JPS6218262A - Sheet-shaped laminated material with pattern and manufacturethereof - 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 [Industrial Field of Application] The present invention relates to a sheet-like composite material having a concavo-convex pattern formed on its sheet surface, and a method for manufacturing the same.

[Conventional technology]

Sheet-like composite materials with textured patterns on their surfaces have the texture of textured leather, for example, and have been in demand in recent years as materials with a three-dimensional feel that cannot be obtained with simple cloth or film. It's growing. The conventional manufacturing method for such a patterned sheet-like composite material is: 1. After forming a resin layer such as vinyl chloride resin or urethane resin on the entire surface of the base material, embossing is performed on this resin layer to give an uneven pattern. Method: ■ A method of forming a resin layer containing a foaming material on the entire surface of the base material, then foaming the resin layer over the entire surface, and applying embossing to the foamed resin layer to give an uneven pattern; ■ A method of forming a foaming agent on the surface of the base material. 3. A method of printing a resin coating solution containing a desired pattern and pre-drying it to form a pattern-shaped resin coating film, and then foaming this resin coating film to give an uneven pattern.
There are different methods.

However, in the above method of embossing the resin layer, the uneven pattern is formed by embossing the resin layer and partially immersing it, so if you want to create a three-dimensional effect, it is necessary to apply the resin layer thickly to some extent. There is a need,
There is a problem in terms of economics. Furthermore, the embossing method has the disadvantage that the uneven surface has the same gloss, the contrast of the uneven surface is weak, and the uneven pattern visually lacks a three-dimensional effect. In addition, even with the method of embossing the foamed resin layer described in (2) above, since the foamed resin layer is partially immersed by embossing to form an uneven pattern, it is still necessary to apply a thick resin layer, which is not economical. There is a problem with this. Moreover, the uneven pattern formed is
As with # above, lack of contrast is unavoidable. Furthermore, in the print foaming method described in (■), when printing a resin coating solution containing a foaming agent, it is inevitable that the coating solution flows around the surrounding area, making it difficult to obtain a concave-convex pattern with sharp foamed edges. If the adhesion between the resin coating film and the resin coating is insufficient, the fine pattern parts tend to fall off easily, making it unsuitable for forming fine patterns, or changing the pattern can be very troublesome. However, there are drawbacks such as problems with productivity.

[Problem that the invention seeks to solve]

In this way, conventional methods not only have problems from an economical perspective, but also have problems such as the contrast of the uneven pattern obtained is weak and the three-dimensional effect is poor, and it is difficult to form fine patterns. As the demand for this type of composite material is increasing significantly, there is a strong demand for improvements.

The present invention was developed in view of the above circumstances, and the contrast between the concave and convex portions is strong due to the difference in gloss, and the concavo-convex pattern has a rich three-dimensional effect, and the pattern does not stand against the base material. The purpose of the present invention is to provide a sheet material composite material that has strong adhesion, is easy to manufacture, and is inexpensive, and a method for manufacturing the same.

[Means for solving problems]

In order to achieve the above object, the present invention includes a sheet-like base material and a thermally expandable microcapsule-containing resin layer formed on at least one of the front and back surfaces of the sheet-like base material, and the resin layer is The first aspect is a patterned sheet-like composite material that is partially raised due to thermal expansion of thermally expandable microcapsules, and a pattern is formed by the raised portion, and the thermally expandable microcapsule-containing resin layer is formed on the surface and A sheet-like base material formed on at least one of the back surfaces is prepared, and a heating device equipped with a heating body having a convex pattern formed on the heating surface is prepared, and the convex pattern of the heating body of this heating device is prepared. A patterned sheet that is brought into contact with the surface of the resin layer of the sheet-like base material in a heated state to expand thermally expandable microcapsules contained in the resin layer in the contact area to form a raised convex pattern. The second gist is the manufacturing method of shaped composite materials.

Among the three conventional methods for producing patterned sheet-like composite materials, the present inventors applied a resin liquid containing foamed microcapsules (thermally expandable microcapsules) to a base material to form a resin layer.
In the process of conducting research on improving the method (2) above, which involves foaming the entire surface and then embossing it to partially form recessed portions to form an uneven pattern, we discovered that a foamed microcapsule-containing resin layer, similar to the method (2) above, Instead of foaming the entire surface and then embossing it to form recessed parts to form an uneven pattern, the pattern-forming convex part of an embossing roll is brought into contact with the surface of the foamed microcapsule-containing resin layer in a heated state. We have discovered that if the resin layer portion of the contact area is foamed and raised in the opposite manner to method (1) above, a difference in gloss between the concave and convex portions occurs, resulting in a strong contrast and a sharp uneven pattern, which led us to the present invention. did.

The patterned sheet-like composite material of the present invention is obtained by preparing a sheet-like base material in which a resin layer containing thermally expandable microcapsules (foamed microcapsules) is formed on the sheet surface, and applying the resin layer to the sheet-like base material. This can be obtained by contacting the convex pattern of the heating body of the heating device in a heated state.

The sheet-like base material used in the present invention includes natural fibers such as cotton, wool, and linen, and acrylic.

Non-woven fabrics made from synthetic fibers such as nylon, polyester, and rayon, and mineral fibers such as glass fibers and carbon fibers, either singly or by blending or weaving two or more of them.

Examples include woven fabrics and knitted fabrics. In addition to these, plastic films made of nylon, polyester, etc. may also be used. A plugging coating agent may be applied to these base materials in advance, prior to the formation of a resin layer containing thermally expandable microcapsules as a foaming agent. When forming the resin layer by coating resin liquid, etc., if the base material is rough, the resin liquid will penetrate into the base material, impairing the flexibility of the base material itself, or requiring a large amount of resin liquid. A filling coating agent is applied as necessary. As a filling coating agent,
Any material may be used as long as it has good adhesion to the substrate and the resin liquid and can be coated with a general coating machine, but generally the same kind of polymer as used in the resin liquid above is used. Emulsions or aqueous solutions (optionally thickened with thickeners) of the substances are used.

The resin layer formed on the sheet surface of the above-mentioned sheet-like base material contains thermally expandable microcapsules and becomes a pattern-forming layer. It is formed by coating (brushing, spraying, etc.) and drying. The polymer that is the main component of the resin liquid is preferably a heat-softening resin that softens when the resin layer is heated by a heating device and does not inhibit the expansion of the heat-expandable microcapsules. Specific examples of polymers include homopolymers of acrylic esters and methacrylic esters or copolymers thereof (ethyl acrylate/methyl methacrylate copolymer, 2-ethylhexyl acrylate/methyl methacrylate copolymer). etc.), polyvinyl acetate, ethylene-vinyl acetate copolymer, polyurethane, polyvinyl chloride, polyvinylidene chloride, etc., which may be used alone or in combination. Among these polymers, weather resistance.

From the viewpoint of wear resistance, texture, etc., polyurethane or acrylic resin is suitable, and may be used alone or in combination. Usually, these resins are used in the form of an emulsion. Among these emulsions, polyurethane emulsions have a 100-% modulus of 70 kg.
The most preferred is one that can form a film with an elongation of 400% or more, more preferably 500 to 1000% at a weight of 50 kg/cn or less, more preferably 50 kg/cn.

The thermally expandable microcapsules distributed and contained in the resin layer formed on the sheet-like base material contain a liquid having a boiling point lower than the softening temperature of the resin forming the shell in a thermoplastic resin shell. This is a well-known blowing agent in which the low boiling point liquid boils and vaporizes when heated, causing the shell to expand as it softens and form fine closed cells. This type of blowing agent is a general inorganic blowing agent (foaming temperature 7
Because the foaming temperature is higher than that at temperatures below 0°C, there is no problem of foaming in the unfoamed areas during post-processing (ironing), and it is highly temperature sensitive and can be heated for a short time by heat embossing, etc. It shows a high foaming ratio. In addition, the above-mentioned foaming agent generates a large number of fine closed cells during foaming, makes the surface of the foamed part matte, and creates a significant difference in gloss (contrast) between the foamed part and the unfoamed part, making the foamed part look three-dimensional. This phenomenon was discovered by the present inventors when the resin layer was partially foamed rather than the entire resin layer, and the gloss of the foamed portion and the unfoamed portion were significantly different. This is the biggest feature of In addition, general organic blowing agents, like the inorganic blowing agents mentioned above, have the disadvantage of slow foaming speed.
The foaming temperature is high at 160℃ or higher, and during heat embossing, etc., the coating layer is baked onto the embossing roll, making it impossible to get clean embossing.In addition, unless the coating is applied thickly, it is impossible to avoid gas escape or the formation of pinholes. This cannot be used because the pores tend to become coarse continuous pores.

In addition, the above-mentioned thermally expandable microcapsules used in the present invention preferably have a foaming temperature of 80 to 160°C, and further, from the viewpoint of workability of heat embossing as described below,
Further, from the viewpoint of preventing trouble from occurring during post-processing, it is more preferable that the foaming temperature is 100 to 140°C.

The patterned sheet-like composite material of the present invention can be manufactured, for example, as follows.

First, the above-mentioned thermally expandable microcapsules are blended into an emulsion or aqueous solution of a film-forming polymer such as a polyurethane emulsion so as to have a predetermined expansion ratio, and if necessary, a filler, a colorant, and a water repellent are added. , softeners, viscosity modifiers, antifoaming agents.

A polymer emulsion (aqueous solution) containing thermally expandable microcapsules is prepared by adding an anti-aging agent, etc. and dispersing it uniformly using a general method using a stirrer such as a homomixer or a disilver.
Create. Here, the foaming ratio can be expressed as [coating film thickness before foaming]. In this case, in order to make the foamed portion of the coating film have a predetermined foaming ratio, the blending ratio of the polymer in the emulsion and the microcapsules is set to 100% in terms of solid content.
It is preferable to set it to /20 to 100/l OO,
More preferably it is 100/40 to 100/80. If this compounding ratio is followed, the expansion ratio will be 5 times or more, and the difference in height between the foamed and non-foamed areas will be clearly determined by heating and foaming (1
The difference is 60 μm or more, and a three-dimensional uneven pattern can be recognized by touching with a finger). However, if the amount of microcapsules is too small compared to this blending ratio, the desired expansion ratio cannot be obtained even if the coating amount is increased, and conversely, if the amount of microcapsules is too large, the expansion ratio will be too high and the foamed surface will be uneven. The properties increase and the strength decreases. Therefore, it is preferable to set the blending ratio within the above range.

Next, the obtained microcapsule-containing polymer emulsion is applied to the pattern-forming surface of the base material by a known screen method, roll coating method, knife coating method, gravure method, brush coating method, or the like. The amount of coating at this time varies strictly depending on the base material, weave, thickness of the 8@fiber, etc., but as a rough guide, it is 100 to 300 g for a 40% by weight microcapsule-containing polymer emulsion.
/M. If the coating amount is less than 100 g/rrr, if the substrate is something other than a film, for example cloth, the coating film will be thin and the film after foaming will also be thin, making it difficult for the uneven pattern to have a three-dimensional effect. On the other hand, the coating amount is 300g/r
If it exceeds d, it will take a long time to dry, resulting in a decrease in production efficiency, which is not a good idea from a cost standpoint. In particular, 150-200
g/m is the most preferred coating weight.

Next, the coating layer is preliminarily dried. The dryer used at this time may be a known device, such as an infrared heater set, a hot air circulation type, a cylinder roll type, or the like.

In addition, in order to prevent the formation of a dry film on the surface of the microcapsule-containing emulsion coating layer, the coating surface is heated rapidly from above.

It is preferable to avoid drying and dry from the back side of the coated surface. The drying temperature is a temperature at which the blowing agent does not substantially foam, specifically a temperature at which the expansion ratio is 2 times or less, more preferably 1.5 times or less, and a film is formed only on the coated surface. It is appropriate to set the temperature at such a temperature that the evaporation of internal moisture is not inhibited.

After thoroughly drying the coating layer by the above pre-drying,
Using a known embossing device, the coating layer (microcapsule-containing resin layer) is partially heated and foamed. In the conventional embossing method, the resin layer is partially submerged by the convex part of the embossing roll, and the part of the resin layer corresponding to the concave part maintains its initial state to form an uneven pattern. A major feature of this method is that only the convex portions of the coating surface are brought into contact with the coated surface under pressure in a heated state, and only the contact portions are foamed and raised to form an uneven pattern.This is a major feature. In this case, in the present invention, since thermally expandable microcapsules with high extreme temperature properties are used as the blowing agent, a high expansion ratio can be given with short heating during embossing, and furthermore, thermally expandable microcapsules In the case of foaming, a large number of fine closed cells are formed in the foamed area, resulting in a finely uneven surface, resulting in a matte foamed area and a significant difference in gloss (contrast) between the foamed area and the glossy unfoamed area. , the effect of forming a concavo-convex pattern that is visually extremely rich in three-dimensionality can be obtained. This effect is a special effect obtained because the present invention brings only the convex portions of the embossing roll into contact to partially foam and bulge the resin layer.

In the above-mentioned embossing device, it is preferable to use a rubber roller, which has more elasticity than a hard paper tube, as the receiver roller, because this enables embossing evenly over the entire processed surface and forming a uniform pattern. The heating conditions for embossing are 10 to 50°C, preferably 20 to 40°C, higher than the foaming temperature of the thermally expandable microcapsules as the foaming agent.
C is preferably selected from a high temperature range of 100 to 160°C. That is, below the above-mentioned temperature, the foaming agent cannot absorb a sufficient amount of heat, the foaming ratio decreases, and no three-dimensional effect is produced. This is because if the temperature exceeds 160°C, the resin will seize on the embossing roll and contaminate the foaming surface. The contact pressure of the embossing roll is 15kg/co! The following are preferred. Applying more pressure than this will inhibit foaming after pressure contact is released,
This is because there is a risk that the coating layer in the pressurized contact area will be crushed and the base material will be exposed. The lower limit of the contact pressure is not particularly limited. However, when a pressure of about 4 kg/cnl or more is applied, the resin is pushed away and deposited on the periphery of the pressurized contact area, forming a convex part, so that after foaming, the contour of the convex part becomes particularly swollen and convex. Since the upper surface of the part has a concave shape, the boundary between the convex part and other parts becomes clear, and a sharp concave-convex pattern can be obtained. Therefore, it is desirable to set the contact pressure to 4 kg/ct or more.

Further, the embossing speed is preferably 3 to 20 m/min. This is because if the heating rate is less than 3 m/min, the amount of heat applied is too large, crushing the coating film and exposing the base material, and if it is more than 20 m/min, the amount of heat being applied is insufficient and the expansion ratio decreases.

In this way, a patterned sheet-like composite material having an uneven pattern with a difference in gloss between the concave portions and convex portions, a strong contrast, and a rich three-dimensional effect is obtained.

〔Effect of the invention〕

As described above, according to the present invention, only the heating convex portion of a heating device such as an embossing roll is brought into contact with the surface of the microcapsule-containing resin layer, and only the contact portion is foamed and raised to form an uneven pattern. The layers can be made thinner than before. The resulting patterned composite material has a matte appearance, with the convex foamed portions being formed by fine closed cells of thermally expandable microcapsules, and the other portions (which have a gloss). The contrast is strong due to the difference in gloss, and the uneven pattern has a rich three-dimensional effect. Moreover, since the uneven pattern is not created by printing as in the past, even minute patterns will not fall off.

Since the patterned sheet-like composite material of the present invention has the above-mentioned excellent properties, it is extremely useful as an uneven patterned artificial leather, and can also be used as a slip stopper for stairs.

Next, examples will be described.

[Example 1] First, each raw material was blended as shown in Table 1, and this was stirred for 10 minutes using a homomixer to prepare five types of emulsions containing thermally expandable microcapsules from B to F. Note that A is a control example. Next, the above microcapsule-containing emulsion was adjusted to a concentration of 40% and a viscosity of 3000 cps, and coated on a base material (nylon oxford) at a coating weight of 170 g/m (wet), and dried in a hot air dryer. for 10 minutes at 80°C, and further 1)0
It was pre-dried for 1 minute at ℃ and subjected to a foaming test. A hot embossing roller is used for foaming, and the roller heating temperature is 150℃.
°C, and the roller pressure was 5 kg/cta. The results are shown in Table 2.

(Leaving space below)
F has a good performance, and it can be seen that the uneven pattern has a rich three-dimensional effect. On the other hand, in the control product A, no pattern appeared. However, F had a large amount of microcapsules, and a decrease in surface strength was observed.

[Example 2] Each raw material was blended as shown in Table 3 and stirred for 10 minutes using a homomixer to prepare an emulsion containing thermally expandable microcapsules. Next, the above microcapsule-containing emulsion was prepared with a concentration of 25% and a viscosity of 3000 cps.
It was adjusted to the following and applied to the base material (nylon oxford). At this time, change the coating amount from 50g/m to 250g/ry?
It was changed to 5 stages. Next, each of these was dried in the same manner as in Example 1, and then a foaming test was conducted. The results are shown in Table 4.

(Margin below) Beating margin) From the results in Table 4, is the coating amount 50g/rr? It can be seen that the three-dimensional effect of the uneven pattern becomes a little low, but if it is 100 g/n or more, an uneven pattern with a full three-dimensional effect can be obtained.

However, when the coating amount is 250 g/rr (250 g/rr), it takes a long time to dry, resulting in a decrease in production efficiency and an increase in cost.

[Example 3] Each raw material was blended as shown in Table 5, and this was coated on a base material (nylon oxford) at a rate of 150 g/m and dried at 80° C. for 6 minutes using a hot air dryer. Next, using a hot embossing roller, foaming was performed at a roller heating temperature of 120° C. and a roller pressure of 2 kg/cnl to obtain a sheet with an uneven pattern.

On the other hand, the formulation shown in Table 5 above was applied to the entire surface of the substrate (150
g/m) L hot air dryer at 80°C for 6 minutes, then heated at 150°C for 3 minutes to heat and foam the entire surface of the coating layer (resin N), and then with an embossing roll. The foamed resin layer was partially immersed under pressure at 2 kg/crA to form an uneven pattern, which was used as a comparative example.

The foamability and three-dimensional effect of the two types of uneven patterned sheets obtained as described above were investigated and shown in Table 6.

Table 6 From Table 6, it can be seen that in the actual height measurement, there is a difference in gloss between the convex and concave parts of the uneven pattern, and a strong contrast appears, giving the uneven pattern a rich three-dimensional effect.However, in the comparative height measurement, the uneven pattern It can be seen that there is no difference in the gloss between the convex and concave areas, and the three-dimensional effect is lacking.

Claims (2)

[Claims] (1) A sheet-like base material, and a thermally expandable microcapsule-containing resin layer formed on at least one of the front and back surfaces of the sheet-like base material, wherein the resin layer partially expands due to thermal expansion of the thermally expandable microcapsules. It's exciting,
A patterned sheet-like composite material characterized in that a pattern is formed by the raised portions. (2) A heating device equipped with a sheet-like base material having a thermally expandable microcapsule-containing resin layer formed on at least one of the front and back surfaces, and a heating element having a convex pattern formed on the heating surface. The heat-expandable microcapsules contained in the resin layer at the contact portion are prepared by contacting the convex pattern of the heating body of this heating device with the surface of the resin layer of the sheet-like base material in a heated state. A method for manufacturing a patterned sheet-like composite material, which is characterized by expanding and forming a raised convex pattern.