JPH0624832B2 - Patterned sheet composite material and method for producing the same - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a sheet-shaped composite material in which a three-dimensional pattern of depressions and projections is formed on the sheet surface, and a method for producing the same.

[Conventional technology]

A sheet-shaped composite material having an uneven pattern on the surface has a texture such as leather with an uneven pattern, and demand has grown in recent years as a material with a texture and three-dimensional effect that cannot be obtained with simple cloth or film. ing. The conventional method for producing such a sheet-shaped composite material with a pattern is to form a resin layer of vinyl chloride resin, urethane resin or the like on the entire surface of the base material, and then emboss this resin layer to give an uneven pattern. A method of forming a foam-containing resin layer on the entire surface of the base material, then foaming the resin layer over the entire surface, and embossing the foamed resin layer to give an uneven pattern,
After printing the foaming agent-containing resin coating liquid on the base material surface in a desired pattern and predrying it to form a resin coating film in a pattern,
There are three methods: foaming the resin coating film to give an uneven pattern.

However, in the method of embossing the resin layer described above, since the uneven pattern is formed by embossing the resin layer and partially immersing the resin layer, the resin layer is thickly coated to some extent to give a three-dimensional effect. Must be,
There is a problem in terms of economy. Further, the embossing method has a drawback in that the uneven surface has the same gloss, the uneven surface has a low contrast, and the uneven pattern has a visually poor three-dimensional effect. Further, even in the method of embossing the foamed resin layer, the foamed resin layer is partially immersed by embossing to form a concavo-convex pattern, so it is necessary to thickly coat the resin layer as well, in terms of economy. There's a problem. Moreover, similarly to the above, insufficient contrast of the formed uneven pattern is inevitable. further,
In the print foaming method, it is unavoidable that the coating liquid flows around during printing of the foaming agent-containing resin coating liquid, and it is difficult to form a sharp uneven pattern at the foamed end. ) And the resin coating film are not sufficiently adhered, it is not suitable for forming a fine pattern because the fine pattern part tends to fall off, or the pattern switching is very troublesome. However, there are drawbacks such as a problem in productivity.

As described above, the conventional method not only has an economical problem, but also has a problem that the obtained uneven pattern has a weak contrast and becomes poor in three-dimensional effect, and it is difficult to form a fine pattern. In such a situation in which the demand for this type of composite material is significantly increasing, improvement thereof is strongly demanded.

Therefore, as a result of repeating a series of studies on the improvement of the above method in order to solve the above problems, the present inventors have found that the embossing roll pattern-forming projections are formed on the surface of the heat-expandable microcapsule-containing resin layer. When the resin layer portion of the contact portion is heated and the resin layer portion of the contact portion is foamed and raised in the opposite manner to the above method, a difference in gloss between the concave portion and the convex portion is generated, and a strong contrast and a sharp uneven pattern are obtained. After discovering this, a patent application has already been filed (July 16, 1985, Japanese Patent Application No. 60-157526). That is, as described above, the patterned sheet-shaped composite material by this method is one in which the heat-expandable microcapsule-containing resin layer is partially foamed and raised to form an uneven pattern. Is formed by fine closed cells of heat-expandable microcapsules and has a matte appearance, which causes a difference in gloss from other parts (having a gloss) and a strong contrast, resulting in a three-dimensional appearance of uneven patterns. It is rich and excellent. Moreover, since the uneven pattern is formed by the protrusion of the resin layer and is not provided by print printing as in the conventional case, even a fine pattern does not fall off.

[Problems to be solved by the invention]

As described above, the patterned sheet-shaped composite material of the above-mentioned method has excellent characteristics, but since the heat-expandable microcapsule-containing resin layer is formed of the heat-softening resin, it is embossed to form an uneven pattern. If it is exposed to the vicinity of a heating element such as a stove for a long time after being formed, the unfoamed part (glossy concave part) foams and loses gloss, and at the same time the contrast of the uneven gloss decreases and the three-dimensional effect of the uneven pattern is impaired. There is a risk that In addition, even when ironing when the patterned sheet-shaped composite material is sewn to finish into a bag or the like, it is necessary to keep the heating temperature at a relatively low temperature in order to prevent foaming of the unfoamed portion, and caution is required.

The present invention has been made in view of such circumstances, the contrast between the concave portion and the convex portion strongly appears due to the difference in gloss, and the uneven pattern is rich in three-dimensional effect, and the pattern is relative to the substrate. An object of the present invention is to provide a patterned sheet-shaped composite material which is firmly adhered and has heat resistance such that the above-mentioned uneven pattern forming resin layer is not changed by subsequent heating after embossing, and a method for producing the same. And

[Means for solving problems]

In order to achieve the above object, the present invention comprises a sheet-shaped base material and a heat-expandable microcapsule-containing resin layer formed on at least one of the front surface and the back surface of the sheet-shaped base material, wherein the resin layer has a thermal expansion property. The heat-expandable microcapsules are partially bulged by thermal expansion to form bulges having a foaming ratio of 5 times or more and are reinforced by cross-linking by a contained cross-linking agent. The surface of the unexpanded portion of the resin layer maintains a glossy surface, while the independent fine bubbles generated by thermal expansion make it a matte surface, and the three-dimensional pattern is formed by the above-mentioned matte-like raised portion and glossy unfoamed portion. The formed sheet-shaped composite material is defined as a first gist, and a resin layer containing a crosslinking agent and heat-expandable microcapsules is provided on at least one of the front surface and the back surface. A sheet-shaped base material is prepared, in which the compounding ratio of the polymer forming the resin layer and the heat-expandable microcapsule is set to 100/20 to 100/100 in terms of solid content, and the convex pattern is formed. Prepare a heating device with a heating element that is formed on the heating surface,
The convex pattern of the heating element of this heating device is applied to the surface of the resin layer of the sheet-shaped substrate in a heated state, and the weight is 15 kg.
/ Cm ² or less by applying a contact pressure while passing through to expand the heat-expandable microcapsules contained in the resin layer of the contact portion to form a raised convex pattern so that the expansion ratio becomes 5 times or more, A second gist is a method for producing a patterned sheet-shaped composite material in which a crosslinking reaction between a resin and a crosslinking agent proceeds at least in the subsequent steps.

[Action]

That is, the present inventors, (1) do not basically change the manufacturing method of the patterned sheet-shaped composite material according to the previous proposal, (2)
It is possible to maintain the excellent three-dimensional effect of the patterned sheet-shaped composite material according to the previous proposal, and (3) not to lower the basic performance such as the adhesion between the base material and the resin layer of the sheet-shaped composite material. While paying attention to three points, an improvement in heat resistance of the uneven pattern forming resin layer of the patterned sheet-like composite material according to the above proposal was studied. As a result, when a cross-linking agent was previously mixed in the resin liquid forming the resin layer, and the uneven resin pattern-forming resin layer was formed through a series of steps of coating the resin liquid on the substrate, drying, and embossing, The resin layer is reinforced by the cross-linking structure by the agent, the expansion due to foaming is suppressed even if the unfoamed portion of the concave portion is further heated after embossing, the three-dimensional effect of the uneven pattern and the gloss of the unfoamed portion of the resin layer are suppressed. The present invention has been reached by finding that it is not damaged.

Next, the present invention will be described in detail.

The patterned sheet-shaped composite material of the present invention prepares a sheet-shaped base material on which a resin layer containing a heat-expandable microcapsule (foaming microcapsule) and a crosslinking agent is formed on the sheet surface,
It can be obtained by bringing the convex pattern of the heating element of the heating device into contact with the resin layer of the sheet-shaped substrate in a heated state.

Examples of the sheet-shaped substrate used in the present invention include natural fibers such as cotton, wool and hemp, synthetic fibers such as acrylic, nylon, polyester and rayon, and inorganic fibers such as glass fiber and carbon fiber, or two kinds thereof. Examples include non-woven fabrics, woven fabrics, and knitted fabrics made by mixing and weaving the above. In addition to these, plastic films made of nylon, polyester, etc. are also available. A sealing coating agent may be previously applied to these base materials prior to the formation of the resin layer described later. When the resin layer is formed by coating the resin liquid, etc., if the base material has a rough mesh, the resin liquid penetrates into the base material and impairs the flexibility of the base material itself, or a large amount of resin liquid is required. Therefore, a sealing coating agent is applied as necessary. As the sealing coating agent, any material may be used as long as it has good adhesiveness to the substrate and adhesiveness to the above resin liquid and can be applied by a general coating machine, but generally used for the above resin liquid. An emulsion or an aqueous solution of a polymer of the same type as that described above (which is thickened by a thickener if necessary) is used.

The resin layer formed on the sheet surface of the above-mentioned sheet-shaped substrate is a concave-convex pattern-forming layer containing a heat-expandable microcapsule and a cross-linking agent. Is applied to the above-mentioned base material (brush coating, spray spraying, etc.) and dried. The polymer, which is the main component of the resin liquid, is a thermosoftening resin that softens when the heating device heats the resin layer and does not hinder the expansion of the heat-expandable microcapsules, and has a crosslinkable functional group in the molecule. However, after being cross-linked with the cross-linking agent described below, it must be hardened to the extent that it can withstand 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. Examples of the polymer having a carboxyl group in the molecule include unsaturated carboxylic acids such as acrylic acid, methacrylic acid and itaconic acid, and ethylenically unsaturated monomers such as acrylic acid ester, methacrylic acid ester, vinyl acetate and ethylene. Examples of the polymer having a hydroxyl group in the molecule include a partially saponified product of polyvinyl acetate, a hydroxyalkyl ester of acrylic acid and a hydroxyalkyl ester of methacrylic acid as a copolymerization component. Examples thereof include acrylic acid ester-based copolymers and methacrylic acid ester-based copolymers. These may be used alone or in combination of two or more. In particular, among these polymer materials, from the viewpoint of weather resistance, wear resistance, feeling, etc.,
Polyurethane is preferred.

Even a polymer having substantially no such crosslinkable functional group in its molecule can be partially used by blending with the above crosslinkable polymer.

Usually, these resins are emulsified and used.
Among these emulsions, a polyurethane emulsion having a 100% modulus of 70 kg / cm ² or less, more preferably 50 kg / cm ² and an elongation of 400% or more, and more preferably 500 to 1000 as a physical property of a film before crosslinking.
Those satisfying the% are most preferable.

The cross-linking agent contained in the resin layer may be any cross-linking agent capable of cross-linking the cross-linkable polymer forming the resin layer. For example, those having a methylol group such as urea-formaldehyde resin, melamine-formaldehyde resin, polyamide-formaldehyde resin, glyoxal, dialdehyde starch, ketone aldehyde resin (for example, cyclic urea-glyoxal reaction product,
Acrylamide-glyoxal reaction product) having an aldehyde group, glycerin diglycidyl ether, polyamide-polyamine-epichlorohydrin resin having an epoxy group or chlorohydrin group, and polyethyleneimine resin having an ethyleneimine group. I have things that I have. In addition, polyvalent metal compounds such as ammonium zirconium carbonate and zinc sulfate may be used. Of these, the epoxy-based cross-linking agent is particularly preferable in the present invention because it has good compatibility with various polymer substances and can easily control the cross-linking reaction.

In the present invention, a crosslinking accelerator may be used in combination with the above crosslinking agent. As the cross-linking accelerator, known ones suitable for the cross-linking agent used are selected. For example, when a water-soluble epoxy resin is used as the crosslinking agent, an amine-based crosslinking accelerator such as 2,4,6-tris- (dimethylaminomethyl) phenol is used as the crosslinking accelerator.

The heat-expandable microcapsules distributed and contained in the resin layer together with the cross-linking agent are microspheres formed by encapsulating a liquid having a boiling point lower than the softening temperature of the resin forming the shell in the shell of the thermoplastic resin. It is a known foaming agent that boils the low boiling point liquid by heating and naturalizes it, and expands the shell as the shell softens to form fine closed cells. This type of foaming agent is a general inorganic foaming agent (foaming temperature 70 ° C or lower)
Since the foaming temperature is higher than that of, post processing (ironing)
The problem that the unfoamed part foams during
In addition, the temperature sensitivity is sharp and a high expansion ratio is exhibited by heating for a short time by hot embossing or the like. In addition, the above foaming agent creates a large number of fine closed cells during foaming to make the surface of the foamed portion matte, so that a remarkable difference in gloss (contrast) occurs between the foamed portion and the unfoamed portion where the gloss is maintained. This phenomenon is made to appear three-dimensionally, and this phenomenon was found by the present inventor to find out that the resin layer is partially foamed rather than foamed, and the gloss of the foamed portion and the unfoamed portion is significantly different. It is a thing. In addition, the general organic foaming agent has a drawback that the foaming speed is slow like the above-mentioned inorganic foaming agent, and the foaming temperature is 160 ° C. or higher and the coating layer is embossed during hot embossing. It cannot be used because it will not be burned in to give a clean embossing, and if it is not thickly coated, the escape of gas or the generation of pinholes cannot be avoided, and the generated pores 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 of heat embossing as described below,
Further, from the viewpoint of preventing troubles in the post-processing, the foaming temperature of 100 to 140 ° C. is more preferable.

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

First, the above heat-expandable microcapsules are mixed with an emulsion of a film-forming polymer such as polyurethane emulsion or an aqueous solution so as to have a predetermined expansion ratio, and a crosslinking agent such as an aqueous solution epoxy resin is further mixed therein. Here, the expansion ratio is Can be represented by. In this case, the blending ratio of the polymer in the emulsion and the heat-expandable microcapsule may be set to 100/20 to 100/100 in terms of solid content so that the foamed portion of the coating film has a predetermined foaming ratio. It is necessary and more preferably 100/40 to 100/80. According to this blending ratio, the expansion ratio becomes 5 times or more, and the difference in height between the foamed portion and the non-foamed portion is clarified by the heat foaming treatment (a difference of 160 μm or more and a three-dimensional uneven pattern is formed by finger touch). Can be recognized). However,
If the amount of the heat-expandable microcapsules is too small compared to this blending ratio, the desired expansion ratio cannot be obtained even if the coating amount is increased. Conversely, if the amount of the heat-expandable microcapsules is too large, the expansion ratio is too high and the foamed surface is Non-uniformity increases and strength also decreases. Therefore, it is necessary to set the compounding ratio within the above range. Further, the amount of the cross-linking agent blended is 0.
It is preferably set to 1 to 25 parts, more preferably
0.5 to 12 parts. Of these, 1 to 5 parts is particularly preferable. That is, if the amount of the cross-linking agent is less than 0.1 part, the cross-linking will be insufficient, and the effect of limiting the foaming of the concave portions due to heating after forming the uneven pattern will be weakened. On the other hand, if the amount exceeds 25 parts, the crosslinking agent acts as a plasticizer for the polymer to soften the resin layer. Therefore, at the time of embossing for forming a concavo-convex pattern on the resin layer, the resin layer itself is crushed by pressure and the base layer is crushed. Material may be exposed.

When the crosslinking reaction proceeds too much by heating and drying after the emulsion coating, the resin layer is generally cured and foaming for forming the uneven pattern is excessively limited, and the uneven pattern has a poor three-dimensional effect. However, it is desirable to avoid excessive progress of the crosslinking reaction.

In the present invention, in addition to the above, the above-mentioned crosslinking accelerator, filler, colorant, water repellent, softening agent, viscosity modifier, defoaming agent, anti-aging agent, etc. can be added as required. .

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

Next, the polymer emulsion containing the cross-linking agent and the heat-expandable microcapsules is applied to the pattern forming surface of the substrate by a known screen method, roll coating method, knife coating method, gravure method, brush coating method, or the like. Work. Strictly speaking, the coating amount at this time varies depending on the base material, the weave, the thickness of the fiber, etc.
The weight of the polymer emulsion containing the heat-expandable microcapsules at a concentration of wt% is about 100 to 300 g / m ² . When the coating amount is less than 100 g / m ² , when the substrate is something other than a film, such as cloth, the coating film becomes thin and the film after foaming also becomes thin, so that a three-dimensional effect is less likely to appear in the uneven pattern.
On the other hand, when the coating amount exceeds 300 g / m ² , it takes a long time to dry and the production efficiency decreases, which is not a good measure in terms of cost. In particular, 150 to 200 g / m ² is the most preferable coating amount.

Next, the coating layer is preliminarily dried. As a dryer used at this time, a known device, for example, an infrared heater type, a hot air circulating type, a cylinder roll type, or the like can be used.
At this time, in order not to form a dry film on the surface of the heat-expandable microcapsule-containing emulsion coating layer,
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 expansion ratio is 2 times or less, more preferably 1.5 times or less, and a film is formed only on the coating surface, It is appropriate to set the temperature so that evaporation of water is not hindered.

After sufficiently drying the coating layer by the above preliminary drying,
The coating layer (heat-expandable microcapsule-containing resin layer) is partially heated and foamed by using a known embossing device. At this time, in the conventional embossing method, the convex portion of the embossing roll partially immerses the resin layer, and the portion of the resin layer corresponding to the concave portion maintains the initial state to form an uneven pattern. In the embossing, only the convex portion of the embossing roll is brought into pressure contact with the coated surface in a heated state, and only the contact portion is foamed and raised to form an uneven pattern, which is the first feature. Then, the embossing roll rotates, and the sheet-shaped composite material with which the convex portion of the embossing roll is brought into pressure contact is sequentially drawn away from the peripheral surface of the embossing roll. In this case, in the present invention, since the heat-expandable microcapsules having high temperature sensitivity are used as the foaming agent, it is possible to give a high expansion ratio of 5 times or more by heating for a short time during embossing. In the case of foaming with heat-expandable microcapsules, many fine closed cells are formed in the foamed part and the surface becomes fine unevenness, so the foamed part becomes matte and there is a significant difference in gloss from the unfoamed part with gloss. (Contrast) is generated, and an effect of visually forming a concavo-convex pattern that is extremely rich in stereoscopic effect can be obtained. This effect is a special effect obtained by the present invention in which only the convex portions of the embossing roll are brought into contact with each other and the resin layer is partially foamed and raised.

In the above embossing device, it is preferable to use a rubber roller, which is more elastic than a rigid paper tube, as the receiving roller, because the entire processed surface can be uniformly embossed and a uniform pattern can be formed. The embossing heating conditions are 10 to 50 ° C., preferably 20 to 40 ° C., from the foaming temperature of the heat-expandable microcapsules as a foaming agent.
It is preferable to select at a high temperature and in the range of 100 to 160 ° C. That is, at a temperature lower than the above temperature, the foaming agent cannot absorb a sufficient amount of heat and the expansion ratio is reduced, so that a three-dimensional effect cannot be obtained. This is because at 160 ° C. or higher, resin sticking to the embossing roll occurs and the foamed surface is contaminated. The pressure contact pressure of the embossing roll must be set to 15 kg / cm ² or less. This is because if more pressure is applied, foaming after releasing the pressure contact may be hindered and the coating layer in the pressure contact portion may be crushed to expose the base material. The lower limit of the pressure contact pressure is not particularly limited. However, when a pressure of about 4 kg / cm ² or more is applied, the resin is pushed away and accumulates on the peripheral edge of the pressure contact portion to form a convex portion, so that the contour of the raised convex portion is particularly raised after foaming. Since the upper surface of the portion has a concave shape, the boundary between the convex portion and the other portions becomes clear, and a sharp uneven pattern can be obtained. Therefore, it is desirable to set the pressure contact pressure to 4 kg / cm ² or more. Also, the embossing speed is 3
-20 m / min is preferable. If it is less than 3 m / min, the amount of heat applied is too large and the coating film is crushed to expose the base material.
This is because at 0 m / min or more, the amount of heat applied is insufficient and the expansion ratio decreases.

Further, in the present invention, a crosslinking agent is contained in the resin layer (coating layer), and the crosslinking reaction can proceed even at room temperature to cure the resin over time. Therefore, if the period from the resin layer formation to the heat-foaming treatment (for example, embossing) is too long, crosslinking proceeds to increase the hardness of the resin layer and the foaming at the time of heat-foaming may be limited and insufficient. Therefore, it is usually preferable to perform the heat-foaming treatment within one week after forming the resin layer. However, when the cross-linking reaction proceeds and the foaming is insufficient as described above, an appropriate foaming ratio can be adjusted by increasing the heating temperature during heating foaming treatment or increasing the contact pressure of the heating body. Can be obtained.

In addition, when the drying is insufficient and the crosslinking does not proceed so much, or because the amount of the crosslinking agent is too large and the plasticizing effect of the crosslinking agent is superior to the crosslinking effect, contact with the heating body during the heat-foaming treatment is performed. When the resin layer is crushed and the base material is exposed, the resin layer can be adjusted to an appropriate crosslinked state by operations such as re-drying the resin layer and adding a crosslinking accelerator.

Furthermore, during the manufacturing process of the patterned sheet-shaped composite material of the present invention,
Regarding the cross-linking of the resin layer, it is not necessary to perform the heat treatment for the cross-linking because the cross-linking reaction usually proceeds through the resin layer drying step, the heat-foaming treatment step and the subsequent storage to obtain a sufficient cross-linked state. However, in some cases 80-
The heat treatment may be performed at 100 ° C. for about 0.1 to 2 hours.

The patterned sheet-shaped composite material thus obtained has unevenness due to the convex portion in which the resin layer is foamed at a foaming ratio of 5 times or more and being matte, and the concave portion in which the resin layer is unfoamed and has gloss. A pattern is formed. And, since the inside of the resin layer forming this uneven pattern is appropriately cured by crosslinking with a crosslinking agent, this patterned sheet-shaped composite material is subjected to some heating at the stage after manufacturing, and the unfoamed recesses are heated. Therefore, it does not expand even if it tries to expand and expand, and the contrast of the gloss of the uneven pattern and the three-dimensional effect are not impaired. This is the second feature of the present invention.

〔The invention's effect〕

As described above, according to the present invention, only the heating convex portion of the heating device such as an embossing roll is brought into contact with the surface of the heat-expandable microcapsule-containing resin layer to pass therethrough to form the uneven pattern by foaming and raising only the contact portion. The resin layer can be made thinner than before. And, the obtained patterned composite material has its convex foaming portion foaming in a free state without any restriction after heating contact, so that it foams at a very high expansion ratio of 5 times or more, and It is formed of fine closed cells of heat-expandable microcapsules and has a matte appearance, and because of the difference in gloss from other parts (having gloss) and strong contrast, the uneven pattern is It is rich in three-dimensionality more than the difference in the height of unevenness. Moreover,
Since the uneven pattern is composed of the resin layer itself and is not provided by print printing as in the past, even a fine pattern will not fall off. Furthermore, the uneven pattern forming resin layer of the patterned sheet-shaped composite material of the present invention,
Since it is cross-linked with a cross-linking agent, this pattern-shaped sheet-shaped composite material is used for ironing at the stage of sewing into products such as bags and the heat received during use as products (placed near heating elements such as stoves). Therefore, the three-dimensional effect of the uneven pattern and the gloss of the concave portion do not disappear or decrease due to the heat applied to the surface. This is the most important feature of the present invention, which makes it possible to significantly improve the practicality of the previously proposed patterned sheet-shaped composite material. When manufacturing such a patterned sheet-shaped composite material, since there is almost no need to change the manufacturing method of the previously proposed one, there is also an advantage that high value-added products can be supplied without increasing the production cost. is there.

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

Next, examples will be described.

[Examples 1 to 4 and Comparative Example 1] First, each raw material was blended as shown in Table 1, stirred for 10 minutes with a homomixer, and emulsions containing four kinds of heat-expandable microcapsules and a crosslinking agent. I made it. In addition, the thing which does not contain a crosslinking agent was made into the control example. Next, the emulsion was added to the emulsion at a concentration of 40% and a viscosity of 3000 cps.
And apply to a base material (nylon oxford) so that the coating amount is 200 g / m ² (wet), and apply this with a hot-air dryer for 10 minutes at 80 ° C and for 2 minutes at 100 ° C. It was pre-dried and then foamed. A hot embossing roller was used for foaming, the roller heating temperature was 150 ° C., and the roller pressure was 6 kg / cm ² . The foaming ratio of each sheet-shaped composite material convex portion thus obtained was determined from the above equation and is also shown in Table 1 below.

The five types of patterned sheet-like composite materials thus obtained were allowed to stand at room temperature for 1 hour, and the heat resistance of each was evaluated by the following procedure. That is, the patterned sheet-shaped composite material was reheated in a hot air dryer (90 ° C. × 5 hr, 10 ° C.).
After 0 ° C. × 2 hr, 110 ° C. × 2 min), a sensory evaluation was given on the three-dimensional effect of the uneven pattern on the surface of each composite material. The sensory evaluation was conducted by visual observation (difference in gloss between concave and convex portions) by 10 panelists and finger touch (difference in concave and convex portions).

The results are shown in Table 2.

From the above results, it can be seen that the uneven pattern of the patterned sheet-shaped composite material of the present invention is not impaired by heat and is extremely excellent in heat resistance. Therefore, it is clear that the patterned sheet-shaped composite material of the present invention exhibits excellent resistance to ironing when sewing products such as bags and accidental heating during use.

[Examples 5 to 8 and Comparative Example 2] The respective raw materials were blended as shown in Table 3, and 5 types of patterned sheet-shaped composite materials were obtained in the same manner as in Example 1. In addition, what did not contain a crosslinking agent was made into the comparative example. Then, the foaming ratio of each sheet-shaped composite material convex portion thus obtained was determined in the same manner, and is also shown in Table 3 below.

The heat resistance and the like of the obtained patterned sheet-shaped composite material were evaluated in the same manner as in Example 1.

The results are shown in Table 4.

[Examples 9 to 12 and Comparative Example 3] Each raw material was blended as shown in Table 5, and 5 kinds of emulsions were obtained in the same manner as in Example 1. In addition, what did not contain a crosslinking agent was made into the comparative example. The emulsion was applied to a substrate in the same manner as in Example 1 and pre-dried, and then left at room temperature for 1 week. And, just before embossing, 100 ℃ ×
After heat treatment for 6 minutes, embossing was performed in the same manner as in Example 1. In addition, the expansion ratio of each convex portion of the sheet material was determined in the same manner as above. The result is the following fifth
It is also shown in the table.

The heat resistance of the obtained patterned sheet-shaped composite material was evaluated in the same manner as in Example 1.

The results are shown in Table 6.

Claims (2)

[Claims] 1. A sheet-shaped base material, and a resin layer containing a heat-expandable microcapsule formed on at least one of a front surface and a back surface of the sheet-shaped base material, wherein the resin layer is partially formed by thermal expansion of the heat-expandable microcapsule. Are formed in a bulge portion having a foaming ratio of 5 times or more and are reinforced by cross-linking by a contained cross-linking agent, and the surface of the bulge portion is a closed fine cell generated by thermal expansion of the heat-expandable microcapsule. The surface of the unfoamed portion of the resin layer maintains a glossy surface, while the matte surface is formed into a matte surface, and a three-dimensional pattern is formed by the above-mentioned matte-shaped raised portion and glossy unexpanded portion. A sheet-shaped composite material with a pattern. 2. A resin layer containing a cross-linking agent and heat-expandable microcapsules is formed on at least one of the front surface and the back surface, and the polymer content of the resin layer and the heat-expandable microcapsules are mixed at a solid content. 100/20 in conversion
A sheet-shaped base material set to 100/100 is prepared, and a heating device including a heating body having a convex pattern formed on the heating surface is prepared, and the convex pattern of the heating body of the heating device is prepared. Heat-expandable microcapsules contained in the resin layer at the contact portion by allowing the resin to pass through the surface of the resin layer in the sheet-like substrate while applying a contact pressure of 15 kg / cm ² or less. Of the patterned sheet-like composite material, comprising forming a raised convex pattern so that the expansion ratio becomes 5 times or more, and proceeding the crosslinking reaction between the resin and the crosslinking agent at least in the subsequent steps. .