JPH05293942A - Plastic sheet having combination pattern of pearl gloss - Google Patents

Abstract

PURPOSE:To enhance the decoration property of a pearl gloss pattern on the basis of the synergistic color mixture effect with the color of a rear plain sheet by using a light pervious soft polyvinyl chloride sheet having a combination pattern of pearl gloss as a surface layer and laminating a light impervious plain plastic sheet or other sheet to one surface of the surface layer. CONSTITUTION:A light impervious plain soft polyvinyl chloride sheet is thermally welded to one surface of a soft polyvinyl chloride sheet produced by a combination pattern producing method to be integrally bonded thereto to form a two-layered sheet. The soft polyvinyl chloride sheet has light permeability. The plain sheet is composed of a soft polyvinyl chloride resin being the same material as the surface layer sheet and both sheets are bonded by thermal welding. Or, other material, for example, an aluminum foil (colored) is used as the plain sheet to be bonded to the surface combination pattern sheet by an adhesive under heating and pressure. In this case, the 60 deg.C mirror surface glossiness of the bonding surface of the plain sheet is set to 30% or more.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention has an object to provide a soft polyvinyl chloride sheet product having a pearly luster pattern pattern having excellent processability and high decorativeness. The sheet products include bags such as handbags, various stationery, cosmetic containers,
It can be effectively used as a footwear, especially as a surface cloth of Japanese dress, or as an interior material of a building.

[0002]

2. Description of the Related Art Soft polyvinyl chloride sheets or films have excellent mechanical properties and can be selected from various joining methods such as electromagnetic induction heating, ultrasonic bonding or heat sealing, and the raw material polyvinyl chloride. BACKGROUND ART Resins are widely used as industrial materials such as various agricultural materials or civil engineering materials because they are produced in large quantities, are inexpensive, and can be easily obtained anywhere. further,
Since polyvinyl chloride resin has excellent properties such as coloring, printing, and surface decoration workability such as embossing, it is often used as a material for various household items such as various packaging materials, tablecloths and interior products. Has been done. Such a soft polyvinyl chloride sheet or film decoration method has been widely used, and its technical method has been established.

On the other hand, as a method for decorating a plastic sheet, a decorative method using a pattern represented by a celluloid decorating method has long been known. The method for decorating celluloid according to this method is as follows.

(1) A suitable amount of camphor as a plasticizer, a dye as a coloring agent, and ethyl alcohol or methyl alcohol, which is a common solvent for nitrification cotton and camphor as a dissolving agent, are added to nitrified cotton, which is a main raw material of celluloid, and a kneading machine. Knead until the mixture is almost uniform. The kneaded product thus obtained has a sticky shape. When the solvent volatilizes, the sticky kneaded product hardens and finally becomes a stone, so while maintaining the sticky morphology, high shearing force is further applied by a two-roll mixer to further refine and completely A uniform coloring composition is obtained.

(2) This sticky colored composition is put into a mold having a rectangular parallelepiped cavity and pressed to shape it into a rectangular parallelepiped.

(3) The colored rectangular parallelepiped composition thus obtained is adjusted to an appropriate thickness (0.1) by using a planing machine (planer).
Slice (~ several millimeters) to make a sheet-shaped colored body.

(4) In this way, a colored sheet of at least two colors or more is manufactured, and this sheet is cut into the size of the side surface of the rectangular parallelepiped mold, and, for example, two color sheets are alternately formed. When they are lined up inside and pressed by applying heat of 40 to 60 ° C., the sheet interface is welded with the residual solvent of the composition due to the effect of heating, and a rectangular parallelepiped molded product having a striped pattern with alternating colors is formed.

(5) The striped rectangular parallelepiped is sliced into a predetermined thickness by a planing machine so that the pattern surface becomes the sheet surface, and then the residual solvent is dried and removed.

(6) Finally, a plated iron plate for luster is brought into close contact with both sides or one side of the sheet and heated and compressed by a press machine to form a celluloid dough having a striped pattern having a mirror gloss.

As can be seen from the above explanation, a considerably complicated pattern can be made by arranging the color sheets (called assembling patterns) and by increasing the number of colors.
The simplest pattern is to cut the mochi-like colored composition of two or more colors into a regular shape or an irregular shape, and then appropriately mix them.
It is a two-color or multicolor fixed or indeterminate braided pattern manufactured by a manufacturing method exactly the same as that of the striped celluloid (for example, a tortoiseshell pattern).

The feature of the decorative sheet having such a pattern is that it is possible to impart a three-dimensional and deep pattern unlike the simple surface printing or resin coloring. In particular,
The pearl luster pattern by the pearl pigment is a field which exhibits the most excellent characteristics of the decorative pattern decoration method, and brings a decorative effect which cannot be realized by the printing method. The reason for this is that incident light or reflected light is scattered or interfered on the surface of the pearl pigment that is three-dimensionally scattered inside the sheet, and the light causes very complicated refraction.

Therefore, if it is possible to manufacture a soft polyvinyl chloride sheet, which is widely used in each field, by a similar pattern decoration method (hereinafter, referred to as a “pattern pattern method”) similar to the method for manufacturing celluloid, and to give a pearly luster decoration. It can greatly contribute to the industrial field.

The soft polyvinyl chloride sheet having a patterned pattern can be obtained by a manufacturing method almost similar to that of celluloid. In this case, since the polyvinyl chloride resin is a thermoplastic polymer and is melted and liquefied by heating, it is not necessary to use a solvent as a solubilizer like celluloid (the nitrified cotton, which is a raw material of celluloid, also has a thermoplastic property). However, rather than heating, it decomposes when heated, so it is necessary to add a solvent to plasticize it in order to obtain a molded product.)

Therefore, except for the use of a solvent in the method for producing celluloid, the kneading step using a kneader and the two-roll mixer, the method for producing celluloid described above is used.
A soft polyvinyl chloride sheet having a braided pattern can be manufactured. That is, instead of the kneading machine and the two-roll mixer in the production of celluloid, a colored sheet or a fixed shape / form which is an element of the pattern is formed by an ordinary extruder.
An irregular colored molded product is obtained.

However, when a soft polyvinyl chloride sheet having a pearly luster pattern is produced using a pearl pigment, the expression of pearl luster depends on the thickness of the sheet.
The pearly luster is rapidly lost in a sheet having a thickness of less than 2 mm, particularly 1 mm or less, which is of practical and economic value.

The expression of pearl luster in the patterned sheet is
As described above, this is due to the interference and refraction of light at the resin / pearl pigment interface due to incident light and reflected light inside the sheet. Therefore, it is considered that the interference and refraction of light largely depend not only on the characteristics of the pearl pigment itself, but also on the characteristics of the dispersion medium of the pearl pigment, that is, the characteristics of the resin used. This means that when a soft polyvinyl chloride resin is used as the dispersion medium, its pearlescent appearance is strongly dependent on the sheet thickness, while nitrified cotton, which is the main material of celluloid, and other cellulose derivatives. For example, even when a cellulose acetate butyrate resin or a cellulose propionate resin is used as the dispersion base material, the pearly luster expression of those sheets is almost not affected by the sheet thickness.

Therefore, even if the conventional celluloid pattern decoration method is used as it is as the pearly luster pattern method of the soft polyvinyl chloride sheet, the intended purpose cannot be achieved.

[0018]

As described above, even if a soft polyvinyl chloride sheet having a pearly luster is produced by the patterning method, the pearly luster hardly appears, or even if the pearly luster is produced, nitrified cotton or acetyl cellulose is produced. The effect of pearly luster is remarkably smaller than when a cellulose resin is used as the base material. The cause of this is considered to be due to the characteristics of the polymer material used, particularly the characteristics of the interface between the pearl pigment and the polymer material that is the base material, so high pearl luster can be achieved simply by improving the manufacturing method and manufacturing conditions. The effect cannot be expected.

In the present invention, the problem to be solved is to produce a pearly luster by a method other than changing the production method or production conditions when producing a soft polyvinyl chloride sheet having a pearly luster pattern by a combined pattern production method. , To find a way to more effectively enhance the decorative properties of the sheet.

[0020]

[Means for Solving the Problems] The pearl luster of a pearl pigment is obtained by applying a strong shearing force to a nitrified cotton / camphor / colorant / pearl pigment composition with a roll mixer in the production of a structured celluloid, for example. It is known to be effectively exhibited by stretching and orientation. The expression effect due to the orientation of such a pearl pigment is not limited to the case of using nitrified cotton, and is similar to that of nitrified cotton in other cellulose derivatives such as cellulose acetate resin, cellulose acetate butyrate resin or cellulose propionate resin. Recognized by.

However, even if the present method is applied to a soft polyvinyl chloride resin, there is some effect, but not only the remarkable effect as in the former case is not recognized, but also the manufacturing cost is increased and the economical efficiency is impaired.

It is clear that the pearl luster in celluloid is manifested by the scattering or interference of the incident light from the sheet surface at the pearl pigment / resin interface. On the contrary, in the soft polyvinyl chloride sheet, sufficient pearly luster is apparently not expressed only by the incident light from the sheet surface, and it is speculated that the effect of adding the pearl pigment is latent. This assumption is also supported by the fact that the pearly luster increases as the thickness of the sheet increases and the amount of light reflected from the inside of the sheet increases.

Therefore, the inventors of the present invention have heat-bonded a plain soft polyvinyl chloride sheet, which does not transmit light, to one surface of the soft polyvinyl chloride sheet manufactured by the pattern manufacturing method and integrally bond them to each other. When a layered sheet was produced and the expression of pearl luster due to reflected light from the plain sheet surface was examined,
Pearl luster A beautiful pearl luster, which is almost the same as that of celluloid with a patterned pattern, was developed. Further, the surface condition of the plain sheet, the method of laminating with the surface layer pattern sheet, and the relationship between the influence of the optical properties of the surface layer sheet and the expression of pearl luster were examined, and the effective pearl luster was as follows. It was found that it was first expressed when certain conditions were met.

The soft polyvinyl chloride sheet made by the pattern manufacturing method is light transmissive. Here, the light transmittance is
It means that at least 6-point alphabetic characters can be discriminated when the sheet is superposed on the blank printing surface and the printing surface is viewed through the sheet surface directly under a 60 watt incandescent lamp about 40 cm away from the sheet surface.

The plain sheet is impermeable to light (
According to the measurement method), and the sheet is made of a soft polyvinyl chloride resin or a hard polyvinyl chloride resin of the same material as the surface layer sheet manufactured by the pattern manufacturing method, and the plain sheet and the surface layer pattern sheet are laminated together. Is performed by heat fusion, and the bonding interfaces of both sheets are fused and completely integrated.

The material of the plain sheet is polyvinyl chloride resin or a polymer material other than polyvinyl chloride resin or other material such as aluminum foil (colored), and the plain sheet and the surface layer patterned sheet are bonded to each other by adhesion. When a two-layer sheet is obtained by heating and press-bonding at a temperature below the melting temperature of the sheet material after bonding with an agent or an adhesive,
The 60 ° specular gloss of the pasting surface of the plain sheet is determined by JISK
5400 "General Test Method for Paint", when measured by the measuring method defined in Section 7.6 Specular gloss, the 60 ° specular gloss of the bonding surface of the plain sheet is 30% or more, preferably 40 or more.
% Or more. When the 60-degree specular gloss of the surface to which the plain sheet is attached is 30% or less, pearl luster is hardly exhibited.

Therefore, in order to effectively carry out the present invention, the above conditions and / or conditions must be satisfied at the same time. Further, the color tone of the plain sheet is an important factor that affects the pearly luster effect and the color mixing effect as described below. The most effective color tone is a dark color tone, and examples thereof include black, blue, and dark green.

Furthermore, another effect of the present invention is
By integrally laminating the plain sheet to the surface layer pattern sheet, the reflected light from the plain sheet and the color of the surface layer pattern sheet act synergistically, resulting in a more effective and deeper color mixture effect. It is possible to develop a certain pearly luster.

The soft polyvinyl chloride in the present invention means
Usually, the plasticizer used as a plasticizer for polyvinyl chloride resin is contained in an amount of 20 to 90 parts by weight per 100 parts by weight of the resin.

The polyvinyl chloride resin used in the present invention preferably has a degree of polymerization of 700 to 2,500. In addition to vinyl chloride homopolymers, vinyl chloride / ethylene copolymers and vinyl chloride / virniacetate copolymers. A combination, a vinyl chloride / polyurethane graft copolymer or a blend may be used. Further, the plasticizer, the stabilizer and the coloring material may be the ones usually used as long as the light transmittance is not impaired.

The pearl pigment, which is a particularly important material for exhibiting the effects of the present invention, is most effectively a finely powdered inorganic pigment obtained by coating the surface of natural mica with a metal oxide such as titanium oxide or iron oxide.

In the practice of the present invention, a light-impermeable plain sheet may be interposed or layered between two flexible polyvinyl chloride sheets made of light-transmitting patterned products to form a three-layer structure. It is possible.

[0033]

EXAMPLES The effectiveness of the present invention will be described below with reference to examples and comparative examples.

Polyvinyl chloride resin manufactured by Tosoh Corporation; product number Luron TH-1000; per 100 parts by weight, pyromellitic acid ester manufactured by Asahi Denka Co., Ltd .; product number UL-
80; 45 parts by weight, Epoxidized linseed oil manufactured by the same company; Part number O
-180A; 10 parts by weight, barium / zinc-based stabilizer manufactured by the same company; Part number AC-186; 1.5 parts by weight, barium / zinc-based stabilizer manufactured by the same company; Part number RUP-14; 1.5 parts by weight, manufactured by Merck Pearl pigment; Part No. Iriodin Ti100; 1 part by weight and an appropriate amount of colorant (dye) are added to a Henschel mixer (high-speed rotation mixer), and the temperature is raised to 120 ° C to cause gelation.

Then, after cooling with a cooling mixer, the resin is molded into a cylindrical shape and a belt shape at a resin temperature of about 170 ° C. using an extruder. The diameter of the cylindrical extrudate is about 6 mm, the width of the strip extrudate is about 25 mm, and the thickness is about 2 mm. Three or four kinds of extruded products are produced by changing the color. The cylindrical molded product is cut into a length of about 7 mm, and the band-shaped molded product is cut into a length of about 25 mm. Mix each color molded product well with a tumbler mixer.

This molded product is 16 cm in width, 35 cm in length,
Put in a mold with a depth of 8 cm, temperature about 135 ℃, pressure about 20 kg
Compress at f / cm ² . The pressing time is about 6 hours. During this time, the molded products are welded to each other in the mold, and a mixture of cylindrical or strip-shaped molded products of substantially the same size as the mold is obtained, which is a rectangular parallelepiped structured block molded product (the thickness of the block is cut and molded. Depends on the filling amount of the body mixture).

The pattern block molded product obtained in this manner was made to have a thickness of 0.2 to 2.0 mm using a planing machine (planer).
Slice into sheets and make into sheets. Since the blade marks of the planar blade remain on the surface of the sheet, the sheet is sandwiched between glossy plates and hot pressed to make the surface of the sheet a mirror surface (hereinafter, the sheet is referred to as "K sheet"), and then the light defined above is used. A permeability test was performed. Several measurement points are performed for each different color. The measurement results are summarized in Table 1.

Next, dioctyl phthalate was added to resin 100.
A polyvinyl chloride resin manufactured by Tosoh Corporation containing 30 parts by weight per part by weight; product number: Lyuron TH-1000 was formed into a film by a casting method (casting method). The film thickness is about 0.05
mm, color is colorless, white, yellow, green, red, brown, blue, and black solid pattern. A light transmittance test was conducted on the cast film thus obtained, and it was determined that light was not transmitted in any color film except the colorless film (hereinafter, the film is referred to as “M film”). ..

Thirdly, the temperature of the K sheet and the M film is about 1
A heat press kept at 60 ° C. was used for pressure bonding, and both were fused to obtain a two-layer sheet integrally laminated. The pearly luster developing property and the color mixing effect of the sheet were visually evaluated, and both were strongly dependent on the thickness (light transmittance) of the K sheet, and superiority or inferiority was recognized depending on the color tone of the M film. The results are shown in Table 1.

In Table 1, the judgment symbol "N" showing the pearly luster developing property and the color mixing effect of the two-layer sheet is very small or no gloss developing property and the color mixing effect are shown, and "Y-1" is very small. Excellent, "Y-2" means excellent and "Y-3" means slightly inferior. In addition, no influence of the pattern (cylindrical or strip) on the pearly luster development or the color mixing effect was observed.

[0041]

[Table 1]

Next, a plain black hard polyvinyl chloride sheet manufactured by Taihei Chemical Co., Ltd. having a thickness of 0.1 mm and a 60 degree specular gloss of 73%; product number Evilon HS-B (hereinafter referred to as "P sheet"), And a plain black hard polyvinyl chloride sheet manufactured by Taihei Chemicals Co., Ltd. with a thickness of 0.1 mm and a mirror gloss of 60 degrees of 5%; product number Evilon HS-B (matte)
(Hereinafter referred to as "Q sheet"), a vinyl chloride product made by Union Carbide Co., Ltd.
Vinyl acetate copolymer resin; product number VYGH; 15% by weight, methyl ethyl ketone 25% by weight and toluene 60% by weight
Was uniformly applied and then almost dried to obtain two types of resin-coated P sheet and Q sheet.

On the resin liquid coated surfaces of the P sheet and the Q sheet, the strip-shaped K sheet having a thickness of 0.2 mm used in Examples 1 to 7 and Comparative Example 1 was placed in an overlapping manner, and about 13
A two-layer sheet was obtained by thermocompression bonding using a hot press maintained at 5 ° C and bonding. When the expression of pearly luster of the two-layer sheet was visually evaluated, it was clearly recognized that the appearance of pearly luster was superior or inferior depending on the surface state (difference in glossiness) of the plain black sheet used. That is, the 60 degree specular gloss is 7
The pearly luster and color mixing effect of the double-layered sheet of 3% P sheet and K sheet was very beautiful and excellent,
The two-layer sheets of Q sheet and K sheet having a 60 ° specular gloss of 5% were inferior to the former.

[Procedure amendment]

[Submission date] May 8, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0036

[Correction method] Change

[Correction content]

This molded product has an inner width of 16 cm and a length of 35 c.
It is placed in a mold having a depth of 8 cm and a depth of 8 cm, and compressed at a temperature of about 135 ° C. and a pressure of about 20 kgf / cm ² . The pressing time is about 2 hours. During this time, the molded products are welded to each other in the mold, and a mixture of cylindrical or strip-shaped molded products of substantially the same size as the mold is obtained, which is a rectangular parallelepiped structured block molded product (the thickness of the block is cut and molded. Depends on the filling amount of the body mixture).

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0042

[Correction method] Change

[Correction content]

Next, a plain black hard polyvinyl chloride sheet manufactured by Taihei Chemical Co., Ltd. having a thickness of 0.1 mm and a 60 degree specular gloss of 73%; product number Evilon HS-B (hereinafter referred to as "P sheet"), And a plain black hard polyvinyl chloride sheet manufactured by Taihei Chemicals Co., Ltd. having a thickness of 0.1 mm and a 60 degree specular gloss of 5%; product number Evilon HS-B (mat) (hereinafter referred to as "Q sheet") As an adhesive on the mirror surface and the matte surface, a vinyl chloride / vinyl acetate copolymer resin manufactured by Union Carbide Co .; product number VAGH; 15% by weight, methyl ethyl ketone 25% by weight and toluene 60.
After uniformly coating a resin solution consisting of wt%, it was almost dried to obtain two kinds of resin-coated P sheet and Q sheet.

Claims (4)

[Claims] 1. A soft polyvinyl chloride sheet which is light-transmissive and has a pearly luster pattern pattern is used as a surface layer, and a plain plastic or other sheet having no light-transmissive property is laminated on one surface thereof. The pearly luster effect is realized by doing so, and the decorativeness of the pearly luster pattern is enhanced by the synergistic color mixing effect of the pearly luster pattern on the surface layer and the color of the plain sheet on the back surface. Layer plastic sheet. 2. The plastic sheet according to claim 1, wherein the soft polyvinyl chloride sheet on the surface layer and the plain sheet on the back surface are integrally bonded by heat fusion or an adhesive. 3. The non-light-transmitting plain sheet is made of hard or soft polyvinyl chloride, and is adhered to the surface layer sheet by heat fusion.
Or the plastic sheet described in 2. 4. A plain plastic sheet having no light-transmitting property is made of polyvinyl chloride resin or a polymer material other than polyvinyl chloride resin or other material, and is formed on the surface to be bonded to the surface layer sheet. 60 degree specular gloss is 30
% Or more, and the plastic sheet according to any one of claims 1 to 3, which is obtained by bonding with the surface layer sheet with an adhesive, or by thermocompression bonding after bonding with the adhesive. ..