JP3426310B2 - Vinyl chloride resin composition for powder molding - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyvinyl chloride for powder molding.
-Based resin composition, more specifically, powder suitable for automotive interior materials
Vinyl chloride resin for rotary molding or powder slush molding
It relates to a composition. 2. Description of the Related Art In recent years,
Crash pads and armless as automotive interior materials
Or headrest, console, meter cover or
Is lightweight for covering materials such as door trim.
Excellent and soft feeling and high-quality leather grain pattern
And stitched patterns are more demanding
I have. Conventionally, as these covering materials,
Is a soft plastic mainly composed of vinyl chloride resin and ABS resin.
PVC resin and plasticizer for vacuum molded products and pastes
And slush-molded sol mainly composed of
(Hereinafter, referred to as “sol molded product”).
However, vacuum molded products are not
Achieved purpose, but lacked softness and hard feeling
You can only get a touch, and you can even get a high-quality
Shape or complex shape with stitch pattern
It was difficult to shape something. In addition, vacuum
Mold products have large residual distortion during molding and have been used for a long time
Also, there is a disadvantage that cracks easily occur in molded products
You. On the other hand, sol molded products have a soft feeling.
Low melting temperature in the metal due to the low gelation temperature
Phenomenon such as low mark, lip or sol stringing
This may cause lack of surface smoothness or zoning from the mold.
It takes too long to discharge
However, it has disadvantages such as thickening. In addition, sol formation
For models, it is very difficult to clean tanks and pipes when changing colors.
Or the viscosity changes with time,
There is also a problem that it cannot tolerate preservation for a while. [0005] To solve these drawbacks and problems,
Recently, the powder molding method has been spotlighted. This powder
Powder molding methods generally include fluid immersion, electrostatic coating, powder
Thermal spraying, powder rotary molding or powder slush molding
But especially for covering materials for automobile interior materials.
Suitable for powder rotary molding or powder slush molding
You. [0006] Such powder rotary molding method or powder slush
The molding method uses a mold at 180 ° C or higher and powder supply.
Rotate or swing, or jet
Powder to weld the inner surface of the mold.
Or forcedly collect it in the powder supply box
is there. Heating of a mold used for such a powder molded product
The method includes gas heating furnace method, heat medium oil circulation method, heat medium
Immersion method in oil or hot fluidized sand or high frequency induction heating
There is a thermal method. The powder composition used in the above powder molding method
Can complete processing in a short time due to high temperature
It has excellent thermal stability
Of course, it quickly gelled in the mold and demolded
It is required to have excellent moldability and low mold contamination.
You. For example, Japanese Patent Application Laid-Open No. 62-270645
Report, JP-A-1-65157 discloses a salt for powder molding.
Ba-Zn stabilizer and metal salt of perchloric acid
Add perchlorate ion type hydrotalcite
And Japanese Patent Application Laid-Open No. 63-125553.
In the official gazette, a combination of basic lead silicate and perchlorate is added.
Japanese Patent Laid-Open No. 4-359949 is proposed.
The report includes hydrotalcite compounds or zeolite compounds.
Substances, calcium oxide and halogen oxyacid salts or
It has been proposed to add a metal salt in combination,
The point could not be improved sufficiently. Further, Japanese Patent Application Laid-Open No. 53-13659 discloses
Can be used to add a metal carboxylate or
Enolates, basic inorganic acid salts and halogen oxyacid salts
It has been proposed to add them together.
No. 2951, an organic acid metal salt is added to a halogen-containing resin,
Addition of hydrotalcites and halogen oxyacids
It has been proposed in Japanese Patent Application Laid-Open No. 61-78874.
In the publication, perchloric acid-treated metal silicate is added to halogen-containing resin.
It has been proposed to add
No. 636 discloses that silicic acid or silicic acid is added to a chlorine-containing polymer.
A powdered material containing perhalogen oxyacid in the salt
It has been proposed that they be combined.
In the publication, dehydroacetic acid and polyvinyl chloride
And perchloric acid and calcium, magnesium, barium,
It is proposed to add a complex salt with a metal selected from lead
Japanese Patent Application Laid-Open No. Hei 4-15260 discloses a quaternary
Ammonium salt-perchlorate complex held in silicate
It has been proposed to blend the coalescable into a polar resin polymer
However, these are simply applied to chlorine-containing resin for powder molding.
However, the above-mentioned drawbacks could not be improved. [0011] Under these circumstances, thermal stability, heat aging, and
Good gelling, demolding and mold contamination
To provide powder compositions with excellent moldability such as formability
Was. [0012] Accordingly, the object of the present invention is to provide heat stability, heat aging.
Excellent gelling and coloring properties, as well as gelling properties, mold release properties and
Provide powder composition with excellent moldability such as mold contamination
It is in. Means for Solving the Problems The present inventors have conducted intensive studies.
As a result, the specific silicate compound
, Perchlorates and β-diketone compound
Vinyl chloride resin composition,
The inventors have found that the present invention has been completed and completed the present invention. That is, the present invention provides a vinyl chloride resin 100
In parts by weight, (a) the following [Chemical Formula 2] (same as the above [Chemical Formula 1])
At least one of the silicate compounds represented by the general formula (I)
0.001 to 10 parts by weight of a seed, (b) a metal salt of perchloric acid,
Ammonium salt of perchloric acid, perchloric acid treated hydrotal
Site or perchloric acid treated silicate 0.001 to 10 weight
Part and at least one of the (c) β-diketone compounds
Powder-forming salt obtained by adding 0.001 to 10 parts by weight
It is intended to provide a vinyl chloride resin composition. Embedded image M (O) _a ・ NSiO _Two ・ MH _Two O (I) (where M is an alkaline earth metal Or Alminium Time table
A is 1 when M is an alkaline earth metal, and M is
In the case of minium, represents 3/2, n represents 1 to 5,
m represents any positive integer. Hereinafter, a vinyl chloride-based resin for powder molding according to the present invention will be described.
The fat composition will be described in detail. The vinyl chloride resin used in the present invention and
Is prepared by suspension polymerization, bulk polymerization or emulsion polymerization.
Copolymerized with vinyl chloride polymer or vinyl chloride
Co-polymerization with ethylene, propylene, vinyl acetate, etc.
Combined or ethylene and vinyl acetate copolymer and chloride
Graft copolymer with vinyl or two or more of these
A mixture of polymers, but is not necessarily limited to this
Not. In the composition of the present invention, the component (a)
At least one of the silicate compounds represented by the general formula (I)
Seeds are used. In the above general formula (I), M is an alkali
Represents earth metal or aluminum, said alkaline earth gold
The genus includes magnesium, calcium, barium, sulfur
Trontium and the like, especially magnesium, calcium
Cium and aluminum are preferred. In addition, the above general formula
In (I), n represents the number of 1-5. When n is less than 1
Lowers the coloring property, and when n exceeds 5,
Poor synergistic effect with other components on qualitative and moldability. The above-mentioned silicate compounds may be natural or synthetic.
It may be a product. The amount of the silicate compound added is vinyl chloride.
0.001 to 10 parts by weight, based on 100 parts by weight of the system resin,
Preferably it is 0.01 to 5 parts by weight. The above addition amount
If the amount is less than 0.001 part by weight, a sufficient effect cannot be obtained.
In addition, the improvement of the effect is not seen even if it exceeds 10 parts by weight.
Not. One of the components (b) used in the present invention
Metal component of the perchloric acid metal salt
, Sodium, potassium, strontium, barium
, Zinc, cadmium, lead, aluminum, etc.
And the metal salts of perchloric acid composed of these metals are:
It may be anhydrous or hydrated.
Alcohol and butyl diglycol adipate
And its dehydrates dissolved in solvent and ester solvents
May be. One of the components (b) used in the present invention
Ammonium salt of perchloric acid can be anhydrous or hydrated.
Good. One of the components (b) used in the present invention
Perchloric acid-treated hydrotalcite
Place some or all of the carbonic acid in the
It is a modified perchloric acid modified product. Here, the hydrotalcite compound is
Magnesium and / or zinc and aluminum charcoal
An acid double salt compound, which is usually represented by the following general formula (I)
The compound represented by I) is used. Embedded image The above hydrotalcite compound is a natural product
Or a synthetic product. The synthetic product
As for the method for synthesizing the compound, JP-B-46-2280,
JP-B-50-30039, JP-B-51-29129
JP-A-61-174270 and JP-A-61-174270.
Known methods can be exemplified. In addition, the present invention
In addition, the crystal structure of the above hydrotalcite compound
Restriction on crystal particle size or presence and amount of water of crystallization
Can be used without being done. In addition, the above hydrochloride treated with perchloric acid
The surface is coated with a higher fatty acid such as stearic acid,
Metal salts of higher fatty acids such as alkali metal salts of maleic acid;
Organic, such as alkali metal decylbenzenesulfonate
Sulfonic acid metal salt, higher fatty acid amide, higher fatty acid S
Use coated with tel or wax
Can be. One of the components (b) used in the present invention
Calcium silicate, silicic acid
Metal silicate salts such as magnesium, barium silicate and zinc silicate
And various siliceous clay minerals or their processed products, for example,
Olin, bentonite, mica powder, talc, diatomaceous earth, acid
Natural or synthetic silica such as clay, activated clay and zeolite
The acid salt is treated with an aqueous solution of perchloric acid.
Among these perchloric acid-treated silicates, calcium silicate,
Magnesium silicate, barium silicate, kaolin, bentona
Treatment of litter, talc, acid clay, activated clay and zeolite
Are particularly preferred. The above perchloric acid-treated hydrotalcite or
Is a perchloric acid treated silicate, for example, hydrotalcite
Or adding silicate to a dilute aqueous solution of perchloric acid
Stir while heating more, then, if necessary, filter,
Can be easily manufactured by dehydration or drying
it can. Perchlorine with the hydrotalcite or silicate
The molar ratio with the acid can be set arbitrarily, but generally,
Per mole of hydrotalcite or silicate
Chloric acid can be used at a ratio of 0.1 to 2 mol.
preferable. Among the above-mentioned perchloric acids as the component (b),
However, ammonium perchlorate is particularly excellent in powder moldability.
And all or other components of the component (b) in the present invention
It is preferable to use it in combination with chlorates. The above-mentioned metal salts of perchloric acid and ammonia of perchloric acid
Nitrate, perchloric acid treated hydrotalcite or persalt
The addition amount of the silicate treated with acid is 100 vinyl chloride resin.
0.001 to 10 parts by weight, preferably 0.1 to 10 parts by weight, per part by weight.
It is 01 to 5 parts by weight. 0.001 parts by weight
If the amount is less than 10 parts by weight, a sufficient effect cannot be obtained.
Even if it is used, the improvement of the effect is not observed. The component (c) used in the present invention, β-
As the diketone compound, for example, dehydroacetic acid, acetyl
Tyltetralone, benzoyltetralone, 2-benzoi
Lecyclohexanone, dibenzoylmethane, benzoyl
-4-chlorobenzoylmethane, bis (4-methylben
Zoyl) methane, 4-tert-butylbenzoyl-4-meth
Xybenzoylmethane, benzoyl-4-isopropyl
Benzoylmethane, bis (4-methoxybenzoyl) meth
Tan, acetylbenzoylmethane, acetylbenzoyl
Allylmethane, propionyl-3-methoxycarbonyl
Benzoylmethane, isovaleroylbenzoylmethane,
Octanoylbenzoylmethane, palmitoylbenzoy
Methane, stearoylbenzoylmethane, dipivaloy
And methane and distearoylmethane. Ma
In addition, the metals (lithium, natrium) of these β-diketone compounds
Thorium, potassium, magnesium, calcium, burr
, Zinc, etc.) salts can be used as well. The amount of the β-diketone compound added is
0.001 to 10 weight per 100 parts by weight of vinyl resin
Parts by weight, preferably 0.005 to 5 parts by weight. Above
If the added amount is less than 0.001 part by weight, a sufficient effect can be obtained.
And the effect is improved even when used in excess of 10 parts by weight.
Is not seen. In the present invention, it is used as a stabilizer.
The silicate compound of the above component (a), and the above component (b)
Ammonium perchlorate and metal perchlorate,
Chloric acid treated hydrotalcite or perchloric acid treated silicic acid
The salt and the β-diketone compound of the component (c) are
Can be separately compounded with vinyl chloride resin
However, these can be mixed and used. In this case,
Is a so-called compound containing other stabilizer components, if necessary.
It can also be used as a combined stabilizer. Further, the composition of the present invention is usually used in the form of powder molding.
Other stabilizers used in vinyl chloride resin compositions
Plasticizers and other additives can be used in combination. Other stabilizers that can be used in combination with the present invention include:
Gold of organic carboxylic acids, phenols and organic phosphoric acids
Genus salts, epoxy compounds, organic phosphite compounds,
Nol or sulfur antioxidants, UV absorbers,
Hindered amine light stabilizer, pure organic stabilizing aid, c
Hydrotalsite compound, zeolite compound and its
Other inorganic compounds are exemplified. The above organic carboxylic acids, phenols and
Lithium is a metal that constitutes metal salts of organophosphoric acids.
, Potassium, sodium, calcium, barium, ma
Gnesium, strontium, zinc, tin, cesium,
Luminium or organic tin is exemplified. The organic carboxylic acid may be vinegar.
Acid, propionic acid, butyric acid, valeric acid, caproic acid, enane
Tonic acid, caprylic acid, pelargonic acid, 2-ethylhexyl
Acid, neodecanoic acid, capric acid, undecanoic acid, lauri
Acid, tridecanoic acid, myristic acid, palmitic acid,
Sostearic acid, stearic acid, 12-hydroxystearic acid
Aric acid, behenic acid, montanic acid, benzoic acid, monoc
Lorbenzoic acid, p-tert-butylbenzoic acid, dimethyl hydride
Roxybenzoic acid, 3,5-ditert-butyl-4-hydroxy
Benzoic acid, toluic acid, dimethyl benzoic acid, ethyl ammonium
Benzoic acid, cumic acid, n-propylbenzoic acid, aminobenzo
Perfumed acid, N, N-dimethylaminobenzoic acid, acetoxy ammonium
Benzoic acid, salicylic acid, p-tert-octylsalicylic acid, d
Raidic acid, oleic acid, linoleic acid, linoleic acid,
Thioglycolic acid, mercaptopropionic acid, octyl
Monovalent carboxylic acids such as mercaptopropionic acid;
Acid, malonic acid, succinic acid, glutaric acid, adipic acid,
Meric acid, suberic acid, azelaic acid, sebacic acid,
Tar acid, isophthalic acid, terephthalic acid, hydroxy
Shiftal acid, chlorophthalic acid, aminophthalic acid,
Maleic acid, fumaric acid, citraconic acid, metaconic acid,
Itaconic acid, aconitic acid, thiodipropionic acid, etc.
Divalent carboxylic acids or their monoesters or monomers
Noamide compound; butanetricarboxylic acid, butanete
Lacarboxylic acid, hemicellitic acid, trimellitic acid, melo
Trivalent or tetravalent carbohydrates such as fanic acid and pyromellitic acid
And di- or triester compounds of acid. Further, as the phenols, a third butyl
Tylphenol, nonylphenol, dinonylphenol
, Cyclohexylphenol, phenylphenol,
Octylphenol, phenol, cresol, xyle
Knol, n-butylphenol, isoamylphenol
, Ethyl phenol, isopropyl phenol, iso
Octylphenol, 2-ethylhexylphenol,
Tertiary nonylphenol, decylphenol, tertiary octy
Phenol, isohexylphenol, octadecyl
Phenol, diisobutylphenol, methylpropyl
Phenol, diamylphenol, methylisofoxyl
Phenol, methyl tertiary octyl phenol, etc.
Can be [0040] The organic phosphoric acids include mono- or mono-phosphoric acids.
Or di-octyl, -decyl, -dodecyl, -tridecyl
, -Tetradecyl, -hexadecyl, -octadecyl
, -Phenyl, -tolyl, -xylyl, -octylph
Phenyl, -nonylphenylphosphoric acid, pyrophosphoric acid or
Phosphorous acid and the like. The above carboxylic acids, phenols and the like
Metal salts of organic and phosphoric acids, acid salts, neutral salts, basic salts
Alternatively, part or all of the base of the basic salt is neutralized with carbonic acid
Overbased complex may be used. The above organic carboxylic acids, phenols and
The amount of the metal salt of the organic phosphoric acid is 1
0.01 to 10 parts by weight with respect to 00 parts by weight
Parts, more preferably 0.05 to 5 parts by weight. Further, as the epoxy compound, bis
Phenol type and novolak type epoxy resin, epoxy resin
Natural fats and oils such as xylated soybean oil and epoxidized linseed oil
Epoxidized, epoxidized tall oil fatty acid octyl
Which epoxidized unsaturated fatty acid alkyl ester, vinyl
Alicyclic epoxy compounds such as rucyclohexene diepoxy
Things. The amount of the epoxy compound to be added is
0.01 to 100 parts by weight of
20 parts by weight, more preferably 0.05 to 10 parts by weight.
You. Examples of the above organic phosphite compounds include
For example, diphenyldecyl phosphite, triphenylpho
Sphite, tris (nonylphenyl) phosphite,
Tridecyl phosphite, tris (2-ethylhexyl
Le) phosphite, tributyl phosphite, dilauri
Ruacid phosphite, dibutyl acid phosphite
G, tris (dinonylphenyl) phosphite, trila
Uryl trithiophosphite, trilauryl phosphite
G, bis (neopentyl glycol) -1,4-cyclo
Hexane dimethyl phosphite, distearyl pentae
Lithritol diphosphite, diphenyl acid phos
Fight, tetradecyl-1,1,3-tris (2′-
Methyl-5'-tert-butyl-4'-hydroxyphenyl
Le) butane diphosphite, tetra (C12-15 mixed alcohol
Kill) -4,4'-isopropylidenediphenyldiphos
Fight, tris (4-hydroxy-2,5-ditert-butyl)
Phenyl, phosphite, tris (mono, di
Nylphenyl) phosphite, hydrogenated-4,4′-iso
Propylidene diphenol polyphosphite, diphenyl
Le bis [4,4'-n-butylidenebis (2-tert.
Tyl-5-methylphenol)] thiodiethanol dipho
Sphite, bis (octylphenyl) bis [4
4'-n-butylidenebis (2-tert-butyl-5-methyl
Phenol)]-1,6-hexanediol diphosph
Aitite, phenyl-4,4'-isopropylidene dife
Nord pentaerythritol diphosphite, phenyl
Rudiisodecyl phosphite, tetratridecyl (2-
Tert-butyl-5-methylphenol) diphosphite,
Tris (2,4-di-tert-butylphenyl) phosphite
And the like. The amount of the organic phosphite compound added is
For 100 parts by weight of the vinyl chloride resin, preferably
0.01 to 10 parts by weight, more preferably 0.05 to 5 parts
Parts. Examples of the above phenolic antioxidants include
For example, 2,6-di-tert-butyl-p-cresol, 2,6
-Diphenyl-4-octadecyloxyphenol,
Allyl (3,5-di-tert-butyl-4-hydroxyphenyl)
Le) propionate, distearyl (3,5-ditert-butyl)
Tyl-4-hydroxybenzyl) phosphonate, thiodi
Ethylene glycol bis [(3,5-di-tert-butyl-4
-Hydroxyphenyl) propionate], 1,6-he
Xamethylenebis [(3,5-ditert-butyl-4-hydride
Loxyphenyl) propionate], 1,6-hexame
Tylene bis [(3,5-ditert-butyl-4-hydroxy
Phenyl) propionamide], 4,4'-thiobis
(6-tert-butyl-m-cresol), 2,2′-methyl
Lenbis (4-methyl-6-tert-butylphenol),
2,2'-methylenebis (4-ethyl-6-tert-butyl
Phenol), bis [3,3-bis (4-hydroxy-
3-tert-butylphenyl) butyric acid] glyco
Ester, 4,4'-butylidenebis (6-tert-butyl)
Tyl-m-cresol), 2,2′-ethylidenebis
(4,6-di-tert-butylphenol), 2,2′-ethyl
Ridenbis (4-tert-butyl-4-tert-butylphenol
), 1,1,3-tris (2-methyl-4-hydroxy
C-5-tert-butylphenyl) butane, bis [2-third
Butyl-4-methyl-6- (2-hydroxy-3-tertiary
Butyl-5-methylbenzyl) phenyl] terephthalate
G, 1,3,5-tris (2,6-dimethyl-3-hydrid
Roxy-4-tert-butylbenzyl) isocyanurate,
1,3,5-tris (3,5-ditert-butyl-4-hydride
Roxybenzyl) isocyanurate, 1,3,5-tri
(3,5-ditert-butyl-4-hydroxybenzyl)
-2,4,6-trimethylbenzene, 1,3,5-tri
[(3,5-di-tert-butyl-4-hydroxyphenyl)
L) propionyloxyethyl] isocyanurate,
Trakis [methylene-3- (3,5-di-tert-butyl-4)
-Hydroxyphenyl) propionate] methane, 2-
Tert-butyl-4-methyl-6- (2-acryloyloxy
C-3-tert-butyl-5-methylbenzyl) phenol
, 3,9-bis [1,1-dimethyl-2-((3-
Tributyl-4-hydroxy-5-methylphenyl) pro
Pionyloxy) ethyl) -2,4,8,10-tetra
Oxaspiro [5.5] undecane, triethylene glycol
Coal bis [(3-tert-butyl-4-hydroxy-5-
Methylphenyl) propionate]. The amount of the phenolic antioxidant added is
For 100 parts by weight of the vinyl chloride resin, preferably
0.01 to 10 parts by weight, more preferably 0.05 to 5 parts
Parts. The sulfur-based antioxidants include, for example,
Dilauryl thiodipropionate, dimyristylyl, disis
Dialkylthiodipropioates such as tearyl
Nantaerythritol tetra (β-dodecyl mercaptop
Β-alkyl mercap of polyols such as
And topropionic acid esters. The amount of the sulfur-based antioxidant added is
0.01 parts by weight based on 100 parts by weight of
10 to 10 parts by weight, more preferably 0.05 to 5 parts by weight.
You. As the above-mentioned ultraviolet absorber, for example,
4-dihydroxybenzophenone, 2-hydroxy-4
-Methoxybenzophenone, 2-hydroxy-4-oct
Toxicbenzophenone, 5,5'-methylenebis (2-
2- (hydroxy-4-methoxybenzophenone)
Droxybenzophenones; 2- (2′-hydroxy-
5′-methylphenyl) benzotriazole, 2-
(2′-hydroxy-3 ′, 5′-di-tert-butylphenyl)
B) benzotriazole, 2- (2'-hydroxy-
3 ', 5'-ditert-butylphenyl) -5-chloroben
Zotriazole, 2- (2'-hydroxy-3'-third
Butyl-5'-methylphenyl) -5-chlorobenzot
Riazol, 2- (2′-hydroxy-5′-tert-oct)
Tylphenyl) benzotriazole, 2- (2′-hydrido)
Roxy-3 ', 5'-dicumylphenyl) benzotria
Sol, 2,2'-methylenebis (4-tert-octyl-
2- (2′-) such as 6-benzotriazolyl) phenol
Hydroxyphenyl) benzotriazoles; phenyl
Salicylate, resorcinol monobenzoate, 2,
4-di-tert-butylphenyl-3 ', 5'-di-tert-butyl
-4'-hydroxybenzoate, hexadecyl-3,
Bases such as 5-di-tert-butyl-4-hydroxybenzoate
Nzoates; 2-ethyl-2'-ethoxyoxanil
And 2-ethoxy-4'-dodecyloxanilide
Substituted oxanilides; ethyl-α-cyano-β, β-dif
Phenyl acrylate, methyl-2-cyano-3-methyl
Shears such as -3- (p-methoxyphenyl) acrylate
And acrylates. The amount of the ultraviolet absorber added is vinyl chloride.
0.01 to 1 part by weight based on 100 parts by weight of the base resin.
0 parts by weight, more preferably 0.05 to 5 parts by weight. As the above hindered amine light stabilizer
Is, for example, 2,2,6,6-tetramethyl-4-pipe
Lysyl stearate, 1,2,2,6,6-pentamethyl
Le-4-piperidyl stearate, 2,2,6,6-te
Tramethyl-4-piperidyl benzoate, N- (2,
2,6,6-tetramethyl-4-piperidyl) dodecyl
Succinimide, 1-[(3,5-di-tert-butyl-4-
[Hydroxyphenyl) propionyloxyethyl]-
2,2,6,6-tetramethyl-4-piperidyl-
(3,5-ditert-butyl-4-hydroxyphenyl) p
Lopionate, 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-piperidi
) -2-butyl-2- (3,5-di-tert-butyl-4-
(Hydroxybenzyl) malonate, N, N'-bis
(2,2,6,6-tetramethyl-4-piperidyl)
Xamethylenediamine, tetra (2,2,6,6-tetra
(Lamethyl-4-piperidyl) butanetetracarboxyle
Or tetra (1,2,2,6,6-pentamethyl-4
-Piperidyl) butanetetracarboxylate, bis
(2,2,6,6-tetramethyl-4-piperidyl)
Di (tridecyl) butanetetracarboxylate, bis
(1,2,2,6,6-pentamethyl-4-piperidi
Le) di (tridecyl) butanetetracarboxylate
G, 3,9-bis [1,1-dimethyl-2- (tris
(2,2,6,6-tetramethyl-4-piperidyloxy
Cicarbonyloxy) 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-
Piperidyloxycarbonyloxy) butylcarbonyl
Oxy) ethyl] -2,4,8,10-tetraoxas
Pyro [5.5] undecane, 1,5,8,12-tetra
Kiss [4,6-bis (N- (2,2,6,6-tetrame
Tyl-4-piperidyl) butylamino) -1,3,5-
Triazin-2-yl] -1,5,8,12-tetraa
Zadodecane, 1- (2-hydroxyethyl) -2,2,
6,6-tetramethyl-4-piperidinol / succinic acid
Dimethyl condensate, 2-tert-octylamino-4,6-di
Chloro-s-triazine / N, N'-bis (2,2,
6,6-tetramethyl-4-piperidyl) hexamethyle
Diamine condensate, N, N'-bis (2,2,6,6-
Tetramethyl-4-piperidyl) hexamethylene diamine
And dibromoethane condensates. Addition amount of the above hindered amine light stabilizer
Is preferably based on 100 parts by weight of the vinyl chloride resin.
Is 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight.
Parts by weight. Examples of the pure organic stabilizing aid include bisulfite.
Phenols such as enol A and hydrogenated bisphenol A
Pentaerythritol, dipentaerythritol,
Dipentaerythritol adipate, mannitol,
Polyhydric alcohols such as rubitol and their
Stele compounds or partial ester compounds; 2,6-di
Methyl-1,4-dihydropyridine-3,5-dicarbo
Acid dododecyl ester, 2-phenylindole,
Organic nitrogen-containing compounds such as lamin are exemplified. The amount of the pure organic stabilizing aid added is
Preferably, the amount is 0.0
01 to 5 parts by weight, more preferably 0.005 to 3 parts by weight
It is. The above hydrotalcite compound is
Magnesium (and zinc) and aluminum represented by the general formula (II)
Double salt compound consisting of luminium
Surface treated like hydrotalcite
No. Addition amount of the above hydrotalcite compound
Is preferably based on 100 parts by weight of the vinyl chloride resin.
Is 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight.
Parts by weight. The zeolite compound has a unique three-dimensional
Alkali or alkaline earth having zeolite crystal structure
Aluminosilicate of a class of metals.
Are A, X, Y and P zeolites, monodena
Site, analsite, sodalite aluminosilicate
Salt, clinobutyrolite, erionite and chabasa
And zeolite compounds.
Water containing crystallization water (so-called zeolite water)
Or any of the anhydrides from which water of crystallization has been removed.
Can have a particle size of 0.1 to 50 μm.
Preferably, the thickness is 0.5 to 10 μm. The amount of the zeolite compound added is
0.01 parts by weight based on 100 parts by weight of
10 to 10 parts by weight, more preferably 0.05 to 5 parts by weight.
You. Other inorganic compounds usable in the present invention
Calcium phosphate, calcium oxide,
Gnesium, magnesium oxide, magnesium hydroxide
And so on. As the plasticizer which can be used in the present invention,
Any plasticizer used for vinyl chloride resin can be used
can do. As the plasticizer, for example, Djibouti
Ruphthalate, butylhexyl phthalate, diheptyl
Phthalate, dioctyl phthalate, diisononyl phthalate
, Diisodecyl phthalate, dilauryl phthalate
G, dicyclohexyl phthalate, dioctyl terephthalate
Phthalate plasticizers such as phthalate; dioctyl avipe
G, diisononyl adipate, diisodecyl adipate
Adip such as di- or di (butyldiglycol) adipate
Phosphate plasticizers: triphenyl phosphate, tricresedge
Lephosphate, trixylenyl phosphate, triphosphate
(Isopropylphenyl) phosphate, triethylpho
Sulfate, tributyl phosphate, trioctylpho
Sulfate, tri (butoxyethyl) phosphate octane
Phosphate plasticizers such as tildiphenyl phosphate
System: polyhydric alcohols such as ethylene glycol and die
Tylene glycol, triethylene glycol, 1,2-
Propylene glycol, 1,3-propylene glycol
1,3-butanediol, 1,4-butanediol
1,1,5-hexanediol, 1,6-hexanediol
As a dibasic acid with cellulose, neopentyl glycol, etc.
Oxalic acid, malonic acid, succinic acid, glutaric acid, adipine
Acid, pimelic acid, suberic acid, azelaic acid, sebacin
Acid, phthalic acid, isophthalic acid, terephthalic acid, etc.
If necessary, monohydric alcohol and monocarboxylic acid
Polyester plasticizer and epoxy used for stopper
Soybean oil, epoxidized linseed oil, epoxidized tung oil, epo
Xylated fish oil, epoxidized tallow oil, epoxidized safflower
Oil, epoxidized methyl stearate, -butyl, -2-
Ethylhexyl, -stearyl ester, epoxidized poly
Libutadiene, epoxidized tall oil fatty acid ester, d
Epoxy plastics such as fatty acid esters of oxilated linseed oil
Agent; other, tetrahydrophthalic acid plasticizer, azela
In-acid plasticizer, sebacic acid plasticizer, stearic acid
Plasticizer, citric acid plasticizer, trimellitic acid plasticizer
And so on. In addition, if necessary, the composition of the present invention
Is, for example, a crosslinking agent, a filler, a pigment, a foaming agent, an antistatic
Agent, plate out prevention agent, surface treatment agent, lubricant, flame retardant
Agents, fluorescent agents, photodegradants, fungicides, bactericides, non-metal stable
Agents, processing aids, release agents and the like. The vinyl chloride resin composition for powder molding of the present invention
The product is manufactured, for example, as follows. Suspension polymerization or
Essential components for vinyl chloride resin manufactured by bulk polymerization
The above components (a), (b) and (c);
Plasticizer, organic carboxylic acid, organic phosphorus
Metal salts of acids or phenols, hydroxy fatty acids
Lubricants such as rigoester or its salt, and other additives
Is evenly dispersed with a mixer such as a super mixer.
Dry blend if flow improver is added
After cooling with a cooling mixer
Dry blended vinyl chloride resin with improver added
To form a composition. The composition and the composition of the present invention are described below by way of Examples.
The stabilizing effect will be specifically shown. However, the present invention
Is not limited by these examples. Example 1 A vinyl chloride resin composition having the following
-After drying in an oven at 110 ° C for 1 hour,
Stir for 15 minutes using a sifter to create a compound
did. Place the chrome mirror plate in a 300 ° C gear oven
After 15 minutes, remove the mirror plate to 240 ℃
At that point, quickly spread the compound to a uniform thickness
The molded sheet is left for 10 seconds. Put the mold upside down,
After leaving for 30 seconds as it is, it is immersed in a water bath and cooled.
The gelation state of the sheet at that time was evaluated according to the following evaluation criteria
did. [Evaluation Criteria] ◎ Completely gelled ○ Gelled, but particulate matter remains inside. 化 し Gelled, but with irregularities on the surface. × Ungelled portion. 24 gelled sheets
Put in a gear oven at 0 ° C, decomposition time (thermal stability)
Was measured. In addition, the initial coloring and
After accelerated deterioration for 500 hours in an oven at 130 and 130 ° C
Properties (heat aging properties) were evaluated in 10 steps [Evaluation criteria:
Good 1 ← ─ → 10 bad (relative comparison). The results are shown in the following [Table 1]. [Combination] parts by weight suspension polymerization PVC 90 paste PVC 10 di (C9-11 mixed alkyl) phthalate 65 epoxidized soybean oil 5 zinc stearate 0.3 Alkamizer 1 ^{* 1} 1.0 Calcium silicate 0.5 (Composition formula: CaO.SiO _Two ・ 2H _Two O) Test compound (shown in [Table 1] below) [Table 1] Tetra (C12-15 mixed alkyl) bisphenol A 1.0 diphosphitedibenzoylmethane 0.05 * 1: Synthetic hydrotalcite manufactured by Kyowa Chemical Industry [Table 1] Example 2 A gel sheet was prepared in the same manner as in Example 1 by the following [formulation].
It was prepared and the gelation state was evaluated. 60 ° C in the cooling stage
, The gel sheet is peeled off, and the chrome
Check the degree of release and the degree of peeling of the sheet to determine the mold release and mold contamination.
The dyeing property was evaluated in 10 steps [Evaluation criteria: good
1 ← ─ → 10 evil]. Further, the molded sheet on the mirror plate made of chromium is formed on the sheet.
Foam urethane is injected at a certain thickness, and the urethane backing sheet is
Created. Place this sheet in a 120 ° C oven
Coloration of sheets after 300 and 450 hours
Measure the degree using a Hunter colorimeter and compare the color with the original.
Finding the difference (ΔE), colorability when exposed at relatively low temperature
And The results are shown in Table 2 below. (Combination) parts by weight suspension polymerization PVC 100 tri (C7-9 mixed alkyl) trimellitate 65 epoxidized linseed oil 5 bisphenol A diglycidyl ether 3 calcium stearate 1.5 basic zinc octylate 1.0 test compound (Shown in Table 2 below) 1.0 Na-A zeolite 2.0 di (tridecyl) phenyl phosphite 1.0 tetra (2,2,6,6-tetramethyl-4-0.2 piperidyl) Butanetetracarboxylate ammonium perchlorate 0.2 barium perchlorate 0.2 dibensoylmethane 0.05 Example 3 A gel sheet was obtained in the same manner as in Example 1 by the following [formulation].
Make the gelled sheet heat stable and heat aging
Was tested. The results are shown in Table 3 below. [Combinations] Parts by weight Suspension polymerized PVC 90 Paste PVC 10 Di (C9-11 mixed alkyl) phthalate 65 Epoxidized soybean oil 5 Zinc stearate 0.3 Ammonium perchlorate 0.3 Alkamizer 50 3 Alkamizer 1 1.0 Calcium silicate 0.5 (Composition formula: CaO.2SiO _Two ・ 2H _Two O) Tetra (C12-15 mixed alkyl) bisphenol A 1.0 diphosphite test compound 0.05 As apparent from Tables 1 to 3 above,
In addition, silicate compounds, perchlorates, etc.
And β-diketone compound are added together (
Examples 1-1 to 3-5) are each alone or in them.
When only two types are used (Comparative Examples 1-1 to 3-1)
Thermal stability during processing, gelling properties, molds unexpectedly unexpected
Stainability, mold release and workability after processing, thermal stability, heat aging
It has remarkably excellent performance such as chemical properties. According to the present invention, a vinyl chloride resin set for powder molding according to the present invention.
The product is excellent in heat stability, heat aging property and coloring property, and
Excellent moldability such as gelling, mold contamination and mold release
It is a thing.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-6-279640 (JP, A) JP-A-4-359949 (JP, A) JP-A-4-15237 (JP, A) JP-A-4-199 50250 (JP, A) JP-A-6-200103 (JP, A) JP-A-7-173354 (JP, A) JP-A-7-166017 (JP, A) (58) Fields investigated (Int. ⁷ , DB name) C08L 27/06

Claims (1)

(57) [Claims] [Claim 1] 100 parts by weight of a vinyl chloride resin,
(A) 0.001 to 10 parts by weight of at least one silicate compound represented by the following formula (I) represented by the general formula (I);
Perchloric acid metal salt, perchloric acid ammonium salt, perchloric acid-treated hydrotalcite or perchloric acid-treated silicate 0.001 to 10 parts by weight and (c) at least one of β-diketone compounds 0.001 to 0.001 part by weight A vinyl chloride resin composition for powder molding, comprising 10 parts by weight. ## STR1 ## _{M (O) a · nSiO 2} · mH 2 O (I) ( wherein, M is the table <br/> alkaline earth metal or aluminum, a is when M is an alkaline earth metal 1, when M is aluminum, represents 3/2, n represents 1 to 5,
m represents any positive integer. )