JPS58211449A - Soft vinyl chloride laminated sheet - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a flexible vinyl chloride laminate sheet with little plasticizer migration.

Soft vinyl chloride sheets using conventional plasticizers are
It had many drawbacks due to plasticizer migration. For example, when used as a desk mat or document holder, if it comes into contact with documents copied by an electrostatic copier, the printing ink will adhere to the soft PVC sheet in a very short period of time, causing damage to the document. However, there was an inconvenient problem in that characters etc. on the printed surface could not be read through the soft vinyl chloride sheet.

Additionally, when such soft vinyl chloride sheets are used as packaging materials for polystyrene or acrylic resin molded products, the plasticizer in the soft vinyl chloride sheets migrates to the polystyrene or acrylic resin, dissolving the surface of the molded product and causing damage to the molded product. There was a problem that it spoiled the appearance.

As a method to improve this drawback of conventional soft vinyl chloride sheets, it has been proposed to use plasticizers with low migration (e.g. polyester plasticizers, trimellitic acid plasticizers, etc.), but these plasticizers Since it is a special plasticizer, it is expensive and the products in which it can be used are extremely limited. Another method that has been proposed is to laminate different types of films that do not contain plasticizers, but the laminated sheet obtained by this method is
Since the elongation and flexibility of the soft vinyl chloride sheet and the different film are different, there is a drawback that wrinkles appear when the sheet is folded.

As a result of intensive research to improve the shortcomings of these conventional products and improved products, the present inventors have developed a flexible vinyl chloride laminate that has less plasticizer migration, is economical, and does not wrinkle when folded. This led to the invention of the sheet.

That is, the soft vinyl chloride laminate sheet of the present invention comprises a soft vinyl chloride sheet (1) using a plasticizer with little migration;
In a laminated sheet of soft vinyl chloride sheets (■) using a plasticizer that easily migrates, the plasticizer in the soft vinyl chloride sheets (■) is placed between the soft vinyl chloride sheets (I) and the soft vinyl chloride sheets (■). It is formed by forming a synthetic resin layer that prevents the transition to.

Plasticizers with low migration include phthalic acid plasticizers such as talohexyl phthalate, which is solid at room temperature, phthalate esters whose alcohol has 9 or more carbon atoms, and polyhydric alcohols such as dipentaerythritol fatty acid esters. trimellitic acid plasticizers such as trioctyl trimellitate, trinonyl trimellitate, tridecyl trimellitate, sepacic acid, adipic acid, phthalic acid, etc. and polyhydric alcohols such as polyethylene glycol and polypropylene glycol. These include polyester plasticizers that are reaction products with epoxidized oils such as epoxidized soybean oil and epoxidized linseed oil. Of course, a plasticizer that easily migrates to the extent that there is no problem with migration may be used in combination.

Examples of plasticizers that tend to migrate include heptatalic acid ester-based movable agents having an alcohol carbon number of 8 or less, such as dibutyl phthalate, dioctyl phthalate, and dioctyl phthalate.

The synthetic resin forming the synthetic resin layer that prevents the plasticizer of soft vinyl chloride sheet) II from migrating to soft vinyl chloride sheet) has good adhesion to the soft vinyl chloride sheet and also prevents migration of the plasticizer. It must be a material with good performance, and examples include acrylic resin, polyester resin, polyamide resin, polyethylene, polypropylene, and polyurethane resin.

5- In order to form a synthetic resin layer that prevents the plasticizer of the soft vinyl chloride sheet (■) from migrating to the soft vinyl chloride sheet (I), the synthetic resin may be laminated in the form of a film on the soft vinyl chloride sheet. However, among the synthetic resins mentioned above, those that have a sharp coating may be applied to a soft vinyl chloride sheet and dried to form a synthetic resin layer. From the viewpoint of cost and plasticizer migration prevention effect, it is particularly preferable to apply an acrylic resin paint.

Soft vinyl chloride sheet I using plasticizer with little migration
It appears that the purpose of the present invention can be achieved by simply laminating a flexible vinyl chloride sheet ■ made with a plasticizer that easily migrates. However, over time, soft vinyl chloride seaweed) I
Since the plasticizer in I migrates to the soft vinyl chloride sheet I, which has the drawbacks of conventional soft vinyl chloride sheets, there is no plasticizer between the soft vinyl chloride sheet I and the soft vinyl chloride sheet If. A synthetic resin layer that prevents migration of agents is essential.

The vinyl chloride resin forming the soft vinyl chloride sheet 6- used in the present invention includes vinyl chloride homopolymer, vinyl chloride and other monomers such as ethylene, propylene, vinyl acetate, vinyl ether, and acrylic acid. Copolymers of esters, methacrylic esters, maleic esters, etc., and blend resins of vinyl chloride resin and other resins are also included.

As for other additives used in the soft vinyl chloride sheet, commonly used additives such as stabilizers, lubricants, pigments, fillers, and ultraviolet absorbers can be used, and there are no restrictions at all.

An example of manufacturing the flexible vinyl chloride laminate sheet of the present invention will be described. The soft vinyl chloride laminate sheet 5 is made by processing a soft vinyl chloride sheet (1) using a plasticizer with little migration and a soft vinyl chloride sheet (2) using a plasticizer that easily migrates by calendering or extrusion processing, respectively. Separately prepared, either one side of the soft vinyl chloride sheet is laminated with a synthetic resin film that prevents plasticizer migration, or a synthetic resin paint that prevents plasticizer migration is applied. Dry to form a synthetic resin layer (3) that prevents migration of plasticizer, and attach the other soft vinyl chloride sheet to this, and the synthetic resin layer (3) that prevents migration of plasticizer contains a plasticizer with little migration. A soft vinyl chloride sheet (1) using a plasticizer and a soft vinyl chloride sheet (2) using a plasticizer that easily migrates are sandwiched together and bonded with an adhesive (4) or multi-bonded by thermal lamination. It can be obtained by

Since the present invention is configured as described above, even if it comes into contact with documents copied by an electrostatic copying machine for a long period of time, copy ink will not adhere to it, and even if it comes into contact with polystyrene molded products, etc., the plasticizer will not adhere. does not migrate, so there is no risk of damaging the surface of the PS molded product. In addition, since both sides are made of soft vinyl chloride sheets and there is no synthetic resin layer on the surface to prevent plasticizer migration, wrinkles do not appear even when folded, which is preferable.

Examples of the present invention are listed below, but the present invention is not limited thereto.

Example 1 Acryloid BR-6 was applied to both sides of the sheet 10 shown in Table 1.
0 (acrylic resin; manufactured by Mitsubishi Rayon Co., Ltd.) toluene 10
After applying and drying the solution using a gravure roll, sheet 2 shown in Table 1 was thermally laminated on both sides of the sheet to obtain a flexible vinyl chloride laminate sheet.

The obtained soft vinyl chloride laminated sheet was subjected to a copy ink adhesion test), a transition test to a PS injection molded product, and a wrinkling test when bent.

Next is Soft Jj! PVC laminated sheet at 70℃ for 24 hours
After the heat treatment for a period of time, the copy ink adhesion test and the transfer test to PS injection molded products were conducted. The results are shown in Table 2.

Example 2 A soft vinyl chloride laminate sheet was obtained under the same conditions as in Example 1, except that Sheet 6 was used in place of Sheet 2 in Example 1, and the same tests as in Example 1 were conducted. The results are shown in Table 2.

Example 3 A soft 9-vinyl chloride laminate sheet was obtained under the same conditions as in Example 1, except that Sheet 4 was used in place of Sheet 2 in Example 1, and the same tests as in Example 1 were conducted. The results are shown in Table 2.

Example 4 A polyester film having a thickness of 15 μm was laminated on both sides of the sheet 10 shown in Table 1 using an adhesive, and a sheet 2 shown in Table 1 was further laminated on both sides of the sheet using an adhesive. Laminate to obtain a soft vinyl chloride laminated sheet,
The same test as in Example 1 was conducted. The results are shown in Table 2.

Comparative Example 1 Three sheets of Sheet 1 in Table 1 were thermally laminated to obtain a laminated sheet, and the same test as in Example 1 was conducted on this laminated sheet. The results are shown in Table 2.

Comparative Example 2 Sheet 2 was thermally laminated on both sides of Sheet 1 in Table 1 to obtain a laminated sheet, and the same test as in Example 1 was conducted on this laminated sheet. The results are shown in Table 2.

Comparative Example 3 A laminated sheet was obtained under the same conditions as in Comparative Example 2, except that Sheet 5 was used in -1 row instead of Sheet 2 in Comparative Example 2, and the same tests as in Example 1 were conducted on this laminated sheet. The results are shown in Table 2.

Comparative Example 4 A laminated sheet was obtained under the same conditions as Comparative Example 2 except that Sheet 4 was used instead of Sheet 2 in Comparative Example 2, and the same tests as in Example 1 were conducted on this laminated sheet.

Comparative Example 5 Acryloid BR- was applied to both sides of the laminated sheet obtained in Comparative Example 1.
A 10-titoluene solution of 60 was applied and dried using a gravure roll to obtain a laminated sheet, and the same test as in Example 1 was conducted on this laminated sheet.

The results are shown in Table 2.

Each test was conducted as follows.

[Copy ink adhesion test].

Xerox 400 on one side of the 5c111 square laminated sheet
0 (Fuji Xerox Co., Ltd.'s Shizuka Copy Machine), touch the printed side of the paper, sandwich it between glass plates, and make a 5kg
The sample was heated at 45° C. for 8 hours, and after cooling, the copy paper was peeled off and the state of ink adhesion to the surface of the laminated sheet was observed.

Evaluation criteria ◎・・・・・・There is no ink adhesion at all.

○: There is some ink adhesion.

Δ: Ink adhesion covers about half of the area.

×...Ink adheres to the entire surface.

[Transition test to PS injection molded product] A 5 cIn square polystyrene injection molded product was brought into contact with one side of a 5 crn square laminated sheet, heated at 50°C for 24 hours under a load of 10 Kf, and after cooling, the laminated sheet was peeled off. , p
The state of damage on the surface of the molded product was observed.

Evaluation criteria ◎・・・・・・No change in appearance at all.

△・・・・・・Slight change.

×...The change is significant.

[Wrinkle generation test during bending]

A 5α×10 cIn square laminated sheet was bent at the center in the longitudinal direction and the occurrence of wrinkles was observed.

Evaluation criteria ◎・・・・・・No wrinkles.

To... There are some wrinkles.

×: Large amount of wrinkles.

Table 1 *Polyester available TMLJ manufactured by Dainippon Ink Co., Ltd. Note) The sheets used were calendered to α6M thickness for each compound.

15-Table 2 As is clear from Table 2, the product of the present invention was heat-treated (plasticizer migration acceleration test), and the effect of preventing plasticizer migration was sustained, and the ink adhesion and plasticizer migration prevention effect persisted over a long period of time. It is good with no migration and no wrinkles.

[Brief explanation of drawings]

1 to 3 are cross-sectional views showing embodiments of the present invention, respectively. 14- (1) ... Soft vinyl chloride sheet using a plasticizer with little migration (2) ... Soft vinyl chloride sheet using a plasticizer that easily migrates (3) ... ...Synthetic resin layer to prevent plasticizer migration (4)...-Adhesive (5)...Soft vinyl chloride laminate sheet Figure 1, Figure 3, Figure 255-

Claims (1)

[Claims] Soft vinyl chloride sheet using plasticizer with little migration■
In the laminated sheet of soft vinyl chloride sheet ■ using a plasticizer that easily migrates, the soft vinyl chloride sheet ■ is placed between the soft vinyl chloride sheet I and the soft vinyl chloride sheet ■.
A soft vinyl chloride laminate sheet with less plasticizer migration formed by forming a synthetic resin layer that prevents the plasticizer inside from migrating to the soft vinyl chloride sheet I.