JP2840086B2 - Vinyl chloride resin composition for powder molding - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a vinyl chloride resin composition for powder molding, and more particularly, to a powder chloride for powder rotational molding or powder slush molding suitable for automotive interior materials. The present invention relates to a vinyl resin composition.

[Problems to be solved by conventional technology and invention]

In recent years, for covering materials such as crash pads, armrests, headrests, consoles, meter covers and door trims as interior materials for automobiles, lightweight, soft and high-quality leather grain and stitch patterns have been applied. What has been done is required more.

Conventionally, as these covering materials, a vacuum molded product of a soft sheet mainly composed of a vinyl chloride resin and an ABS resin, or a rotary molded or slush molded product of a sol mainly composed of a vinyl chloride resin for a paste and a plasticizer ( (Hereinafter referred to as a sol molded product). However, vacuum molded products have achieved their purpose in terms of weight reduction,
It was difficult to form a material having a complicated feel with a poor feeling of softness and only a hard feel, and further having a luxurious grain or stitch pattern. Further, the vacuum molded product has a disadvantage that a large residual strain is generated at the time of molding and a crack is easily generated in a long-time use.

On the other hand, although the sol molded product has a soft feeling, the melting temperature in the mold is high because the gelation temperature is low, and phenomena such as flow mark, lip or sol stringing occur. Therefore, there are disadvantages such as a lack of surface smoothness, an excessively long time for discharging the sol from the mold, and an increase in the thickness of the covering material. In addition, in the case of sol molding, there are problems that it is difficult to clean tanks and pipes at the time of color change, and that it cannot withstand long-term storage because the viscosity changes with time.

In order to solve these drawbacks and problems, a powder molding method has recently been spotlighted. The powder molding method generally includes a fluid immersion method, an electrostatic coating method, a powder spraying method, a powder rotational molding method, and a powder slash molding method. Powder slush molding is suitable.

Such powder rotation molding method or powder slush molding method is
The mold at 180 ° C or higher and the powder supply box are integrated, and the powder is welded to the inner surface of the mold by rotating, swinging, or spraying. It is a method of collecting.

The method of heating the mold used in the powder molding method includes a gas heating furnace method, a heating medium oil circulation method, a dipping method in heating medium oil or hot fluidized sand, or a high-frequency induction heating method.

The powder composition used in the powder molding method must be excellent in powder fluidity and moldability. It is well known that a powder composition is prepared by dry blending a vinyl chloride resin with a plasticizer, a stabilizer, a pigment and the like using a blender or a high-speed mixer equipped with a heating jacket.

It is also well known that inorganic fillers such as finely divided vinyl chloride resin and finely divided calcium carbonate and silica are dry-blended and then added at the cooling stage in order to improve powder flowability (Rubber Digest Vol. 14). No. 8, pages 32 to 40 and polyvinyl chloride-its chemistry and industry-II, 365-370
1986, and Japanese Patent Publication No. 37-1575).

In addition, there is a high need for a powder-based composition for a covering material by powder molding, which is excellent in mold contamination prevention performance during powder molding (hereinafter referred to as mold contamination resistance) and exhibits an effect of excellent peelability. . Further, in these powder moldings, since the powder composition is welded to the high-temperature mold and molded as described above, the mold gradually becomes dirty as the number of molding shots increases.

When the mold becomes contaminated, the surface inside the mold becomes shallow, causing a gloss on the surface. If there is any sticky material in the mold, the surface material is removed from the mold. It is not preferable because of poor quality and in some cases lack of meat.

In such a case, the molding must be temporarily interrupted for cleaning the mold, and the productivity is significantly reduced. Also,
If extra work and chemicals (alkali cleaning solution, acid cleaning agent, halogenated hydrocarbon solvent, etc.) are required for cleaning the mold, or if the dirt is extremely difficult to clean, mechanical brushing Brass brushing or a method in which fine glass beads are forcibly sprayed with air to perform brushing). However, if such brushing is performed frequently, it will lead to a shallow phenomenon and shorten the life of the mold.

Therefore, it is extremely important both industrially and economically to develop a powder composition having less mold stains, that is, excellent mold stain resistance, and excellent mold stain resistance. Development of a vinyl chloride resin composition has been desired.

[Means for solving the problem]

In view of the present situation, the present inventors have conducted intensive studies to find a vinyl chloride resin composition having excellent mold contamination in powder molding and good releasability. , (A) a plasticizer, (b) a carboxylic acid,
Metal salts of organic phosphoric acids or phenols and (c)
The present inventors have found that excellent effects can be obtained by blending a specific hydroxy fatty acid oligoester or a metal salt thereof, and completed the present invention.

That is, the present invention relates to 100 parts by weight of a vinyl chloride resin, (a) 30 to 100 parts by weight of a plasticizer, (b) a carboxylic acid,
A powder obtained by mixing 0.05 to 10 parts by weight of a metal salt of an organic phosphoric acid or a phenol and (c) 0.1 to 5 parts by weight of a hydroxy fatty acid oligoester represented by the following general formula (I) or a metal salt thereof. An object of the present invention is to provide a vinyl chloride resin composition for body molding.

(Wherein, R represents a hydrogen atom or a saturated or unsaturated monovalent organic group having 1 to 12 carbon atoms, and A represents 1 carbon atom.
X has a saturated or unsaturated divalent organic group of up to 12, and X is a hydrogen atom or And m represents a number of 2 to 10, and R 'represents 1 to 1 carbon atoms.
An alkyl group which may have a substituent of 18 or an aryl group which may have a substituent having 6 to 12 carbon atoms,
Y represents a hydrogen atom, a metal atom of Ia, IIa, IIb of the periodic table or alkyltin. Hereinafter, the vinyl chloride resin composition of the present invention will be described in detail.

As the plasticizer used in the present invention, dibutyl phthalate, butylbenzyl phthalate, diheptyl phthalate, dioctyl phthalate, diisononyl phthalate,
Phthalate plasticizers such as diisodecyl phthalate, dilauryl phthalate, dicyclohexyl phthalate, dioctyl terephthalate, adipate plasticizers such as dioctyl adipate, diisononyl adipate, di (butyl diglycol) adipate, triphenyl phosphate, tricresyl phosphate, tricixile Phosphate plasticizers such as nyl phosphate, tris (isopropylphenyl) phosphate, tributyl phosphate, trioctyl phosphate, tri (butoxyethyl) phosphate, octyl diphenyl phosphate, other polyester plasticizers, tetrahydrophthalate plasticizers, azelate plasticizers Agent, sebacate plasticizer,
Stearic acid type plasticizer, citric acid type plasticizer, trimellitate type plasticizer and the like can be mentioned.

The addition amount of these plasticizers is 30 to 100 parts by weight, preferably 40 to 80 parts by weight based on 100 parts by weight of the vinyl chloride resin.

In addition, the vinyl chloride resin composition of the present invention includes epoxidized soybean oil, epoxidized linseed oil, epoxidized tung oil, epoxidized fish oil, epoxidized tallow oil, epoxidized castor oil, epoxidized safflower oil and other epoxy resins. Petroleum and vegetable oil, epoxidized methyl stearate, -butyl, -2-
Tatylhexyl, -stearyl, epoxidized polybutadiene, tris (epoxypropyl) isocyanurate,
Add an epoxy compound such as epoxidized tall oil fatty acid ester, epoxidized linseed oil fatty acid ester, bisphenol A diglycidyl ether, vinylcyclohexene diepoxide, dicyclohexene diepoxide, 3,4-epoxycyclohexyl-6-methylepoxycyclohexanecarboxylate can do.

The carboxylic acids, organic phosphoric acids or phenols used in the present invention (Li, Na, K, Ca, Ba, Mg, Sr, Zn, C
d, Sn, Cs, Al, organic Sn) The carboxylic acid constituting the salt includes, for example, 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, arachinic acid, behenic acid, erucic acid Mixtures of the above naturally occurring acids such as brassic acid and similar acids and tallow fatty acids, coconut oil fatty acids, tung oil fatty acids, soybean oil fatty acids and cottonseed oil fatty acids, benzoic acid, pt-butylbenzoic acid, ethylbenzoic acid, Isopropyl benzoic acid, toluic acid, xylic acid,
Salicylic acid, 5-t-octylsalicylic acid, naphthenic acid, monovalent carboxylic acids such as cyclohexanecarboxylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid Monoesters of dicarboxylic acids such as acid, isophthalic acid, terephthalic acid, oxyphthalic acid, chlorophthalic acid, aminophthalic acid, maleic acid, fumaric acid, citraconic acid, metaconic acid, itaconic acid and aconitic acid.

Examples of the organic phosphoric acids include mono- or dioctyl phosphoric acid, mono- or di-dodecyl phosphoric acid, mono- or di-octadecyl phosphoric acid, mono- or di (nonylphenyl) phosphoric acid, nonylphenyl phosphonate, stearyl phosphonate, and the like. .

Further, as phenols, phenol, cresol, ethylphenol, cyclohexylphenol,
Nonylphenol, dodecylphenol and the like can be mentioned.

The addition amount of these metal salts is 0.05 to 10 parts by weight, preferably 0.3 to 5 parts by weight, based on 100 parts by weight of the vinyl chloride resin.

The hydroxy fatty acid oligoester represented by the general formula (I) or a metal salt thereof used in the present invention has a formula: (Wherein, R represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and A represents an alkylene group having 1 to 12 carbon atoms) or from such a hydroxycarboxylic acid or a hydroxy group And a metal salt thereof derived from a mixture with a carboxylic acid having no.

Examples of such hydroxycarboxylic acids include ricinoleic acid, a mixture of 9- and 10-hydroxystearic acid (obtained by sulfating oleic acid and subsequent hydrolysis), 12-hydroxystearic acid, Commercially available hydrogenated castor oil fatty acids containing stearic acid and palmisic acid.

Hydroxyl-free carboxylic acids which can be used together with hydroxycarboxylic acids to obtain polyesters are preferably saturated or unsaturated aliphatic carboxylic acids, especially alkyl and alkenyl carboxylic acids having 2 to 20 carbon atoms. It is. Examples of such acids include acetic acid, lauric acid, myristic acid, palmitic acid, stearic acid and oleic acid.

Accordingly, specific examples of the hydroxy fatty acid oligoester represented by the general formula (I) or its metal salt used in the present invention include the compounds shown in Table 1 below.

The amount of these hydroxy fatty acid oligoesters or metal salts thereof is 0.1 to 5 parts by weight, preferably 0.2 to 3 parts by weight, per 100 parts by weight of the vinyl chloride resin.

The composition of the present invention exhibits an excellent synergistic effect when used in combination with an organic phosphite compound.

Examples of the organic phosphite compound include, for example, diphenyldecyl phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite, and tris (2-ethylhexyl)
Phosphite, tributyl phosphite, dilauryl acid phosphite, dibutyl acid phosphite,
Tris (dinonylphenyl) phosphite, trilauryl trithiophosphite, trilauryl phosphite,
Bis (neopentyl glycol) -1,4-cyclohexanedimethylphosphite, distearylpentaerythritol diphosphite, diphenylacid phosphite, tris (lauryl-2-thiolytyl) phosphite, tetradecyl-1,1,3-tris ( 2'-methyl-
5'-tert-butyl-4'-hydroxyphenyl) butanediphosphite, tetra ( _C12-15 mixed alkyl) -4,
4'-isopropylidene diphenyl diphosphite, tris (4-hydroxy-2,5-di-tert-butylphenyl)
Phosphite, tris (nonylphenyl mono- and di-mixed)
Phosphite, tris (nonylphenyl mono- and di-mixed)
Phosphite, hydrogenated-4,4'-isopropylidene diphenol polyphosphite, diphenyl bis [4,4 '
-N-butylidenebis (2-tert-butyl-5-methylphenol)] thiodiethanol diphosphite, bis (octylphenyl) bis [4,4'-n-butylidenebis (2-tert-butyl-5-methylphenol) )] − 1,
6-hexanediol diphosphite, phenyl-4,4 '
-Isopropylidene diphenol pentaerythritol diphosphite, phenyl diisodecyl phosphite, tetratridecyl (2-tert-butyl-5-methylphenol) diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, etc. can give.

The addition amount of these organic phosphite compounds is 0.01 to 5 parts by weight, especially 0.1 to 5 parts by weight, based on 100 parts by weight of the vinyl chloride resin.
Preferably it is 3 parts by weight.

The vinyl chloride resin used in the present invention is a suspension polymerization method,
Grafting of vinyl chloride polymer produced by bulk polymerization method or emulsion polymerization method or copolymers of ethylene, propylene, vinyl acetylate, etc., or copolymers of ethylene, vinyl acetylate copolymer and vinyl chloride which can be copolymerized with vinyl chloride Copolymers and mixtures of two or more of these polymers are also included, but are not necessarily limited to these.

In addition, if necessary, additives usually used for vinyl chloride resins, for example, crosslinking agents, fillers, foaming agents, antistatic agents, antifogging agents, plateout preventing agents, surface treatment agents, lubricants, difficulties Flame retardants, fluorescent agents, fungicides, bactericides, metal deactivators, mold release agents, pigments, processing aids, antioxidants, light stabilizers, metal hydroxides such as magnesium hydroxide, calcium hydroxide, and magnesium oxide , Oxides, metal carbonates such as calcium carbonate, zeolites, powdered silicic acid (silica), perchlorates, hydrotalcites, basic salts, heat resistance improvers, and the like.

The resin composition for powder molding of the present invention is produced as follows. That is, (a) a plasticizer, (b) a metal salt of a carboxylic acid, an organic phosphate or phenol, and (c) a vinyl chloride resin produced by a suspension polymerization or bulk polymerization method.
Hydroxy fatty acid oligoester or its salt, other additives, etc. are evenly dispersed with a mixer such as a super mixer, or when adding a fluidity improver, after dry blending, cool it with a cooling mixer, etc. A flow improver is added, and the surface of the dry-blended vinyl chloride resin is uniformly coated to obtain a composition.

〔Example〕

Next, examples will be described, but the present invention is not limited to these examples.

Example 1 A vinyl chloride resin composition having the following composition was dried up in a gear oven at 110 ° C. for 1 hour, and then stirred for 15 minutes using a crusher to prepare a compound. The compound is spread on a mirror plate made of chrome (a photographic ferro plate) so as to have a uniform thickness, placed in a gear oven at 250 ° C., and heated and melted (gelled) for 3 minutes. This was taken out and cooled with air, and the molded sheet was peeled off. The degree of haze of the mirror plate made of chromium and the degree of peeling of the sheet were examined to evaluate the demolding property and mold contamination.

The evaluation was divided into 10 grades and expressed as good 110 bad. The results are shown in Table 2 below.

(Blend) Suspension polymerized PVC 100 parts by weight Dioctyl phthalate 60 Epoxidized soybean oil 5 Ba / Zn complex stabilizer 1.5 Tetra (C _12-15 mixed alkyl) -4,4'-isopropylidene diphenyl diphosphite 1 Synthetic hydro Talcite 3 oligoester (Table 1) 0.5 Example 2 With respect to the composition having the following composition, demoldability and mold contamination were evaluated in the same manner as in Example 1, and the results are shown in Table 3.

(Blending) Suspension blended PVC 100 parts by weight Di (C _9-11 mixed alkyl) phthalate 60 Epoxidized soybean oil 5 Zinc octylate 0.8 Barium octylate 1.2 Barium stearate 0.3 Trisnonylphenyl phosphite 0.8 Synthetic zeolite 1 Oligoester ( Table-2) 0.5 [Effects of the Invention] The vinyl chloride resin composition for powder molding of the present invention not only has excellent demolding properties, but also has excellent effects on mold contamination.

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Yoshito Oka 5-2-13-1 Shirahata, Urawa City, Saitama Prefecture Inside Adeka Argus Chemical Co., Ltd. (56) References JP-A-50-102644 (JP, A) ( 58) Field surveyed (Int.Cl. ⁶ , DB name) C08L 27/06 C08K 5/101

Claims (1)

(57) [Claims] 1. 100 parts by weight of a vinyl chloride resin, (a) 30 to 100 parts by weight of a plasticizer, (b) 0.05 to 10 parts by weight of a metal salt of a carboxylic acid, an organic phosphoric acid or a phenol, and (c) A vinyl chloride resin composition for powder molding, comprising 0.1 to 5 parts by weight of a hydroxy fatty acid oligoester represented by the general formula (I) or a metal salt thereof. (Wherein, R represents a hydrogen atom or a saturated or unsaturated monovalent organic group having 1 to 12 carbon atoms, and A represents 1 to 1 carbon atoms.
X has 12 saturated or unsaturated divalent organic groups, and X is a hydrogen atom or a formula And n represents a number of 2 to 10, and R ′ represents 1 to 1 carbon atoms.
An alkyl group optionally having 18 substituents or an aryl group optionally having 6 to 12 carbon atoms, and Y is a hydrogen atom or Ia, IIa, IIb Represents a metal atom or alkyl tin. )