JPH01260071A - Production of sheetlike substance - Google Patents

Abstract

PURPOSE:To obtain a sued-like sheetlike material, laminating a resin containing microcapsules having a volatile substance such as butane to the surface of a polyvinyl chloride resin backed with paper or cloth in the whole face of the layer or in a pattern state. CONSTITUTION:A treating solution of a synthetic resin containing microcapsules having a volatile organic compound such as butane in an organic solvent is laminated to the surface of a synthetic resin layer consisting essentially of a nonexpandable, unexpanded or expanded polyvinyl chloride layer optionally backed with a base material such as paper or cloth in the whole face of the layer or in a pattern state, then the microcapsules are expanded by drying and heating or heating of the sheetlike material in an after-process, the sheetlike material is made into a napped state and a napped part is formed on the synthetic resin layer to give a sued-like sheetlike material having strong bond with a resin component of the treating solution.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a sheet-like material used for wall covering materials, flooring materials, leather, etc.

<Prior art and problems> Copolymers of vinylidene chloride and acrylonitrile are highly expansive, and if they are microencapsulated with volatile organic compounds such as butane, they can replace azodicarbonamide. It is well known that it can be used as a blowing agent.

When this microcapsule is heated, the volatile organic compound contained therein expands, and the microcapsule itself expands. After expansion, the microcapsules become soft yet elastic spheres. Based on this fact, it was expected that by incorporating the microcapsules into a synthetic resin, it would be possible to give the synthetic resin a suede-like touch.

As a result of the above prediction, in Japanese Patent Publication No. 62-28481, the microcapsules were dispersed in a plastisol paint whose main component was polyvinyl chloride, and the microcapsules were applied onto a substrate! !
I was able to obtain a suede-like sheet-like product. The sheet-like product created according to this recipe has a suede-like appearance due to the fine irregularities provided by the microcapsules.

The above paint is based on polyvinyl chloride resin 10
30 parts by weight of the microcapsules are added to a basic formulation consisting of about 70 parts by weight of a plasticizer and about 5 parts by weight of a liquid stabilizer. The paint is applied over the entire surface or in an arbitrary pattern onto a sheet-like material in which a synthetic resin layer containing polyvinyl chloride as a main component is laminated in advance on a base material. This is gelled by heating, and this heating causes the microcapsules contained in the paint to expand, which causes a suede-like sheet (Figure 1).
can be obtained.

Wall covering materials manufactured using the above formulation have attracted attention for their texture, which was completely absent in the past, and are widely used as interior materials for buildings. However, since this formulation uses plastisol made of polyvinyl chloride, it lacks physical strength.

For this reason, it has been pointed out that the drawback is that it will fall off when you scratch it with your nails. In addition, although it is praised for its voluminous suede feel, it does not have the softness of natural materials, and due to these two drawbacks, its use is avoided in areas where it comes in direct contact with people's hands, such as leather. ing.

Means for Solving the Problem> The formulation for laminating a synthetic resin layer containing polyvinyl chloride as a main component on a base material can be roughly divided into two types.

One is a method in which polyvinyl chloride obtained by suspension polymerization is compounded with a plasticizer, stabilizer, etc., and the compound is sheeted and laminated on a base material. This includes the so-called calendar method and extrusion molding method.

Another formulation is a method in which polyvinyl chloride obtained by emulsion polymerization is made into a plastisol paint with a plasticizer, stabilizer, etc., and this is coated on a base material and further gelled to form a laminated layer.

When a synthetic resin layer containing polyvinyl chloride as a main component obtained by the former suspension polymerization method is laminated on a base material, a sheet-like product with excellent surface strength is obtained. On the other hand, the latter formulation produces a sheet-like material that does not have very good surface strength, but is more advantageous than the former formulation from a cost standpoint.

Representative examples of sheet products made by laminating polyvinyl chloride on a base material include leather and wall covering materials. In the case of leather, there are many uses that require abrasion resistance, so many products are laminated using the former formulation.However, in the case of wall coverings, there are generally fewer uses that require surface strength, and there are differences between manufacturers. The latter formulation is widely adopted due to intense cost competition.

As mentioned above, in the formulation according to Japanese Patent Publication No. 62-28481, a plastisol paint containing polyvinyl chloride obtained by an emulsion polymerization method as a main component was used as a binder to contain the microcapsules. As mentioned above, sheet materials made from this formulation are excellent as wall covering materials, but their use as leather is avoided because they do not have excellent surface strength. However, the reality is that suede-like textures have been sought after not only for wall coverings but also for leather. Tokuko Showa 62-2848
An attempt was made to obtain suede-like leather with excellent surface strength using recipe 1, but it was not possible.

In contrast, in the present invention, an organic solvent solution of synthetic resin (including commercially available synthetic resin treatment agents, synthetic resin ink diluents, etc.) is used as the binder to contain the microcapsules. By adding and dispersing the microcapsules and using them as a treatment agent, this formulation is used to impart a suede-like texture not only to wall covering materials but also to general sheet-like materials such as leather.

Among the organic solvent solutions of synthetic resins employed as binders in the present invention, surface treatment agents are most commonly used.

This surface treatment agent is used for the purpose of adjusting the surface condition of sheet materials, such as gloss or touch. The resin component of the treatment agent includes polyvinyl chloride, polyurethane, acrylic resin, etc., and these resins are dissolved in an organic solvent alone or in a mixture. In some cases,
Some contain additives such as melanin and amino acids.

Of course, the synthetic resin used varies depending on the purpose; for example, when the surface treatment agent requires moisture permeability, a moisture permeable polyurethane or the like is used. The gloss, touch, and other properties of surface treatment agents are largely determined by the synthetic resin in which they are dissolved. Microcapsules are added to these surface treatment agents to create a mixed treatment agent, and this is used to give a suede-like texture to sheet-like products. When used for the purpose of imparting a suede-like sheet, the various properties of the treatment agent can be utilized as they are as the physical properties of the suede-like sheet. Figure 2 is a cross-sectional view of the suede-like sheet according to the present invention. On the synthetic resin layer 7, the expanded microcapsules 6 are covered with the resin 5, which is a component of the solidified processing agent, to form a raised shape. Resin IO is a single substance or a mixture of resins such as polyurethane resin, polyvinyl chloride, acrylic resin, etc.
These resins have strong bonds between resin molecules.The suede-like sheet material according to the present invention has raised portions made of resin with strong bonds, and therefore has strong physical strength.

However, in the case of synthetic resins whose main component is polyvinyl chloride obtained through emulsion polymerization, the bonds between resin molecules are weak.

Therefore, the physical properties of the suede-like sheet obtained by Japanese Patent Publication No. 62-28481 are weak.

In addition, the diluent for printing ink used in gravure printing etc. is usually made by dissolving resins such as acrylic resin and polyvinyl chloride in an organic solvent, but microcapsules are added to this and used. In fact, when microcapsules were contained in these diluents and sheet-like materials were prepared according to the formulation of the present invention, suede-like sheet materials with excellent physical strength could be obtained.

A solution of a synthetic resin in an organic solvent, such as the surface treatment agent shown above, is used as a binder, and the microcapsules are contained therein to form a mixed treatment agent (hereinafter referred to as a mixed treatment agent). If the microcapsules are expanded by heating after being coated on a material, a suede-like sheet material with excellent surface strength can be obtained.

Prescriptions for laminating this mixed treatment agent on a base material include transfer by intaglio printing such as gravure, coating by a doctor, and the like.

Immediately after the mixed treatment agent is laminated on the substrate according to the above-mentioned recipe, the organic solvent is removed in a drying oven and the resin content is dried.

If sufficient heating is applied during drying to cause the microcapsules to expand, a suede-like sheet material can be obtained at this point. In addition, microcapsules expanded by -degrees deteriorate due to heat, so when heating is applied in the post-process,
The heating performed during drying must be kept to a level that does not cause the microcapsules to expand.

<Example> Commercially available microcapsules encapsulating a volatile organic compound such as butane are divided into grades depending on the temperature at which they give a maximum volume in a certain period of time (for example, 1 minute). For example, the temperature at which the microcapsule P-1'8 manufactured by Dainichiseika Chemical Co., Ltd. gives its maximum volume after heating for minutes is approximately 140°C;
1 is approximately 160°C. Therefore, microcapsules must be selected depending on the type of heat processing to be performed on the sheet-like material.

Example 1 Non-yellowing polyurethane was dissolved in an organic solvent, and microcapsules (Dainichi Seikagaku Co., Ltd. Co., Ltd. p-tg) 5
A mixed treatment agent was obtained by adding parts and dispersing this with a stirrer. Furthermore, 10 parts of a coloring agent for polyurethane was added to color it dark brown.

On the other hand, a black colored foamable synthetic resin layer having the composition shown in Table 1 was laminated on the woven fabric by a calendaring method, and a non-foaming synthetic resin layer having the composition shown in Table 2 was further laminated thereon.

Table-1 Resin: PVC 100 parts Plasticizer: DOP 75 parts Filler:
CaC0, 30 parts blowing agent, A
DCA type ・・・・・・・・・ 3-part stabilizer:
・・・・・・・・・・・・ 5 two-point pigment: ・・・
...... IO section table-2 Resin: PVC ......100 parts Plasticizer: DOP ......65 parts Filler:
CaC0, 30 parts Stabilizer:
・・・・・・・・・ 32-point pigment: ・・
A sheet-like material laminated with 10 parts and two synthetic resin layers was heated to approximately 225° C. in a foaming furnace to foam the synthetic resin layer (lower layer).

After foaming, add 10% of the mixed treatment agent prepared in advance.
The entire surface of the sheet-like material was coated once using a 0-mesh gravure printing roll. Gravure printing is a type of so-called intaglio printing, in which the processing agent is transferred by the recesses of a printing roll. Therefore, the mixed processing agent is transferred to the areas where the concave portions of the printing roll contact, but hardly any of it is transferred to the areas where the convex portions contact.

Therefore, the mixed treatment agent is transferred according to the fine mesh pattern of the printing roll, and each applied area is independent, so when the microcapsules are expanded, the mixed treatment agent applied area becomes a suede-like raised area. grow into

After application, the mixed treatment agent was dried and solidified by hot air, but the microcapsules did not expand at this time. A cross-sectional view of the sheet-like material at this time is shown in FIG.

Next, the sheet material was passed through a drying oven kept at 150° C. at a line speed of about 50 seconds to expand the microcapsules in the solidified mixed treatment agent. The sheet-like material obtained by this heating was suede-like leather with excellent surface strength and a pleasant wet touch.

In addition, since each of the dark brown raised parts is independent, the black polyvinyl chloride layer underneath can be seen through the gaps, giving depth to the color and an excellent design. Ta. In addition, FIG. 4 shows a cross-sectional view of this suede-like leather.

Example 2 Microcapsules that give maximum volume by heating at 180°C for about - minutes (P-21 manufactured by Dainichi Seikagaku Co., Ltd.)
10 parts were added and dispersed in an ink diluent for gravure printing (Medium II manufactured by Nippon Print Ink Co., Ltd.) to obtain a mixed processing agent. Furthermore, 10 parts of a coloring agent was added to give the mixture a brown color.

The mixture was transferred twice over the entire surface of a black sheet (unfoamed) having two synthetic resin layers having the composition shown in Tables 1 and 2 using a 100-mesh gravure print roll. At this time, the sheet-like material was dried with hot air, but the microcapsules did not expand.

In order to supply the resin to the area where the mixed treatment agent is applied, which grows into the raised area due to the expansion of the microcapsules. 00
A non-yellowing polyurethane treatment agent was further transferred using a Metsch gravure print roll. (In terms of strength, there is no problem even if resin is not supplied to the raised area, but this was done to further improve this physical property.) After transfer,
Although it was dried with hot air, no expansion of the microcapsules was observed. Figure 1-5 shows a cross-sectional view of the sheet-like material at this time.

Next, the sheet material was heated to 225°C in a foaming furnace.
The polyvinyl chloride foam layer 21 was foamed, but at this time,
Expansion of the microcapsules could be observed.

A mixed treatment agent layer 19 containing microcapsules is sandwiched between a polyurethane treatment agent coating layer 18 and a non-foaming synthetic resin layer 20. Therefore, when the microcapsules existing between the two expand, the microcapsules try to pull the resin layers 18 and 20, which have been softened by heating.

Further, as mentioned above, each of the mixed treatment agent application layers 19 is independent. Since the coated part and the non-coated part are separated by microscopic units, expansion and contraction occurs in the three layers 18, 19, and 20 when the microcapsule expands, creating a suede-like raised part spanning these three layers. I was able to do something. The sheet-like product (Figure 6) obtained with this formulation was good as a leather with excellent physical strength and design. Moreover, compared to the leather described in Example 1, it had a raised part with a feeling of volume.

Example 3 A plastisol paint having the composition shown in Table 3 was laminated on a flame-retardant paper having a thickness of 0.13 mm by a coating method, and was turned into a semi-gel by heating to obtain a sheet-like material.

Table-3 Resin: PVC 100 parts Plasticizer: DOP 50 parts Filler:
CaCO5,,---0-0AOO part Foaming agent: A
DCA type・・・・・・・・・ 1 part stabilizer:
・・・・・・・・・・・・ 3 parts white pigment: Ti0g,
, , , , -, , 20 parts Microcapsules (P-21 manufactured by Dainichi Seikagaku Co., Ltd.) that give a maximum volume by heating at 180°C for minutes 5 parts were added to The mixture was added and dispersed in Medium 11 to obtain a mixed treatment agent. Note that this mixed treatment agent was not colored.

The mixed treatment agent was transferred once onto the entire surface of the sheet by gravure printing with 120 meshes. Immediately after the transfer, the microcapsules were dried with hot air, but no expansion of the microcapsules was observed.

Next, we used gravure printing again to create a desired design by synchronizing the two-color patterns. Furthermore, for the purpose of gloss adjustment and supply of resin to the suede-like raised area, a polyurethane-based matte treatment agent was transferred according to the above-mentioned formulation. No expansion of the microcapsules was observed when this treatment agent was dried.

Finally, an embossing machine was used to create irregularities on the sheet material that matched the design created during the shipping process.

A sheet-like product has several resin layers, but in order to create irregularities with this embossing machine, it is necessary to soften the resin layer by heating or the like.

The embossing machine used was equipped with a far-infrared heater, and was able to supply enough heat to soften the sheet material. Furthermore, expansion of the microcapsules was observed due to this heating.

The sheet-like material (Figure 7), which has been made with unevenness by this embossing machine and the mixed treatment agent has grown into a suede-like raised part, is a suede-like wall covering with an unevenness and two-color pattern design. It was excellent. It also had excellent surface strength.

Example 4 A design in which a plastisol paint having the composition shown in Table 4 was applied in the previous step to the sheet-like material (before embossing) obtained using the recipe described in Example 3 by screen printing. I painted it while keeping it in sync. Immediately after coating, it was heated to semi-gel, and a synthetic resin layer was partially laminated. At this time, no expansion of the microcapsules was observed - Table 4 Resin: PVC 100 parts Plasticizer: DOP 50 parts Filler: CaC0, 50 parts Stabilizer: 3.5 parts Pigment:
・・・・・・・・・Next, when the microcapsules were flowed through a foaming furnace kept at 225°C at a line speed of about 30 seconds, the microcapsules expanded and were coated by screen printing. The resin layer was completely gelled.

The sheet-like product thus obtained (FIG. 8) had soft suede-like raised parts 35 to 38, and the resin layer 34 laminated by screen printing had a hard accent. Further, since the resin layer 34 was laminated on the mixed processing agent transfer portion containing microcapsules, it had fine irregularities. This suede-like sheet material with fine irregularities has a surface condition that was obtained for the first time by using a synthetic resin treatment agent containing microcapsules, which is a formulation according to the present invention. I couldn't find anything that had it.

The sheet material was excellent as a suede-like wall covering material with excellent surface strength and design.

[Brief explanation of the drawing]

FIG. 1 shows a cross-sectional view of a suede-like sheet material obtained using the formulation according to Japanese Patent Publication No. 62-28481. Figure-2
1 is a cross-sectional view of a suede-like sheet material obtained using the formulation according to the present invention, and is shown for comparison with FIG. 3 and 4 show cross-sectional views of the sheet-like material (leather) according to Example 1; FIG. 5 and FIG. 6 show the sheet-like material (leather) according to Example 2; Figure-7
is a sectional view of the completed suede-like sheet material (wall covering material) of Example 3. FIG. 8 is a cross-sectional view of the sheet-like material according to Example 4. G... Microcapsule binder layer (polyvinyl chloride layer), 2... Microcapsule 3... Synthetic resin layer, 4... Base material, 5... Microcapsule binder Layer, 6...Microcapsule, 7.
...Synthetic resin layer, 8...Base material, 9...Mixed treatment agent coating layer, IO...Non-foaming synthetic resin layer, 11.
... Foaming synthetic resin layer, 12... Woven fabric, 13...
...Mixed treatment agent coating layer (raised part), 14...Microcapsule, 15...Synthetic resin layer, 16...Synthetic resin layer (foam), 17...Woven fabric , 18...
Polyurethane treatment agent coating layer, 19...Mixed treatment agent coating layer, 20...Non-foaming synthetic resin layer, 21...
・Foamable synthetic resin layer, 22... woven fabric, 23...
Polyurethane treatment agent coating layer, 24...Mixed treatment agent coating layer, 25...Microcapsule, 26...
Synthetic resin layer, 27...Synthetic resin layer (foam), 28
... Woven fabric, 29... Matting treatment agent, 30...
・Colored layer, 31... mixed treatment agent application, 32...
Microcapsule, 33...Synthetic resin layer, 34...
...Flame retardant paper, 35...Synthetic resin coating layer, 36...
- Matting treatment agent coating layer, 37... Colored layer 38...
・Mixed treatment agent coating layer 39...Microcapsule, 4
0...Synthetic resin layer, 41...Flame retardant paper Patent applicant Kanto Leather Co., Ltd. CEO Akinori Seki-1 Figure-2 Figure-3 Figure-4 Figure-6 Figure-7

Claims (1)

[Claims] Volatile organic compounds such as butane are encapsulated on the surface of a synthetic resin layer mainly composed of non-foamed, unfoamed or foamed polyvinyl chloride, which is lined with a base material such as paper or cloth as necessary. A synthetic resin-based treatment agent containing microcapsules is laminated on the entire surface or in an arbitrary pattern, and then the treatment agent is heated when drying the treatment agent, or by heating in a post-process of the sheet-like material. A method for producing a sheet-like product characterized by expanding microcapsules containing a suede-like appearance.