JPS59105045A - Production of highly non-staining non-rigid sheet - Google Patents

Abstract

PURPOSE:To obtain the titled sheet which does not stain objects in contact therewith by the migration of plasticizers, by molding a vinyl chloride polymer compsn. contg. a specified ethylene polymer and a specified polyester plasticizer blended therewith into a sheet. CONSTITUTION:A vinyl chloride polymer (A) such as polyvinyl chloride or a vinyl chloride/ethylene copolymer, a high-molecular ethylene polymer (B) such as a terpolymer composed of 40-80wt% ethylene, 10-60wt% vinyl acetate and 3- 30wt% carbon monoxide and a polyester plasticizer (C) having an average MW of 1,200-3,000 such as adipate polyester plasticizer (a product of A deka Argus Kagaku K.K.) are mixed together in such a proportion as to satisfy the relationship represented by formulas I to IV (the shaded portion surrounded by straight lines in the triangular composition diagram). The mixture is molded into a sheet by a conventional method.

Description

DETAILED DESCRIPTION OF THE INVENTION A process, in particular for the migration of plasticizers in vinyl chloride-based soft sorts containing plasticizers.

It is an object of the present invention to provide a method for manufacturing a soft sheet-like material that eliminates the contamination of the sheet-like material due to diffusion and does not contaminate objects to be contacted.

Conventionally, when producing flexible/tab-shaped products using vinyl chloride polymers (hereinafter referred to as PVc), it has been essential to add a plasticizer to impart flexibility to the product. is compatible with PVc, has a relatively low molecular weight, and is usually in liquid form (typically DOP, molecular weight about 390), which is commonly used as a secondary plasticizer.

However, these secondary plasticizers are monomeric and have low molecular weight, and because they diffuse and move within the product, they can bleed or migrate to the surface, impairing the appearance and feel of the product. It is well known that this causes contamination of polystyrene or ABS, and contamination is particularly severe for certain types of coated materials such as alkyd lacquers, and in some cases has the serious disadvantage of eroding surfaces.

In order to alleviate the above-mentioned drawbacks, it is somewhat effective to use a polymeric polyester plasticizer (hereinafter referred to as polyester plasticizer) made of adipic acid polyester as a plasticizer, but this polyester plasticizer Because it has a large molecular weight compared to so-called secondary plasticizers, especially phthalate plasticizers (usually about 600 to 8000
), it has excellent retention properties and has little bleeding or migration, but on the other hand, it has poor plasticizing effect and needs to be used in a large amount to obtain a flexible sheet-like material, and the effect of reducing the above-mentioned contamination is not necessarily sufficient. As mentioned above, although contamination of polystyrene plates or ABS plates can be reduced to some extent, considerable contamination is observed on certain types of lacquered materials, which may cause the appearance of musical instruments, electrical appliances, furniture, etc. If it comes into contact with a painted surface, the painted surface will be contaminated or eroded, resulting in a significant loss of appearance and performance.

In recent years, P
A high molecular weight ethylene-based polymer (hereinafter referred to as terpolymer) consisting of a terpolymer of ethylene/vinyl acetate/-carbon oxide has been developed for VC, and a method using this has been proposed. , this terpolymer has a molecular weight of 25
It is a polymer with a molecular weight of more than 1,000,000, so there is no problem of bleeding or migration, and it also has a high molecular weight and has a moderate polar group. It is a special substance.

However, the plasticizing efficiency of the terpolymer is even lower than that of the polyester plasticizer, and therefore, in order to obtain a flexible sheet-like material, it is not only necessary to add a particularly large amount of the terpolymer. Since the polymer has a high molecular weight, it has poor miscibility with PVc, resulting in insufficient kneading, which often causes cracking due to poor deltization of PVc, and has strong stickiness at processing temperatures, resulting in a poor balance with the strength of the melt. However, it has the disadvantage that seeding is extremely difficult. For example, in the case of calender processing, the adhesiveness is strong, but unless the molten material has a corresponding strength, the sheet cannot be peeled off from the roll during processing, or even if it can be peeled off, when it is taken off by a take-off roll, the sheet is cut and the take-off occurs. The drawback is that it is extremely difficult.

As a result of various studies on the production method of highly non-staining soft notebook materials, the inventors of the present invention have found that they use both a terpolymer and a polyester plasticizer in a certain proportion as plasticizers to add polymer to PVC. By blending, the advantages and disadvantages of both polymers are complemented, and the miscibility with PvC is improved, as well as the stability of the compound composition and the balance between tackiness and melt strength during seeding. Highly non-staining. The present invention was completed by discovering that a flexible sheet-like product can be manufactured.

Note that the notebook-like material referred to in the present invention is a film.

shall mean sheets or their processed products, laminates and composite products.

As the PVc used in the present invention, PVc can be used as long as the terpolymer and the polyester plasticizer are compatible with each other.
Not limited to C alone, but also copolymers with other synthetic resins, such as PVC/ethylene copolymer, PVC/7″ L/N copolymer, PVC/vinyl ester copolymer, PVC/vinyl ether copolymer , PVC/vinylidene chloride copolymer or PVc graft copolymer to ethylene/vinyl acetate copolymer, etc. can be used, but in the sense that it is industrially produced and widely used, PVc and PVc/ethylene copolymer are suitable.

In addition, ternary copolymers are already known as modified materials for PVc in recent years (see Japanese Patent Publication No. 55-50063), and for soft applications 40 to 80% ethylene and 10 to 10% vinyl acetate are used. 6゜wt%, -carbon oxide 3-30wt%
It is a special terpolymer with a molecular weight of 250,000 or more.

There are still various types of polyester plasticizers depending on the type of polybasic acid and polyhydric alcohol used as raw materials, but the one that is well-balanced in terms of practical and physical properties and is widely used is Haboadipine. It is limited to acidic polyesters, which are also used in the present invention. Pol)
Ester plasticizers tend to produce migration as their molecular weight decreases, and as their molecular weight increases, their plasticization efficiency and compatibility tend to deteriorate, and their viscosity increases, resulting in poor workability. .

Therefore, in the present invention, in addition to considering the physical properties and properties described above, the present invention has particularly good compatibility with the terpolymer, compensates for the disadvantages of processability of the terpolymer, and has a high degree of non-staining property. In order to satisfy this requirement, it is preferable to select a medium molecular weight polyester plasticizer having an average molecular weight (P) within the range of L200 to 3,000.

The terpolymer is PVC (A), which functions to impart flexibility to the PVC sheet while satisfying the high degree of non-staining properties of the sheet.

The terpolymer (B), medium molecular weight polyester system, requires a relatively large amount of polyester plasticizer to compensate for flexibility, and as a result, high non-staining properties are not satisfied. If it exceeds 47% by weight, the melting temperature of the terpolymer is 40 to 70°C, whereas the crosstalk of PVC usually occurs at about 150 to 160°C, so the terpolymer will It melts at the beginning of the process and becomes a low-viscosity melt,
Since PVC becomes suspended in the terpolymer, it becomes difficult to crush and melt the PVC particles by the shear force of kneading, and as a result, it becomes difficult to mix with PVC, or to compensate for this. In order to achieve this, it becomes necessary to increase the amount of polyester plasticizer blended, and the high level of non-staining properties may be inferior, or the atomic weight of the plasticizer relative to PVC may become excessive, and the physical properties required for notebook-like materials may no longer be met. You won't be satisfied. Therefore, the terpolymer (B), on the other hand, the polyester plasticizer, together with the terpolymer, functions as a plasticizing substance that imparts flexibility to the ternary copolymer, and at the same time It has the function of compensating for the disadvantages of copolymers in processability, but on the other hand, the disadvantages of staining properties of polyester plasticizers are compensated for by the terpolymer.

If it is less than 3% by weight, the effect of improving the crosstalk with PVC will be insufficient, and if it exceeds 45% by weight, the high level of non-staining property will be poor or the weight of the plasticizing substance will be excessive compared to the PVC, resulting in a sheet-like product. The required physical properties can no longer be satisfied. Therefore, the polyester plasticizer (C) is A −+
-B + C is 3 to 45% by weight.

However, the above-mentioned terpolymer and polyester plasticizer satisfy the physical properties of PVC in 7-1, and can complement each other in terms of flexibility and high non-staining property. Total weight of coalescence and polyester plasticizer (B+C
) is (B+
If C)/(A-4-B+C) is less than 15% by weight, the flexibility will be insufficient and a soft sheet material, which is one of the objects of the present invention, will not be obtained, and if it exceeds 50% by weight, it will not be PvC. The above-mentioned (B 10C)
/(A+B+C) is in the range of 15 to 50% by weight.

The blending ratios of the PVC, terpolymer and photoester plasticizer as described above can be seen as hatched in the accompanying drawings.

The present invention is a special compound composition in which the above-mentioned PVC, terpolymer, and polyester plasticizer are blended in the above-mentioned proportions, and is used for the PV
c. Compounds other than the terpolymer and the polyester plasticizer can be those commonly used for flexible PVC. For example, stabilizers 5, pigments, fillers, lubricants.

Antioxidants, ultraviolet absorbers, and the like can be appropriately selected and used depending on the purpose of the product.

The compound composition is a terpolymer in which a polyester plasticizer is added to PVC and the polyester plasticizer is absorbed or not absorbed.

Stabilizers, as well as pigments, fillers, and other compounding agents are added as necessary, and the mixture is mixed and kneaded using a Hennel mixer, and/or bread/dairy, etc. After mixing with a kisser, calendar processing and extrusion processing.

It is processed into a sheet-like product using a conventional method such as inflation processing.

The above-mentioned /-1. shaped product can be used as it is, or it can be retated or laminated with other films, sheets or foams, or it can be made into a laminated product, or it can be given an uneven pattern on its surface. Of course, various processing methods such as printing can be applied.

EXAMPLES The present invention will be specifically explained below with reference to Examples, but the present invention is not limited thereto in any way.

Example 1 Using the raw materials listed in Table 1, 65 g of mixed raw materials with different blending ratios of these raw materials was put into a Brabender Plastograph, kneaded at 1500C for 5 minutes to obtain a compound composition, and this 3 at 170'C in a heat press machine.
A sheet with a thickness of 2 mm was created by heat pressing for 1 minute.
A transparent and flexible sheet was obtained.

As a result of examining the physical properties and staining properties of this sheet, as shown in Table 2, it was confirmed that it had sufficient physical properties for practical use, and almost no staining was observed on the polystyrene plate and Acrekilad lacquer coated plate.

Table 2: Mixing ratio and test results (Note) (1) Physical property test method It was carried out according to JISK7113.

(2) Stainability test method (a) Polystyrene plate: Lay 7 sheets on a polystyrene plate and apply a load of 500 g/cIrL2 to the 7 sheets.
After being left at 0°C for 24 hours, the contamination status was visually observed and determined.

(b) Lacquer coated board: Among coated plywood, the sheets are layered on a coated plywood coated with alkyd paint, which is particularly sensitive to the effects of plasticizers, and then a load of 10 g/crn2 is applied to this and the plate is heated to 150 °C at 50'C.
After leaving it for a while, the contamination status was visually observed and determined.

(3) Evaluation of contamination, ◎No contamination observed.

○Is there almost no contamination detected? Or a level that does not pose a problem in practice.

Comparative Example 1 Using the raw materials listed in Table 3, the raw materials were mixed in different proportions and processed in the same manner as in Example 1 to create a sheet. As a result, the results shown in Table 4 were obtained. Obtained.

That is, from the results in Table 4, when a phthalate ester plasticizer or a polyester plasticizer was used alone, the polystyrene plate was found to be contaminated, and the lacquer coated board was particularly contaminated.

Furthermore, as shown in Table 4, even when a terpolymer and a polyester plasticizer are used in combination, it is recognized that the high degree of non-staining property is poor.

Table 4 (Note) Evaluation of contamination ×Contamination is clearly observed.

XX Severe contamination, swelling and erosion are observed.

Example 2 80 kg of the formulation shown in Table 5 was charged into a Panbury mixer and kneaded at 150'C for 5 minutes to obtain a compound composition. When this compound composition was examined to see if it was mixed, it was found that it was mixed uniformly.

When the compound composition was sorted by conventional calender processing, there were no processing problems (Q, 2).
A flexible sheet of m+a thickness was obtained. The ungelled particles of this notebook were measured, and their physical properties and contamination properties were investigated as shown in Table 5.

Table 5 (Note) The unmelted particles were measured by observing the unmelted PVC particles contained in 1cTL2 using a microscope.

Comparative Example 2 80 kg of the formulation shown in Table 6 was placed in a Banbury mixer and kneaded at 150°C for 5 minutes to form a compound.
When the crosstalk state of the compound was investigated, the compound was not transparent, and when a thin section of the compound was prepared and examined under a microscope, a large number of ungelled particles were observed.

The cause of this is that undissolved PVC is present in the molten terpolymer.
It is presumed that this is because the particles are in a suspended state and sufficient shearing force does not act on the PVC particles.

Furthermore, when I tried to transfer the compound to two rolls and knead it and calender it into a sheet using a conventional method, it adhered strongly to the calender rolls, and even if it was partially peeled off from the rolls, the sheet would break immediately. Couldn't get a good seat.

Table 6

[Brief explanation of drawings]

The drawing is a graph showing the blending ratio of the present invention. Patent applicant Kyowa Shizu Co., Ltd. Rihito City Kawa Riyoshi

Claims (1)

[Claims] (]) For vinyl chloride polymers, high molecular weight ethylene polymers such as terpolymer of ethylene/vinyl acetate/-carbon oxide and medium molecular weight polyesters are used as plasticizing substances. When describing a method for manufacturing a highly non-staining soft sheet material, which is characterized by forming a compound composition in which a polymer blend of a plasticizer in the following proportions into a sheet by a conventional method, 2 x 100 = 50 ~ 85, weight % A+B+C -X 100 = 5 to 47 weight % A 10 B 10 C -
C (2) The highly non-staining soft sheet material according to claim 1, wherein the medium molecular weight polyester plasticizer is an adipic acid polyester having an average molecular weight L of 200 to 3,000. Production method.