JPS6216221B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a flexible polyvinyl chloride resin composition for films, sheets, leather, etc., more specifically, a vinyl chloride resin composition that prevents ink from fading or fading for facsimile printing, non-carbon printing, and image ink. Pertains to. Recently, facsimiles have become extremely popular along with computers. Papers used for facsimile paper include electrolytic recording paper, discharge recording paper, electrostatic recording paper, electrophotographic paper, electrically conductive thermal recording paper, thermal paper, and plain paper (inkinit). recently,
Great progress has been made in the electrostatic recording method and the thermal recording method, and the thermal recording method is attracting particular attention from the viewpoint of economic efficiency. By the way, examples of ink-resistant vinyl chloride for printing on general recording paper include JP-A-58-111847, Trimellitic acid ester plasticizer, JP-A-58-162650.
Bis, amide-based lubricants, reaction products of alkylamine compounds and dicyanate compounds have been proposed in JP-A No. 59-49251, and various patent applications filed in Japanese Patent Application No. 58-30379 filed by the present applicant have been proposed. It has resistance to ink for recording paper, discharge recording paper, and plain paper, but no resistance to ink for heat-sensitive recording paper. The present invention has solved this problem, and is vinyl chloride which has excellent ink deterioration prevention properties for inks for heat-sensitive recording paper and pressure-sensitive paper, such as those using crystal violet lactone as a colorless dye and bisphenol A as a color developer. The object is to provide a resin composition. The present invention provides excellent long-term effects for all types of recording printing that are currently widely used by using vinyl chloride resin, chlorinated paraffin, and a polyester plasticizer or trimellitic acid plasticizer, either alone or in combination. It was completed by discovering something. In particular, chlorinated paraffin, which is effective in preventing ink deterioration, can bleed when used alone in large amounts, impairing commercial value, so in practical terms it can only be used at a maximum of about 60% of the plasticizer. When used, it is effective from a cost standpoint to use polyester plasticizers or trimellitic acid plasticizers that are effective at 60% or less of chlorinated paraffin, either alone or in combination. Chlorinated paraffin is known for its flame retardant effect and low cost, while polyester plasticizers have excellent durability and migration resistance, and trimellitic acid plasticizers are effective in heat aging resistance and stain resistance, and are heat sensitive. The effect of preventing ink from disappearing on paper is not known. The chlorinated paraffin used in the present invention has 7 to
Contains 40 carbon atoms and about 30-75% chlorine by weight
Polyester plasticizers are dibasic acids (generally succinic acid, curtaric acid, adipic acid, azelaic acid, sebacic acid, maleic acid, phthalic acid, etc.) and glycols (generally ethylene glycol). , 1,2-propylene glycol, 1,3-butylene glycol,
(1,4-butanediol, neopentyl glycol, etc.) and usually reacts with a molecular weight regulator (medium/higher alcohol or fatty acid) to form a linear polymeric polyester structure, and generally has a molecular weight 500-5000. Trimellitic acid plasticizers generally include trialkyl trimellitates such as trioctyl trimellitate, triisodecyl trimellitate, tri-n-octyl trimellitate, tris(2-ethylhexyl) trimellitate, tributyl trimellitate, and trimethyl trimellitate. To tell. In addition, thermal recording paper and non-carbon paper develop color through the reaction of a colorless dye and a color-forming acidic substance (color developer).For example, the colorless dye is crystal violet lactone, and the color developer is bisphenol. There are A, etc. The vinyl chloride resin composition referred to in the present invention includes a vinyl chloride resin, a stabilizer, an epoxy compound, a lubricant,
Sulfating agents, ultraviolet absorbers, antistatic agents, colorants,
Consists of filler, chlorinated paraffin, polyester plasticizer, and trimellitic acid plasticizer. As the vinyl chloride resin, a vinyl chloride resin or a copolymer resin of vinyl chloride and other monomers such as vinyl acetate, acrylic acid ester, or acrylonitrile can be used. Cd, Ba, Mg, Ca, Zn, which are commonly used as stabilizers in vinyl chloride resin.
Metal salts such as Sn and Pb can be used alone or in combination with other stabilizing aids. Further, the amount of plasticizer added is not particularly limited and may be determined depending on the flexibility of the sheet to be obtained. But in practical terms
A limit of 20 to 60 parts by weight that does not cause blooming is good. The method of molding the ink deterioration-preventing vinyl chloride resin composition of the present invention is not limited to the calendar method, but the effects of the present invention can also be obtained by processing methods such as the inflation method, extrusion molding, and casting method. Of course. The present invention provides a vinyl chloride resin composition that prevents ink from fading and disappearing by using a chlorinated paraffin polyester plasticizer and a trimellitic acid plasticizer as plasticizers in the vinyl chloride sheet. Can be molded. Next, the results of a basic dropping test of a plasticizer, which served as the basis for completing the present invention, are shown in Table ().

【table】

[Table] Drop various plasticizers onto the thermal paper used in Panafax 8000 manufactured by Matsushita Electric Industrial Co., Ltd. and observe the degree of ink disappearance on the thermal paper one hour later. The results are shown in the table. As is clear from the above table, chlorinated paraffin is superior to DOP, followed by polyester plasticizers and trimellitic acid plasticizers, which are effective in preventing ink loss. Next, we will explain blending examples and experimental results in conjunction with the table (): 100 parts by weight of vinyl chloride resin (degree of polymerization 1100), chlorinated paraffin in the proportion shown in the table below,
2 parts by weight of PN-310.TOTM and Ba-Zn composite stabilizer (paste) are mixed, and the mixture is 160%
A sheet sample with a thickness of about 0.33 mm was obtained by kneading with two rolls at ℃ for 5 minutes. Furthermore, in order to obtain smoothness of this sheet, it was heated at a steam pressure of 8Kg/cm for ² hours and 5 minutes, and then heated to 75Kg/cm.
A pressure of cm ² was applied for 5 minutes and then cooled to obtain a sheet sample of approximately 0.3 mm. Cut this sheet into 5cm x 5cm pieces and make the same size pieces made by Matsushita Electric Industrial Co., Ltd.
Lay out the thermal paper used in Panafax 8000 and place a 500g load between the glass plates so that the paper and sheet are in close contact. This sample was left in a dark place at 23°C ± 2°C for 14 days, and then at 45°C for 8 hours.
Check the degree of image disappearance. For evaluation, the state of the plasticizer bubbling was visually observed after leaving it at room temperature for one month. Regarding workability, the test conditions for observing the degree of peeling from the roll were 175°C and a sheet thickness of 0.3 mm, and the results are shown in the table. For comparison, a sheet was created using the same method of DOP composition. The table shows that chlorinated paraffin, polyester plasticizer, and trimellitic acid plasticizer are superior to DOP. It is also found that polyester plasticizers are somewhat more effective than trimellitic acid plasticizers. However, from the viewpoint of calendering, it is better to use a trimellitic acid plasticizer.

[Table] Additionally, vinyl chloride resin (degree of polymerization 1100)
100 parts by weight, 20 parts of E-500, PN-310 and
TOTM-30 parts blend (50 parts by weight) and E-500-20
%, PN-310 60% TOTM20% (24 parts by weight, 41 parts by weight) and epoxidized soybean oil (3 parts by weight)
Part by weight) Ba-Zn composite stabilizer (2 parts by weight) was mixed using a normal mixing roll and molded using a calender at approximately 170°C to a thickness of 300μ.
(0.3m/m) transparent sheet was created. For comparison, the same weight part DOP formulation was created. The test method is 23℃ x 14 days or 45 days according to the example in the table above.
The test was carried out at 500 g for 8 hours at ℃. (Evaluation is the same as the table)

【table】

[Table] From the table above, it can be seen that chlorinated paraffin, polyester plasticizer, and trimellitic acid plasticizer are superior to DOP. Also, the smaller the amount of plasticizer, the less the loss of characters and images. Additional additional examples Vinyl chloride resin (degree of polymerization 1100) 100 parts by weight, E
-500 20%, PN-310 60%, TOTM 20% (29 parts by weight), epoxidized soybean oil (3 parts by weight), Ba-Zn composite stabilizer (2 parts by weight). Sheets of the same thickness were created using the same method as in Example 3. For comparison, a DOP formulation with the same parts by weight was prepared. We investigated manufacturers and models of thermal paper, as well as the disappearance of non-carbon paper. The test method was 45°C for 8 hours and a load of 500g.

【table】

[Table] From the table above, the degree of ink loss differs depending on the thermal paper manufacturer, model, and non-carbon paper, but the blending systems of E-500, PN-310, and TOTM are DOP
There is less loss of characters and images on thermal paper compared to . Therefore, if this is used as a material for card cases, files, decorative boards, desk mats, etc., the ink characters and images on thermal paper for photocopying facsimiles and non-carbon paper will not become blurred and can be preserved for a long time. The vinyl chloride resin composition according to the present invention is not limited to films and sheets such as card cases, files, decorative boards, desk mats, etc., but is also suitable for use with thermal paper and non-carbon paper, where there is a risk that letters and images may disappear. It can be used for certain vinyl chloride resin compositions. As described above, the present invention can achieve the desired objective effects.

Claims (1)

[Claims] 1. Ink deterioration prevention property characterized by blending chlorinated paraffin with vinyl chloride resin and adding polyester plasticizer or trimellitic acid plasticizer alone or in combination. Vinyl chloride resin composition. 2. Chlorinated paraffin is blended within 5 to 30 parts to 100 parts by weight of vinyl chloride resin, and polyester plasticizer or trimellitic acid plasticizer alone or in combination is blended within 20 to 60 parts by weight including the chlorinated paraffin. 1. The ink deterioration-preventing vinyl chloride resin composition according to item 1 of the present invention.