<Weather resistance test>
A 1 mm thick sheet pressed at 180 ° C. for 5 minutes was subjected to an accelerated weather resistance test for 5 days ( 120 hours). The colored state of the sheet was visually observed every 24 hours and evaluated on a scale of 1 to 10. Evaluation 1 has no coloration and is the most excellent in weather resistance, and as the numerical value increases, it is colored and has poor weather resistance, and evaluation 10 is the worst in weather resistance.

Test conditions Light source: Water-cooled metal halide lamp Irradiance: 75 mW/cm ²
Irradiation conditions: Light only BP 63° C. Humidity 50% RH spray Light for 2 hours 120 sec.

(Formulation)
Polyvinyl chloride resin (degree of polymerization: 1300) 100 parts by mass (A) Component: Basic zinc phosphite See Table 1 below (B) Component: Hindered amine light stabilizer See Table 1 below Component (C): Diisononyl phthalate 40 mass Part (C) component: polyester plasticizer ^*1 20 parts by mass organic acid zinc salt ^*2 0.25 parts by mass organic acid barium salt ^*3 0.25 parts by mass β-diketone compound ^*4 0.1 parts by mass hydrotal Site compound ^*5 1.5 parts by mass Filler ^*6 20 parts by mass Organic phosphite compound ^*7 0.5 parts by mass Phenolic antioxidant ^*8 0.05 parts by mass UV absorber ^*9 0.25 parts by mass UV light Absorbent ^{* 10} 0.5 parts by mass * 1: ADEKA CIZER PN-7550 (manufactured by ADEKA Co., Ltd.)
*2: Zinc stearate *3: Barium stearate *4: Dibenzoylmethane *5: Magcellar 1 (manufactured by Kyowa Chemical Industry Co., Ltd.)
*6: Clay *7: Tetra( _C12 - _C15 mixed alkyl)-4,4'-isopropylidene diphenyl diphosphite *8: Pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4 -hydroxyphenyl)propionate]
*9: 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole *10: 2-hydroxy-4-n-octyloxybenzophenone

Hindered amine light stabilizers 1 to 4 having the following structural formulas were used as the component (B) of the hindered amine light stabilizer in Table 1 below.

ヒンダードアミン系光安定剤２

ヒンダードアミン系光安定剤３

ヒンダードアミン系光安定剤４（数平均分子量１９００～２１００）

Hindered amine light stabilizer 1

Hindered amine light stabilizer 2

Hindered amine light stabilizer 3

Hindered amine light stabilizer 4 (number average molecular weight 1900-2100)

表中の各成分の単位は質量部である。

The unit of each component in the table is parts by mass.

From Table 1, it can be seen that the vinyl chloride resin composition for waterproof sheets of the present invention can provide molded articles excellent in heat stability, heat color resistance, weather resistance and durability.

Claims (2)

For 100 parts by mass of vinyl chloride resin,
(A) as a component, the following general formula (1),
_{xZnO.ZnPHO3.yH2O (} 1)
0.01 to 10.0 parts by mass of basic zinc phosphite, where x is a number from 0.1 to 20, and y is 0 or a positive number,
(B) as a component, 0.01 to 10.0 parts by mass of a hindered amine light stabilizer;
30 to 100 parts by mass of a plasticizer as the component (C),
contains ,
The component (B) is represented by the following general formula (2),

wherein R ¹ is a hindered amine light stabilizer having a piperidyl group which is an alkyl group having 1 to 30 carbon atoms . A waterproof sheet obtained from the vinyl chloride resin composition for a waterproof sheet according to claim 1 .