JPS62211132A - Composite sheet material with pattern and manufacture thereof - Google Patents

Abstract

PURPOSE:To obtain a composite sheet with pattern, rich in three-dimensional feeling and provided with heat resistant property, by a method wherein a resin layer is inflated locally by the thermal expansion of thermal expansive micro-capsules and is reinforced by the crosslinking of a crosslinking agent. CONSTITUTION:A resin layer, formed on the surface of a sheet type base material, contains thermal expansive micro-capsules and a crosslinking agent, which become recessed and projecting pattern forming layer, and is formed by coating the liquid of resin, such as high molecular emulsion, solution or the like, on the base material and drying it. The principal constituent of said resin solution or a high molecular substance is a heat softening resin, softened upon heating the resin layer and not precluding the expansion of the thermal expansive micro-capsule, further, contains crosslinking functional group in the molecule thereof and is softened to a degree that it can resist against the expansion of the thermal expansive micro-capsule after crosslinked by crosslinking agent. Any crosslinking agent capable of crosslinking the crosslinking high molecular substance forming the resin layer may be employed as the crosslinking agent, however, epoxy series crosslinking agent is excellent in compatibility with various high molecular substances, therefore, the regulation of crosslinking reaction may be facilitated.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a sheet-like composite material having a three-dimensional pattern of projections and depressions formed on the 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 demand has been growing in recent years as a material with a texture and three-dimensional feel that cannot be obtained with simple cloth, film, etc. ing. 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 applied to this resin layer to give an uneven pattern. Method: ■ After forming a resin layer containing a foaming material on the entire surface of the base material, foaming the resin layer over the entire surface and embossing the foamed resin layer to give an uneven pattern; ■ Adding a foaming agent to 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 in the method of embossing the foamed resin layer described in (■) above, the foaming 1
Since the resin layer is partially immersed by embossing to form a concavo-convex pattern, it is still necessary to apply a thick resin layer, which poses an economical problem. Moreover, the formed uneven pattern inevitably suffers from insufficient contrast, as in the case (2) above. 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.

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, improvements are strongly desired.

Therefore, in order to solve the above problems, the present inventors conducted a series of studies to improve the method (2) above, and as a result, the present inventors created a pattern-forming convex pattern on the surface of the heat-expandable microcapsule-containing resin layer using an embossing roll. When the parts are brought into contact in a heated state and the resin layer part of the contact part is foamed and raised in the opposite way to the above method I discovered what I could do and already filed a patent application (July 16, 1985).

Patent application Sho 6O-457526). That is, the patterned sheet-like composite material produced by this method is one in which the heat-expandable microcapsule-containing resin layer is partially foamed and raised to form an uneven pattern, as described above. It is formed by fine closed cells of heat-expandable microcapsules and has a matte appearance, creating a difference in gloss from other parts (which have gloss), creating a strong contrast, and the uneven pattern gives a three-dimensional effect. It is an excellent product that is rich in Moreover, since the uneven pattern is formed by the bumps of the resin layer and is not provided by printing as in the past, even minute patterns will not fall off.

[Problems that the invention attempts to solve]

As described above, the patterned sheet-like composite material of the above proposed method has excellent properties, but since the resin layer containing thermally expandable microcapsules is formed of a thermosoftening resin, it is difficult to embossing the uneven pattern. After forming, if it is exposed for a long time near a heating element like a stove, the unfoamed parts (shiny depressions) will foam and lose their luster, and at the same time the contrast of the gloss of the unevenness will decrease and the three-dimensional effect of the uneven pattern will be lost. There is a risk of being exposed. Furthermore, care must be taken when ironing the patterned sheet-like composite material when sewing it into a bag or the like, as it is necessary to keep the heating temperature relatively low to prevent foaming in the unfoamed portions.

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 object of the present invention is to provide a patterned sheet-like composite material that is firmly adhered to the skin and has heat resistance such that the above-mentioned uneven pattern-forming resin layer is not affected by subsequent heating after embossing, and a method for producing the same. do.

[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, wherein the resin layer is thermally expandable. A patterned sheet-like composite material that is partially raised due to thermal expansion of the microcapsules and strengthened by crosslinking with a crosslinking agent contained therein, and in which a three-dimensional pattern is formed by the raised portions.
A sheet-like base material having a resin layer containing a crosslinking agent and heat-expandable microcapsules formed on at least one of the front and back surfaces is prepared, and a heating method is performed in which a convex pattern is formed on the heated surface. By preparing a heating device equipped with a heating body and bringing the convex pattern of the heating body of this heating device into contact with the surface of the resin layer of the sheet-like base material in a heated state, the resin layer at the contact portion is heated. A second method for producing a patterned sheet-like composite material in which the heat-expandable microcapsules are expanded to form a raised convex pattern, and a crosslinking reaction between the resin and a crosslinking agent is progressed at least in a subsequent step.
This is the gist of the report.

That is, the present inventors (1) do not fundamentally change the manufacturing method of the patterned sheet-like composite material according to the previous proposal;
2) maintains the excellent three-dimensional appearance of the patterned sheet-like composite material proposed above; and (3) does not reduce basic performance such as adhesion between the base material and the resin layer of the sheet-like composite material. While keeping these three points in mind, we researched ways to improve the heat resistance of the patterned resin layer of the patterned sheet-like composite material proposed above.

As a result, if a crosslinking agent is mixed in advance with the resin liquid that forms the resin layer, and a resin layer with an uneven pattern is formed through a series of steps of coating the resin liquid on the base material, drying, and embossing, the crosslinking The resin layer is strengthened by the crosslinked structure created by the agent, and even if the unfoamed portions of the recesses are further heated after embossing, expansion due to foaming is suppressed, and the sense of subjectivity of the uneven pattern and the gloss of the resin layer are not impaired. They discovered this and arrived at the present invention.

The patterned sheet-like composite material of the present invention is prepared by preparing a sheet-like base material in which a resin layer containing heat-expandable microcapsules (foamed microcapsules) and a crosslinking agent is formed on the sheet surface,
It can be obtained by bringing the convex pattern of a heating body of a heating device into contact with the resin layer of the sheet-like base material 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.

Synthetic fibers such as nylon, polyester, and rayon, and inorganic fibers such as glass fiber and carbon fiber, singly or in combination.
Examples include non-woven fabrics made by blending or interweaving two or more types, and two-woven fabrics. In addition to these, plastic films made of nylon, polyester, etc. may also be used. These base materials may be coated with a filler coating agent in advance, prior to the formation of the resin layer described below. When forming a resin layer by coating a resin liquid, etc., if the texture of 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 filler coating agent is applied as needed. As a filler coating agent, anything can be used as long as it has good adhesion to the base material and the above resin liquid and can be coated with a general coating machine, but it is generally used for the above resin liquid. An emulsion or aqueous solution (thickened with a thickener if necessary) of the same kind of polymer as that used is used.

The resin layer formed on the sheet surface of the above-mentioned sheet-like base material contains heat-expandable microcapsules and a crosslinking agent to form an uneven pattern formation layer, and is made of a resin liquid such as an emulsion or solution of a polymer. It is formed by coating (brushing, spraying, etc.) on the above substrate and drying. The polymer that is the main component of the resin liquid is a thermoplastic resin that softens when the resin layer is heated by a heating device and does not inhibit the expansion of the thermally expandable microcapsules, and also has a crosslinkable functional group in its molecules. However, after being crosslinked with the crosslinking agent described below, it must be hardened to the extent that it can resist the expansion of the heat-expandable microcapsules. Examples of such a polymer include a polymer having a carboxyl group as a crosslinkable functional group in the molecule and a polymer having a hydroxyl group in the molecule. The polymers having carboxyl groups in their molecules include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, and itaconic acid, and ethylenically unsaturated monomers such as acrylic esters, methacrylic esters, vinyl acetate, and ethylene. Polymers having hydroxyl groups in the molecule include partially saponified polyvinyl acetate, (meth)
Examples include (meth)acrylic acid ester copolymers containing acrylic acid hydroxyalkyl ester and the like as a copolymerization component. These can be used alone or in combination of two or more. Among these polymers, polyurethane is particularly preferred from the viewpoints of weather resistance, abrasion resistance, texture, and the like.

Note that even a polymer material that does not substantially have a crosslinkable functional group as described above in its molecule can be partially used by blending it with the crosslinkable polymer material.

These resins are usually used in the form of an emulsion.

Among these emulsions, polyurethane emulsions have a 100% modulus of 70 kg/cj or less, more preferably 5 Q kg/cj as a film physical property before crosslinking.
Cal elongation is 400% or more, more preferably 500~
The one that satisfies 1000% is most preferable.

The crosslinking agent contained in the resin layer may be any crosslinking agent as long as it can crosslink the crosslinkable polymer forming the resin layer. For example, urea-formaldehyde resin, melamine-formaldehyde resin, polyamide-
Those with methylol groups such as formaldehyde resins, those with aldehyde groups such as glyoxal, dialdehyde starch, ketone aldehyde resins (e.g., cyclic urea-glyoxal reaction products, acrylamide-glyoxal reaction products), and glycerin diglycidyl. Examples include those having an epoxy group or a chlorohydrin group, such as ether and polyamide-polyamine-epichlorohydrin resin, and those having an ethyleneimine group, such as polyethyleneimine resin. Further, zirconium ammonium carbonate or zinc sulfate, which are polyvalent metal compounds, may be used. Among these, epoxy-based crosslinking agents are particularly suitable in the present invention because they have good compatibility with various polymers and the crosslinking reaction can be easily controlled.

In addition, in the present invention, a crosslinking accelerator may be used in combination with the above-mentioned crosslinking agent. As the crosslinking accelerator, a known one suitable for the crosslinking agent used is selected. For example, when a water-soluble epoxy resin is used as the crosslinking agent, an amine type crosslinking accelerator such as 2,4°6-dolys(dimethylaminomethyl)phenol is used as the crosslinking accelerator.

The heat-expandable microcapsules distributed and contained in the resin layer together with the crosslinking agent are microspheres formed by enclosing 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, and as the shell softens, the shell expands and forms fine closed cells. This type of blowing agent is a general inorganic blowing agent (foaming temperature 70℃ or less)
Because the foaming temperature is higher than that of , post-processing (ironing)
This may cause the problem of foaming of unfoamed parts during
In addition, it is highly sensitive to temperature and exhibits a high expansion ratio when heated for a short time by heat embossing or the like. 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 they partially foamed the resin layer instead of foaming the entire resin layer, and found that the gloss of the foamed portion and the unfoamed portion were significantly different. General organic blowing agents, like the inorganic blowing agents mentioned above, have the disadvantage of slow foaming speed, and also have a high foaming temperature of 160°C or higher, making it difficult for the coated layer to touch the embossing roll during hot embossing, etc. It cannot be used because it cannot be used because it is baked and cannot produce clean embossing, and it is impossible to avoid gas escape or pinhole formation unless it is coated thickly, and the pores that are generated tend to become coarse continuous pores.

The heat-expandable microcapsules used in the present invention preferably have a foaming temperature of 80 to 160°C, and from the viewpoint of workability in heat embossing as described below.
Further, from the viewpoint of preventing troubles 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 heat-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 a crosslinking agent such as a water-soluble epoxy resin is further blended. Here, the above-mentioned 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 expansion ratio, the blending ratio of the polymer in the emulsion and the heat-expandable microcapsules may be set to 100/20 to 100/100 in terms of solid content. Preferably, it is more preferably 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 unfoamed areas will be clearly visible through the heating and foaming process (the difference is 160 μm or more, and a three-dimensional uneven pattern can be recognized by touch with the finger). ) can be expressed. however,
If the amount of the heat-expandable microcapsules is too small from this blending ratio, the desired expansion ratio cannot be obtained even if the coating amount is increased, and conversely, if the amount of heat-expandable microcapsules is too large, the expansion ratio will be too high and the foaming surface will Non-uniformity increases and strength decreases. Therefore, it is preferable to set the blending ratio within the above range. The amount of the crosslinking agent is 0.1 parts by weight (hereinafter referred to as "parts") per 100 parts by weight of the solid content of the polymer.
It is preferable to set it to ~25 parts, more preferably 0 parts.
．． 5 to 12 parts. Among these, 1 to 5 parts is particularly suitable. That is, if the amount of the crosslinking agent is less than 0.1 part, crosslinking will be insufficient and the effect of restricting foaming in the concave areas due to heating after the formation of the concavo-convex pattern will be weakened. On the other hand, if the amount exceeds 25 parts, the crosslinking agent acts as a plasticizer for the polymer and softens the resin layer, causing the resin layer itself to be crushed by pressure and the base material to be damaged during embossing to create an uneven pattern on the resin layer. There is a risk of exposure.

In addition, if the crosslinking reaction progresses too much due to heating and drying after applying Emulsicon, the resin layer will generally harden and the foaming for forming the uneven pattern will be excessively restricted, and the uneven pattern will lack three-dimensional effect. It is desirable to avoid excessive progress of the crosslinking reaction, as this will result in poor texture.

In the present invention, in addition to the above, the crosslinking accelerator, filler 2 colorant, TA water agent, softener, viscosity modifier, antifoaming agent, anti-aging agent, etc. can be added as necessary. .

The mixture thus obtained is uniformly dispersed by a general method using a stirrer such as a homomixer or a disilver to prepare a polymer emulsion (aqueous solution) containing heat-expandable microcapsules.

Next, a polymer emulsion containing the crosslinking agent and heat-expandable microcapsules 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, etc. . The coating amount at this time varies strictly depending on the base material, weave, fiber thickness, etc., but as a rough guide, 40
It is about 100 to 300 g/rrf for a polymer emulsion containing heat-expandable microcapsules at a concentration of 100 to 300 g/rrf. 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, if the coating amount exceeds 300 g/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, the most preferable coating amount is 150 to 200 g/rrl.

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.

At this time, in order to prevent the formation of a dry film on the surface of the emulsion coating layer containing heat-expandable microcapsules,
It is preferable to avoid rapid heating and drying from above the coated surface, and dry from the back side of the coated surface. The drying temperature is a temperature at which the foaming agent does not substantially foam, specifically a temperature at which the foaming ratio is 2 times or less, more preferably 1.5 times or less,
Moreover, it is appropriate to set the temperature at such a temperature that a film is not formed only on the coated surface and 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 (thermally expandable microcapsule-containing resin layer) is partially heated and foamed. At this time, 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. The first feature of embossing is that only the convex portions of the embossing roll are brought into contact with the coating surface under pressure in a heated state, and only the contact portions are foamed and raised to form an uneven pattern.This is the first feature.

In this case, in the present invention, since heat-expandable microcapsules with high temperature sensitivity are used as the foaming agent, a high foaming ratio can be given by short-time heating during embossing. In this case, a large number of fine closed cells are formed in the foamed part, resulting in a finely uneven surface, resulting in a matte foamed part and a significant difference in gloss (contrast) between it and the unfoamed part, which has a glossy appearance. Therefore, the effect of forming a concavo-convex pattern with an extremely three-dimensional effect 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 apparatus, it is preferable to use a rubber roller, which is more elastic than a hard paper tube, as the receiver roller, since this enables the embossing to be carried out evenly over the entire processed surface and a uniform pattern can be formed. The heating conditions for embossing are 10 to 50°C, preferably 20 to 40°C, higher than the foaming temperature of the heat-expandable microcapsules as the foaming agent.
It is preferable to select a high temperature within the 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 preferably 15 kg/- or less. This is because if the pressure is applied more than this, foaming after the pressurized contact is released may be inhibited, and the coating layer in the pressurized contact area may be crushed and the base material may be exposed. The lower limit of the contact pressure is not particularly limited. However, when a pressure of about 4 kg/- or more is applied, the resin is pushed away and deposited on the periphery of the pressurized contact area, forming a convex part. Since the top surface has a concave shape,
The boundary between the convex part and the other parts becomes clear, and a sharp uneven pattern can be obtained. Therefore, the applied contact pressure is 4 kg/cn! It is desirable to set it to a value higher than that.

Further, the embossing speed is preferably 3 to 20 m/min. This is because if the amount of heat applied 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 the amount of heat applied is more than 20 m/min, the amount of heat applied is insufficient and the expansion ratio decreases.

Furthermore, in the present invention, the resin layer (coating layer) contains a crosslinking agent, and the crosslinking reaction proceeds even at room temperature, allowing the resin to harden over time. Therefore, if the period from the formation of the resin layer to the heating and foaming treatment (for example, embossing) is too long, crosslinking will progress and the hardness of the resin layer will increase, which may limit foaming during heating and foaming, resulting in insufficient foaming. Generally, it is preferable to carry out the heat foaming treatment within one week after forming the resin layer. However, if the crosslinking reaction progresses and foaming is insufficient as described above, the foaming ratio can be adjusted to an appropriate foaming ratio by increasing the heating temperature during the heat foaming treatment or by increasing the contact pressure of the heating element. can be obtained.

In addition, when drying is insufficient and crosslinking has not progressed very much, or because the amount of crosslinking agent is too large and the plasticizing effect of the crosslinking agent is superior to the crosslinking effect, contact with the heating element during heat foaming treatment may occur. If the resin layer collapses and the base material is exposed, the appropriate crosslinked state can be adjusted by drying the resin layer again or adding a crosslinking accelerator.

Furthermore, during the manufacturing process of the patterned sheet-like composite material of the present invention,
Regarding crosslinking of the resin layer, the crosslinking reaction normally proceeds through the resin layer drying process, heat foaming treatment process, and subsequent storage to obtain a sufficient crosslinked state, so there is no need to perform heat treatment for crosslinking in particular. However, in some cases 80~
Heat treatment may be performed at 100° C. and 0° for about 1 to 2 hours.

The patterned sheet-like composite material thus obtained has an uneven pattern formed by convex portions where the resin layer is foamed and matte and concave portions where the resin layer is unfoamed and glossy. . Since the inside of the resin layer that forms this uneven pattern is moderately hardened by crosslinking with a crosslinking agent,
If this patterned sheet-like composite material is subjected to some kind of heating at a stage after manufacturing, the unfoamed concave portions will not expand even if they try to foam and expand due to heating, and the glossy contrast and three-dimensional effect of the uneven pattern will be impaired. There is no. This is the second feature of the present invention.

〔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 thermally expandable microcapsule-containing resin layer, and only the contact portion is foamed and raised to form an uneven pattern. The resin layer can be made thinner than before. In the patterned composite material obtained, the convex foamed portions are formed by fine closed cells of heat-expandable microcapsules and have a matte appearance, and the other portions (
Because there is a difference in gloss and a strong contrast (appears), the uneven pattern is simply placed on the plate with the height of the uneven surface, creating a three-dimensional effect.Moreover, the uneven pattern is Since it is composed of the resin layer itself and is not provided by printing as in the past, even minute patterns will not fall off.Furthermore, the uneven pattern formation of the patterned sheet-like composite material of the present invention The resin layer is cross-linked with a cross-linking agent, so it may not be heated by an iron when it is sewn into products such as bags using this patterned sheet-like composite material, or heated when it is used as a product (near a heating element such as a stove). The three-dimensional effect of the uneven pattern and the gloss of the concave portions do not disappear or decrease due to the heat applied to the patterned sheet-like composite material proposed earlier. In addition, when manufacturing such a patterned sheet-like composite material, it is not necessary to make any changes to the manufacturing method proposed earlier, which eliminates the need to increase production costs. It also has the advantage of being able to supply high-value-added products without the need for additional costs.

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.

[Examples 1 to 4. Comparative Example 1] First, each raw material was blended as shown in Table 1, and this was stirred for 10 minutes using a homomixer to produce four types of emulsions containing heat-expandable microcapsules and a crosslinking agent. Note that a sample containing no crosslinking agent was used as a control example. Next, add the above emulsion to a concentration of 40% and a viscosity of 3000 cps.
The coating amount was adjusted to 200g/rd (ivet) on a base material (nylon oxford), and this was pre-dried in a hot air dryer at 80°C for 10 minutes and then at 100°C for 2 minutes. Afterwards, it was foamed. A hot embossing roller is used for foaming, and the roller heating temperature is 150℃.
°C, and the roller pressure was 6 kg/cri.

(Hereinafter, blank spaces) The five types of patterned sheet-like composite materials thus obtained were left at room temperature for one week, and then their heat resistance was evaluated using the following procedure. That is, the patterned sheet-like composite material was reheated in a hot air dryer (90°C x 5 hours, 1
00°C x 2hr, 110°C x 2m1n) Afterwards, a sensory evaluation was given for the three-dimensional window with the uneven pattern on the surface of each composite material. The sensory evaluation was based on visual observation (difference in gloss between concave and convex parts) and touch (difference in unevenness) by 10 panelists.

The results are shown in Table 2.

○: Present, Δ: Slightly present, ×: None From the above results, it can be seen that the uneven pattern of the patterned sheet-like composite material of the present invention is not damaged by heat and has extremely excellent heat resistance. Therefore, it is clear that the patterned sheet-like composite material of the present invention exhibits excellent resistance to ironing during sewing into products such as bags and accidental heating during use.

[Examples 5-8. Comparative Example 2] Each raw material was blended as shown in Table 3, and five types of patterned sheet-like composite materials were obtained in the same manner as in Example 1.

Note that a sample containing no crosslinking agent was used as a comparative example.

(Hereinafter referred to as blank space) Regarding the obtained patterned sheet-like composite material, heat resistance was evaluated in the same manner as in Example 1.

The results are shown in Table 4.

[Examples 9-12. Comparative Example 3] Each raw material was blended as shown in Table 5, and five types of emulsions were obtained in the same manner as in Example 1. Note that a sample containing no crosslinking agent was used as a comparative example. The above emulsion was applied to a substrate in the same manner as in Example 1, pre-dried, and then left at room temperature for one week. Then, just before embossing, 100℃
After heat treatment for 5 ml, embossing was performed in the same manner as in Example 1.

(Hereinafter referred to as blank space) Regarding the obtained patterned sheet-like composite material, heat resistance was evaluated in the same manner as in Example 1.

The results are shown in Table 6.

Claims (2)

[Claims] (1) A sheet-like base material, and a heat-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 is partially bulged due to thermal expansion of the heat-expandable microcapsules. A patterned sheet-like composite material, characterized in that it is raised and strengthened by crosslinking with a crosslinking agent contained therein, and that a three-dimensional pattern is formed by the raised portions. (2) A heating element is prepared in which a resin layer containing a crosslinking agent and heat-expandable microcapsules is formed on at least one of the front and back surfaces, and a convex pattern is formed on the heating surface. Prepare a heating device equipped with
By bringing the convex pattern of the heating body of this heating device into contact with the surface of the resin layer of the sheet-like base material in a heated state, the thermally expandable microcapsules contained in the resin layer at the contact portion are expanded. Forms a raised convex pattern,
A method for producing a patterned sheet-like composite material, characterized by allowing a crosslinking reaction between a resin and a crosslinking agent to proceed at least in subsequent steps.