JPH04261451A - Vinyl chloride-based resin composition with electron beam resistance - Google Patents

Abstract

PURPOSE:To provide the title transparent composition with transparency. CONSTITUTION:The objective composition can be obtained by incorporating a vinyl chloride-based resin with an organic carboxylic acid metal salt and an organotin-based stabilizer.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vinyl chloride resin composition that is transparent and has excellent electron beam resistance. Specifically, the present invention relates to a vinyl chloride resin composition that maintains transparency and exhibits little discoloration due to electron beam irradiation.

0002

[Prior art] The surface of a molded product based on vinyl chloride resin is coated with paint, the vinyl chloride resin base material is laminated using an adhesive, or the vinyl chloride resin base material itself is coated with paint. In cases where heat deformation resistance is improved by crosslinking, external heat treatment is usually performed to accelerate drying, curing, or crosslinking reactions.

[0003] Heat treatment is widely practiced because the equipment is relatively inexpensive, but there are drawbacks such as the time required for the treatment and the fact that some molded products may become softened and deformed due to heat. In recent years, as a countermeasure to this problem, electron beam irradiation methods have been developed, especially for the purpose of increasing processing speed, but electron beam irradiation can increase processing speed due to its high energy.
Although coating, adhesion, crosslinking, and other treatments can be carried out quickly at room temperature and pressure, it also has a large effect on the substrate. For example, when a vinyl chloride resin base material is irradiated with an electron beam, the energy of the electron beam is greater than the chemical bond energy of the vinyl chloride resin, so a dehydrochlorination reaction occurs, causing discoloration and deterioration of quality. . On the other hand, if the amount of electron beam irradiation is reduced in order to prevent discoloration of the base material, there is a drawback that the treatment will be insufficient.

0004

[Problem to be Solved by the Invention] In the above-mentioned situation, the present applicant has proposed a case in which coating, adhesion, crosslinking, etc. on a base material containing vinyl chloride resin as a main component is carried out by electron beam irradiation. In order to provide a vinyl chloride resin composition with little discoloration due to irradiation, the invention of Japanese Patent Application No. 63-32938 was previously proposed, but the composition of the invention was inferior in terms of transparency; Its use in fields where transparency is required was restricted. As a result of intensive studies to obtain a vinyl chloride-based resin that is transparent and has excellent electron beam resistance, the present inventors found that a vinyl chloride resin using a combination of an organic carboxylic acid metal salt and an organotin stabilizer was found. The present inventors have discovered that a vinyl resin composition is suitable for the above purpose and have completed the present invention.

[0005]

[Means for Solving the Problems] That is, the gist of the present invention resides in a vinyl chloride resin composition prepared by adding an organic carboxylic acid metal salt and an organic tin stabilizer to a vinyl chloride resin. The present invention will be explained in detail below. As the vinyl chloride resin used in the composition of the present invention, vinyl chloride or a mixture of vinyl chloride and a comonomer copolymerizable therewith can be prepared by a suspension polymerization method, a bulk polymerization method, a fine suspension polymerization method, or an emulsion polymerization method. All products manufactured by this method are used. The average degree of polymerization is preferably in the range of 500 to 10,000, preferably in the range of 700 to 4,000. Examples of comonomers that can be copolymerized with vinyl chloride include vinyl esters such as vinyl acetate, vinyl propionate, and vinyl laurate; acrylic esters such as methyl acrylate, ethyl acrylate, and butyl acrylate; methyl methacrylate, ethyl methacrylate, etc. methacrylic acid esters; maleic acid esters such as dibutyl maleate and diethyl maleate; fumaric acid esters such as dibutyl fumarate and diethyl fumarate; vinyl ethers such as vinyl methyl ether, vinyl butyl ether, and vinyl octyl ether; acrylonitrile , vinyl cyanides such as methacrylonitrile; α-olefins such as ethylene, propylene, and styrene; vinylidene halides other than vinyl chloride or vinyl halides such as vinylidene chloride and vinyl bromide; comonomers of these is used in an amount of 30% by weight or less, preferably 20% by weight or less in the constituent components of the vinyl chloride resin. Of course, the comonomers are not limited to those mentioned above.

Examples of the organic carboxylic acids constituting the organic carboxylic acid metal salt which is a component of the composition of the present invention include caproic acid, pelargonic acid, lauric acid, 2-ethylhexylic acid, myristic acid, palmitic acid, stearic acid,
Instearic acid, hydroxystearic acid, oleic acid, linoleic acid, ricinoleic acid, behenic acid, isodecanoic acid, alkinoic acid, erucic acid, naphthenic acid, trialkylacetic acid, tallow fatty acid, coconut oil fatty acid, soybean oil fatty acid, benzoic acid , toluic acid, tert-butylbenzoic acid, etc.
A mixture of these may be used. Furthermore, examples of metals constituting the metal salt include calcium, zinc, barium, cadmium, and lead. Of course, various organic carboxylic acid metal salts may be used in combination.

[0007]The amount of the organic carboxylic acid metal salt added is preferably in the range of 1 to 8 parts by weight per 100 parts by weight of the vinyl chloride resin. If the amount added is less than this range, the effect of preventing discoloration after electron beam irradiation may not be sufficient in combination with the organotin compound described below, and if it is too large, surface contamination due to bleeding, bloom, etc. may easily occur. .

The organotin compounds used in the composition of the present invention are specifically monobutyltin trilaurate, dibutyltin dilaurate, tributyltin monolaurate, dibutyltin distearate, di-n-octyltin dilaurate,
Alkyltin fatty acid ester (RmSn(OOCR')4-m) such as di-n-octyltin distearate, dimethyltin dilaurate, dimethyltin stearate, dibutyltin maleate polymer, di-n-octyltin maleate Dialkyltin maleate polymers such as polymers (-[SnR2 ・OOC-CH2 CH-CCO]
-m), dibutyltin bismaleate butyl ester,
Dialkyltin maleate alkyl esters (R2Sn(OOCCH=CH-COOR')2 such as di-n-octyltinbismaleate-2-ethylhexyl ester)
), or dialkyltin sulfide polymer ((R
2SnS)m), dialkyltin dialkylmercaptide, dialkyltin bis(mercaptocarboxylic acid alkyl ester), and the like. The organotin stabilizer is not limited to those mentioned above.

The amount of these organotin stabilizers added is preferably in the range of 1 to 10 parts by weight per 100 parts by weight of the vinyl chloride resin. If the amount added is less than this range, the effect of preventing discoloration after electron beam irradiation in combination with the above-mentioned metal salt of organic carboxylic acid will not be sufficient, and if it is more than this range, the surface may be affected by bleeding or blooming. contamination can become severe.

[0010] Organic carboxylic acid metal salts and organotin stabilizers are used as heat stabilizers during molding of vinyl chloride resins to prevent the resin from discoloring and decomposing, but the energy of the electron beam Since the thermal energy is high compared to that during processing, it is necessary to use a combination of an organic carboxylic acid metal salt and an organic tin stabilizer in the composition of the present invention, and by doing so, the object of the present invention can be achieved. can do.

In addition to the above-mentioned essential components, the composition of the present invention contains additives that are usually added to vinyl chloride resins, such as plasticizers, lubricants, flame retardants, antioxidants, ultraviolet inhibitors, fillers, Coloring agents, mold release agents, etc. are often used in combination. Further, chelators, rust preventives, crosslinking agents, and crosslinking aids may be added as necessary. As a plasticizer, adipic acid di-
Fatty acid ester plasticizers such as 2-ethylhexyl, di-n-decyl adipate, diisodecyl adipate, di-2-ethylhexyl azelate, dibutyl sebacate, di-2-ethylhexyl sebacate; adivic acid, sebacic acid, etc. Aliphatic polyester plasticizers produced by the esterification reaction between aliphatic dicarboxylic acids and aliphatic diols such as ethylene glycol and 1,4-butanediol; di-n-butyl phthalate, di-2-ethylhexyl phthalate,
Phthalate plasticizers such as diisooctyl phthalate, octyldecyl phthalate, butylbenzyl phthalate, di-2-ethylhexyl isophthalate, and phthalate esters of higher alcohols having about 11 to 13 carbon atoms; n-octyl trimellitate -n-decyl, tri-2 trimellitate
- Trimellitic acid plasticizers such as ethylhexyl, triisodecyl trimellitate, and tri-n-octyl trimellitate; such as tributyl phosphate, tri-2-ethylhexyl phosphate, 2-ethylhexyldiphenyl phosphate, and tricresyl phosphate. Examples include phosphate ester plasticizers.

[0012] The blending amount of the plasticizer is 10% of the vinyl chloride resin.
200 parts by weight or less, preferably 10 to 0 parts by weight
The range is 150 parts by weight. If the amount of the plasticizer is less than 10 parts by weight, the flexibility imparted to the composition is insufficient, and if it is more than 150 parts by weight, mechanical strength tends to decrease, Furthermore, there is a tendency for the surface to become sticky and contaminated due to plasticizer bleed.

As the lubricant, higher fatty acids, various paraffins, higher alcohols, natural waxes, polyethylene wax, fatty acid esters, fatty acid amides, etc. are used. Further, examples of the filler include calcium carbonate, clay, talc, silica-based fine powder, and aluminum hydroxide. Further, as the flame retardant, halogen-based flame retardants such as antimony trioxide, barium borate, zinc borate, zinc oxide, and chlorinated polyethylene can be used.

The vinyl chloride resin composition of the present invention is produced by uniformly mixing a vinyl chloride resin, an organic carboxylic acid metal salt, an organic tin stabilizer, and, if necessary, the other ingredients listed above. For example, the ingredients are uniformly dispersed using a ribbon blender, cake mixer, pickler, high-speed mixer, etc. to form a composition. This composition may be kneaded using a mill roll, a Banbury mixer, a pressure kneader, a single-screw kneading extruder, a twin-screw extruder, a plasticator, a co-kneader, or the like. The sheet or strand obtained by kneading can be pelletized and formed into a desired shape by passing it through a die, rolling it to form it, or press molding, injection molding, or the like.

[0015] Molded products made by coating sheets, films, etc. based on the electron beam-resistant vinyl chloride resin composition of the present invention with paints that are cured by electron beams can be used, for example, as tablecloths, flooring materials, leather, etc. be done. Further, a laminate using a base material made of the composition of the present invention with an adhesive cured by electron beams is used, for example, as an interior material or exterior material for construction such as a colored steel plate. Furthermore, a base material in which the composition of the present invention itself is crosslinked by electron beam irradiation to improve heat deformation resistance is suitable as a wire covering material that requires heat resistance or a cigarette-resistant flooring material. .

[0016]

[Effects of the Invention] The electron beam-resistant vinyl chloride resin composition of the present invention has transparency and little discoloration due to electron beam irradiation, so it is possible to coat the base material with an electron beam-curable paint, adhesive, etc. , lamination, or crosslinking of the composition itself. As a result, compared to external heat treatment, the processing time is shortened, and processing such as coating, adhesion, and crosslinking can be performed quickly at room temperature and under normal pressure, and it can be applied to the various applications mentioned above. . In particular, the composition of the present invention has high utility value in fields where transparency is required, and since it is transparent, it can be colored as desired.

[0017]

[Examples] Next, the composition of the present invention will be explained in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples unless the gist thereof is exceeded.

Examples 1 to 15, Comparative Examples 1 to 8 <
Ingredients> Vinyl chloride resin (average degree of polymerization 1100
) 100 parts by weight Di-2-ethylhexyl phthalate (DOP) 30 parts by weight
Organic carboxylic acid metal salts (listed in Tables 1 and 2) Organotin stabilizers (listed in Tables 1 and 2)
The above-mentioned components were uniformly blended using a high-speed stirrer, then formed into a 100 μm thick film using a calendar roll, and the film was irradiated with an electron beam of 5 Mrad. After irradiation 1
The color difference of the film after 000 hours was measured using the untreated sheet as a standard. The results are shown in Tables 1 and 2. For the measurement of color difference, "COLOR-7" manufactured by Kurashiki Boseki Co., Ltd. was used. In addition, the same film was heated in air at 180℃ for 20 minutes.
The separated samples were visually observed for discoloration. The results are shown in Tables 1 and 2. A "Perfect Oven" manufactured by Tabai Seisakusho was used for heating at 180°C.

[0019]

[Table 1]

[0020]

[Table 2]

Claims (1)

[Scope of Claims] [Claim 1] An electron beam-resistant vinyl chloride resin composition obtained by adding an organic carboxylic acid metal salt and an organic tin stabilizer to a vinyl chloride resin [Claim 2] An organic carboxylic acid metal The electron beam resistant vinyl chloride resin composition according to claim 1, wherein the metal of the salt is calcium, zinc, barium, cadmium or lead.Claim 3: The amount of the organic carboxylic acid metal salt added is 100% by weight of the vinyl chloride resin. Claim 1: 1 to 8 parts by weight per part.
or the electron beam resistant vinyl chloride resin composition according to claim 2.Claim 4.Claim 1, wherein the amount of the organotin stabilizer added is 1 to 10 parts by weight per 100 parts by weight of the vinyl chloride resin.
The electron beam resistant vinyl chloride resin composition according to claim 5.
Plasticizer 10-1 per 100 parts by weight of vinyl chloride resin
The electron beam resistant vinyl chloride resin composition according to claim 1, containing 50 parts by weight.