JPS587443B2 - Colored synthetic resin pellets and manufacturing method thereof - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel colored pellet having excellent fusion properties and a method for producing the pellet.

Conventionally, synthetic resin flooring materials have played an important role as interior materials for buildings, and these are classified as follows based on their shapes.

(1) Regular size: PVC tile (2) Long sheet: non-foamed sheets, foamed sheets, and these synthetic resin flooring materials are available in plain color (simply colored) as well as imitated versions. They are also classified according to the attachment method as follows.

(1) Simple printing method/mixing method a. Marble pattern b. Printed pattern (2) A pattern with embedded small grain-shaped pieces. Items with small chips/pellets embedded in them. (3) A type in which relatively large tile pieces are embedded. (3) A type in which different colored powder particles are aggregated and fused. Items that are the same on the entire surface. Multi-colored/patterned items (4) Items with a distinctive uneven shibori pattern. Physical embossing is applied to (1), (2), and (3) above. Chemical embossing method (synchronized with the printed pattern) These flooring materials are selected depending on the location and purpose of use.
Although it is used for different purposes, recently there has been an increasing demand for flooring materials suitable for heavy walking, that is, floors that are frequently walked on.
Flooring materials that meet these demands are being developed.

Naturally, in the case of flooring materials used for heavy walking, damage such as abrasion or abrasion occurs in proportion to the amount of foot traffic, but such abrasion and abrasion can cause changes in the initial pattern or damage to the printed area. Those that cause the defect of disappearance are unsuitable for use in heavy walking.

Considering each of the above types in view of this point, it can be said that (2) and (3) are the most suitable, and (1) and (4) are inappropriate.

Regarding (2) and (3), (2) has been used for quite some time, and (3), especially (3) bite, has recently attracted attention.

However, since type (2) has the same structure over the entire surface, microscopically the chip pieces and crushed pieces can be recognized as a pattern, but macroscopically, when walking or standing, they do not look like a pattern. It has a poor decorative effect and has little decorative effect.

The same was true for (3)-i in this respect.

However, in (3)-B, the entire layer has the same color and composition, and each pattern is composed of powder particles of a different color, so it has an excellent decorative effect both visually and macroscopically. It is expected that the pattern will not disappear or be damaged due to wear and tear.

This (3)-B flooring material uses the embossing method in combination, that is, by applying synchronized embossing in which only a specific pattern part is pressed into a concave part and other pattern parts are made into a convex part, the decorative effect of the colored pattern is achieved. In addition, the embossing provides a three-dimensional decorative effect, making it extremely useful as a decorative floor covering for heavy walking.

As a method for obtaining this type of bedding material,
No. 6664, JP-A-51-87564, JP-A-52-
No. 21065, Special Publication No. 52-22776, Special Publication No. 53
-8569, etc.

All of these methods use a method of placing powder or chips in a pattern and pressing and fusing the powder or chips together to form a decorative layer, but they are not perfect in terms of fusing. This imperfection is the cause of unexpectedly large wear and tear.

Furthermore, if this fusion is not complete, the pattern boundaries of the powder particles placed in a pattern are likely to collapse, resulting in a disadvantage that the pattern of the resulting floor covering becomes unclear.

In each of the inventions disclosed above, various efforts have been made to overcome these drawbacks.

For example, in Japanese Patent Publication No. 53-8569, blended oil was added to the powder and granules, and salt pipe paste was added to the powder to prevent pattern collapse due to initial adhesion of the powder and granules, and to facilitate the fusion of the powder and granules. Methods such as sprinkling it on the body are used.

However, these methods cause adhesion to the patterning screen due to adhesiveness, resulting in poor addition of powder and granules, clogging and separation due to paste resin, and not only workability but also problems.
This had an unfavorable effect on the physical properties of the product, such as poor fusion and pattern distortion.

In the present invention, we have investigated colored pellets that can be used as a raw material for obtaining thick synthetic resin sheets such as highly decorative floor coverings for heavy walking, which eliminate these drawbacks.

That is, as a method for obtaining fine-grained colored pellets that do not require blend oil or paste resin, yet have good fusion properties and do not cause pattern collapse, the main layer 1 of the colored pellets is a sheet layer with a high softening temperature. This is the main material of the powder, that is, the main material with regard to the physical properties of the decorative layer of the thick multicolor patterned sheet.

A laminated sheet A is prepared by laminating surface layers 2 and 2' having a softening temperature lower than that of the main layer on both sides or one side of the main layer 1, and this is passed through a pulverizing device such as a crusher or a pulverizer to make fine particles. to obtain colored pellets A1 or A2.

In this case, the surface layers 2 and 2' may be colorless transparent layers or may be colored in a different color from the main layer 1; in the former case, the color tone of the main layer is softened and settled. In the latter case, the color mixing effect on the base color of the main layer,
In other words, an effect similar to using colored pellets of different colors is produced.

In addition, colored pellets of a certain thickness are internally divided into a transparent layer and a main layer (base color), or a different color layer and a main layer, so if the pattern layer is composed of colored pellets, the particle size will be smaller than it appears. The effect is similar to that of using small powder particles.

This tendency is more effective when the surface layer 2 is laminated on both sides.

In short, the first point of the present invention is to create a colored pellet having a combination of the main layer 1 having a high softening temperature and the surface layers 2 and 2' having a low softening temperature. In addition to the usual methods of laminating the main layer at the same time as sheeting, such as calendering and extrusion, methods of applying a solution paint are also effective methods for constructing the surface layer 2.

Here, the expressions "high softening temperature" or "low softening temperature" are somewhat abstract, but if defined from the point of concrete formulation technology, DOP for 100 parts by weight of vinyl chloride resin with a degree of polymerization of about 1000. Around 40 parts of plasticizer such as
A filler containing about 100 to 150 parts of heavy calcium carbonate is suitable as the main layer with a high softening temperature, whereas vinyl acetate with a degree of polymerization of about 800 and containing 5% vinyl acetate is suitable as a main layer with a high softening temperature. About 50 parts of a plasticizer such as DOP and a filler such as heavy calcium carbonate are added to 100 parts by weight of a vinyl chloride copolymer, or about 50 parts of a plasticizer such as DOP and a filler such as heavy calcium carbonate to 70 parts by weight of the copolymer and 30 parts by weight of the above-mentioned vinyl chloride resin. A combination containing about 10 to 100 parts is suitable as a surface layer with a low softening temperature.

The expression "low softening temperature" has a relative meaning with respect to the main layer, and also means that strong fusion is obtained when colored pellets are adhered to each other or pressure is applied at a temperature of around 150 to 200°C. It also means things.

Furthermore, the expression "low softening temperature" means flexibility at room temperature, and when colored pellets A1 or A2 are assembled and placed in a pattern, the surface layer 2 and the other surface layer 2' A light adhesion occurs in the areas in contact with the paper, which is effective in preventing the pattern from fading.

This is similar to the stickiness or difficulty in peeling off two soft vinyl chloride films when they come into contact.

In addition to the vinyl chloride resin and vinyl acetate-vinyl chloride copolymer resin mentioned above, the main component resins of the colored synthetic resin pellets include ethylene-vinyl acetate copolymer, chlorinated polyethylene, chlorosulfonated polyethylene, acrylic ester resin, and ABS. , etc. alone or in mixtures with others can be used, whereas DOP, DBP, DHP, TCP, DIDP, D
Combined use of primary plasticizers such as OA, BBP, and TXP and secondary plasticizers such as salt para and chlorinated stearate, plasticizers and stabilizers such as epoxidized soybean oil, fillers such as calcium carbonate, rosin and petroleum resins, etc. Binder, various stabilizers, etc. are added as appropriate.

Naturally, pigments such as titanium oxide are also added depending on the coloring or coloring design.

The thickness of the main layer and the thickness of the surface layer relative to the thickness of the main layer should be determined from the optimum particle size of the powder and granules, and the average particle size is 15.
~20 mesh: 0.8 x 0.8 m/m ~1.
Since the dimensions are about 2 x 1.2 m/m, in the case of double-sided layers, it is suitable to have a main layer of 0.7 m/m and a surface area of 0.15 min each, with a total thickness of around 1.0 m/m. In the case of granules of around 10 mesh, the main layer is 1.0 m/m, the surface area is 0.25% each, and the sheet is made into a sheet with a total thickness of about 1.5 m/m, and it is crushed by a crusher or pelletizer to the specified size. Grind into fine particles.

If a paint is used, the surface layer will be extremely thin compared to the thickness of the main layer, so the thickness of the main layer should be used in determining the surface layer.

Example 1 Manufacture of colored pellets (1) Manufacture of main layer (1) Formulation ■・Main layer (1-1) After kneading the above compound with an intensive mixer, thoroughly knead with a mixing roll, and place in an upright two-roll calender. Pass it through two rolling lines in series to obtain a brown sheet with a thickness of 1.0 m/m.

(2) Formulation ■/Main layer (1-2) A white sheet with a thickness of 1.0 min is obtained using the same equipment as in (1) above, except that only the pigment is replaced with titanium oxide.

(3) Formulation ■/Main layer (1-3) A 0.5 mm black sheet is obtained using the same equipment as in (1) above, except that the same as Formulation ■, except that only the pigment is replaced with carbon black.

(2) Lamination and fine graining of the surface layer (1) Formulation■・Surface layer (2-1) After kneading the above compound with an intensive mixer, thoroughly knead with a mixing roll, and then use an inverted L-shaped 4-roll calender as the main ingredient. A layer of 0.25 mm was laminated on both sides of layer (1-1) to obtain a laminated sheet with a total thickness of 1.5 mm.

This laminated sheet was passed through a pelletizer, with an average particle size of 10
A mesh pulverized body a1 is obtained.

(2) Formulation ■・Surface layer (2-2) By removing heavy calcium carbonate from Formulation ■, a layer of 0.25 mm is formed on both sides of the main layer (1-2) using the same method as in (1) above. Each layer was laminated to obtain a laminated sheet with a total thickness of 1.5 mm.

This laminated sheet is passed through a pelletizer to obtain powder a2 having an average particle size of 10 mesh.

(3) Formulation ■・Surface area (2-3) The above formulation was prepared in the same manner as in (1) above to a size of 0.3 mm.
It is rolled and laminated on one side of the main layer (1-3) to a total thickness of 0.
An 8 mm laminated sheet was obtained.

This laminated sheet is passed through a pulverizer to obtain powder a3 having an average particle size of 20 mesh.

The powders a1, a2, and a3 obtained in this way are each individually or in a mixed state such as a1 and a2, a2 and a3, and are spread over the backing substrate with an adhesive layer to a thickness of 5 to 10 mm. After being dispersed and spread, the powder layer is compacted by heating and pressurizing and is extremely suitable as a colored pellet for producing a decorative walking floor covering. However, in the suction type production method described below, Particularly suitable.

An equipment line that preferably uses the colored pellets of the present invention is shown in FIG. 5, and details of the transfer patterning machines B1, B2, and B3 are shown in FIG. 13.

First, as shown in FIG. 5, an adhesive 6 is applied by a coating machine 5 to the surface of a wide and elongated base material 3 made of synthetic resin that is wound into a roll.

Although the doctor blade method is schematically illustrated in FIG. 5, a reverse roll method is also suitable.

Normally, PVC paste is suitable for the adhesive 6, but
Solution types such as reactive liquid urethane systems and vinyl chloride-acrylic resin solutions are also used.

If it is necessary to heat the adhesive after applying the adhesive on the differential material, passing it through a heating furnace should be optionally adopted and is not particularly limited, but it is suitable for adhering powder and granular materials in the subsequent process. When considering this, excessive drying and gelation to the extent that the adhesive surface loses its tackiness should be avoided.

After applying the adhesive, make a tuning mark 8' on one edge of the substrate.
is attached by the marking machine 8.

Although FIG. 5 shows a method of punching holes at the ends of the base material, other marking methods such as printing methods are also suitable.

In short, this synchronization mark is a necessary means for synchronization embossing in which the pattern and the concave-convex diaphragm precisely match with the synchronization embossing machine 31, and as long as it meets this purpose, it is not limited to the method shown in the figure. do not have.

Especially transfer patterning machines B1, B2, B3...
. The colored pellets are sequentially transferred and patterned in a pattern. The structure of this transfer patterning machine will be explained with reference to FIG. 13.

The colored pellet 11 of the powder or granule material is prepared from (2)-( of Example 1 above).
a1 obtained in 1), (2)-(2), (2)-(3)
, a2, a3, and are housed in the supply hopper 10, and held by the suction endless plate belt 17 and leveling roll 12 located below.

The plate belt 17 is made of a synthetic resin layer such as thermoplastic urethane, soft vinyl resin, or EVA, or a vulcanized rubber layer such as EPT, polyptadiene, polychloroprene, butyl rubber, or a light-activated resin such as an ultraviolet cured film on the wire mesh 17''. A part of this resin layer or rubber layer is punched out and removed in a pattern to form pattern-shaped holes 17', and colored pellets are inserted into the mold holes by the rotation and left-right movement of the leveling roll 12. filled inside.

The plate belt 17, whose mold cavities are filled with colored pellets in this manner, advances at its anchor, and when it reaches the lower part, it is sucked by the suction action of the suction roll 13 and then reversed.

The suction roll 13 has a large number of suction holes 13', and the colored pellets on the wire mesh are suctioned and fixed through these suction holes, so that the colored pellets do not fall off even when the roll is turned over.

Furthermore, since the surface layers 2, 2' adhere to each other slightly, the fixation is further enhanced.

Further, a suction shutoff device 13'' is provided inside the suction roll 13, and is configured to release the suction/fixing action when the pattern-shaped hole reaches a predetermined position, that is, a position where it contacts the base material in parallel. It can be adjusted arbitrarily and has a semi-cylindrical shape that is inscribed in the inner surface of the suction roll.

When this suction action is released, the colored pellets filled in the mold cavity are transported by their own weight or by the action of the dropping device 13''.
The pattern is transferred to the adhesive surface of the base material without disturbing it.

Although the dropping device 13″′ is shown as using a blower nozzle in FIG. 13, it is not limited to this method.
In addition to this, mechanical methods such as bran rolls are also effective.

A feature of the colored pellets of the present invention is that when they fall, the colored pellets of the present invention are prevented from losing their pattern due to the light adhesion between the surface layers.

The endless suction plate belt 17 is suspended on a roll group including a suction roll 13, guide rolls 14, 16, and receiving roll 15, and rotates and moves by driving these rolls.

Further, a brush roll 21 is provided for applying a mold release agent 19 to facilitate the fall of the colored pellets from the surface of the plate belt 17 and to prevent foreign matter from adhering to the surface of the plate belt 17 other than the mold cavity. .

Note that the mold release agent 19 is placed in a container 18 and transferred to a brush roll 21 by a pumping roll 20, and then transferred to the plate belt 1.
70 surface is coated.

Note that the guide rolls 16 are for preventing the plate belt from being stirred and may be omitted, or conversely, if the stirring is large, the number of guide rolls may be increased.

The plate belt 17 should be replaced arbitrarily depending on the pattern of the multicolor pattern sheet, and in the case of the present application, one pattern sheet is made up of a combination of a1, a2, and a3. By replacing the plate belts with other combinations of plate belts such as a1', a2', a3', etc., other pattern sheets can be obtained.

This attachment/detachment is relatively easy; narrowing the gap between the suction roll 13 and the guide roll 14 will loosen the plate belt, so pull out the plate belt laterally, remove it, insert another plate belt, and use the suction The distance between the roll 13 and the guide roll 14 is increased.

In this case, of course, it is necessary to adjust the marking machine for the synchronization mark so as to match this pattern, and also to replace the concavo-convex squeeze roll.

Furthermore, adjustments to the detector are also required. As another embodiment of the transfer patterning apparatus, as shown in FIG. 14, it is extremely effective to use a suction type receiving roll as the receiving roll 15 located below the supply hopper.

In the method shown in FIG. 13, the colored pellets 11 are filled into the mold cavity by their own weight and the feeding action of the leveling roll 12. However, in the case of colored pellets that tend to cause bridging of granules in the hopper, The method shown in Figure 14 is effective.

The suction type receiving roll 15 is also provided with a suction hole 15' and a suction blocking device, so that the suction start position and suction release position can be freely adjusted.

A first pattern (based on the colored pellets a1) is transferred onto the base material 3 by the first transfer patterning machine B1, and then a second pattern (based on the colored pellets a2) is transferred onto the vacant area other than a1 by the second transfer patterning machine B2. However, a third pattern (based on colored pellets a3) is sequentially transferred and patterned onto vacant areas other than a1 and a2 by a third transfer patterning machine B3.

The number of patterns should be set arbitrarily, and in the case of only a1, only a1+a2, a1+a2+a3, or when there are many more colors and patterns, a transfer patterning machine is added and the pattern is created using the same method. It should be done.

It is also effective to install an electric heater between each patterning machine to temporarily fuse the colored pellets, and this is especially effective in preventing pattern shifting during patterning in the next process. If the colored pellets are a fluid material mainly made of vinyl chloride resin paste and mixed with colored granules, this is extremely effective in preventing patterns from mixing together.

However, this heater is omitted in FIG.

After patterning a1, a2, a3... in this way, these patterned sheets (base materials) 3 are heated in a heating furnace 23 to make the colored pellets weldable. When softened, the adhesive layer 6 is completely dried and gelled at the same time, and immediately after the patterned sheet (base material) 3 leaves the heating furnace, that is, in a state where the colored pellets are heated and softened, a press roll is applied. The colored pellets are passed between the devices 24 and 25 to compress them tightly and press them together, and to make the adhesion with the adhesive more complete, while smoothing and leveling the patterned surface.

Next, on the top surface of this leveled patterned sheet (base material) 3,
A transparent resin layer 27 is applied by a coating device 26 .

The transparent resin layer 27 protects the pattern layer, improves abrasion resistance, prevents contamination, and fills the joints between each pattern (open spaces between patterns) with resin, so that it can be used in the subsequent squeezing process. It is applied to prevent excessive pattern bleeding, and uses vinyl chloride resin paste, vinyl chloride resin solution, mixed solution of vinyl chloride resin with acrylic resin, two-component polyurethane resin, etc. alone or in combination, or ultraviolet curable paint. However, it is not particularly limited as long as it satisfies the above purpose.

This transparent resin coating device is used to coat the patterned sheet (substrate) 3, and is capable of applying a coating solution relatively thickly using a reverse roll coater, a flow coater, etc. without applying excessive stress to the patterned surface. The equipment is suitable.

From this point of view, it can be said that a set of round blade doctors is also suitable.

FIG. 5 shows an example of a reverse roll coater, where 27 is a transparent resin liquid, 28 is a squeezing roll, 26 is a reverse roll, and 29 is a backup rubber roll.

The patterned sheet (base material) 28 coated with transparent resin is passed through a heating furnace 30 to complete drying and gelation of the transparent resin layer and coating with colored pellets.

The cross-sectional structure of the patterned sheet in each step is shown in FIG. 7, FIG. 8, FIG. 9, and FIG. 10, respectively.

The heated patterned sheet leaving the heating furnace 30 is immediately passed through synchronized concavo-convex embossing devices 31, 32 to apply concavo-convex embossing 31', 31'', 31''' on the surface of the patterned sheet.

The cross-sectional structure along the line ■-■' is shown in Fig. 11, and the cross-section of 31' is shown in Fig. 12. In Fig. 11, the third pattern a3 is the concave part, and the first pattern a1 is the convex part. , the second pattern a2 is an example of pressing to form a convex part in the middle, but this should be arbitrarily selected according to the pattern.
It is not limited to the three stages of high, middle, and low as shown in Figure 1.

This synchronized concave and convex diaphragm pressing must match the patterns a1, a2, and a3.

As the device, first, the detection mark 8' made by the marking machine 8 is detected by the synchronized mark detector 33 provided immediately or immediately before the squeezing devices 31 and 32, and the squeezing roll is rotated at the correct position. Control as if you were doing it.

This control is normally performed by issuing a slight rotational slowing speed command, since it is sufficient to follow the slight expansion and contraction of the base material 3 during the process.

The multicolor pattern sheets obtained in this way have patterns a1 and a2.
By changing the color and pattern of each of , a3, various design effects can be obtained, and since the concave and convex embossing is applied to match the pattern, it is an extremely excellent product that adds a three-dimensional effect to the above design effect. It becomes a multicolored patterned sheet.

Furthermore, unlike printed products, this sheet is made up of colored pellets that have the same pattern on all layers, so when used for flooring, etc., even if it wears out, the same pattern will appear, resulting in a pattern effect. is never lost.

In addition, since it has a protective layer on its surface, it has excellent stain resistance and abrasion resistance, and can be waxed easily.

[Brief explanation of the drawing]

The drawings show an example of the implementation of the present invention, and FIGS.
The figure is an enlarged sectional view of the laminated sheet, FIGS. 2 and 4 are enlarged sectional views of colored pellets, FIG. 5 is an explanatory diagram of the manufacturing process of the patterned sheet, and FIGS. 6 to 11 are - ■′
12 is a partially enlarged sectional view of FIG. 10. , FIG. 13 is a partially cutaway perspective view of the transfer patterning machine, and FIG. 14 is a sectional view of the transfer patterning machine in another embodiment. In the figure, 1 is the main layer, 2 and 2' are the surface layers. Layers, A is a laminated sheet, A1 and A2 are colored pellets, 3 is a base material, a1, a2, a3...... are transfer pattern parts, 27 is a transparent resin layer, 31', 31'', 31″′...
. . . is a concave and convex diaphragm.

Claims (1)

[Scope of Claims] 1 The main layer is formed of a colored synthetic resin with a high softening temperature, and both or one side thereof has a softening temperature lower than that of the main layer and is colorless and transparent or colored in a different color from the main layer. Fine-grained colored synthetic resin pellets with a surface layer. 2 A surface layer made of a synthetic resin that has a lower softening temperature than the main layer and is colorless and transparent or colored in a different color from the main layer is provided on both or one side of the main layer made of a colored synthetic resin sheet with a high softening temperature. 1. A method for producing colored synthetic resin pellets, which comprises forming a single layered sheet, and pulverizing the laminated sheet using a crusher, a pulverizer, or the like.