JP2003027377A - Flame resistant printing sheet and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a printing sheet comprising a fabric as the base material and a polyurethane resin porous layer on the fabric and having sufficient flame resistance without injuring smoothness of printing. SOLUTION: This flame resistant printing sheet comprises a porous layer giving the printing surface, a base fabric and a resin layer, wherein the resin layer contains a flame proof agent and the porous layer is obtained by coating a resin solution containing polyurethane resin and performing wet coagulation. The method for producing the sheet comprises applying a resin solution containing a flame proof agent on at least one surface of the base fabric by coating method, then, coating a resin solution containing polyurethane resin on at least one surface of the obtained sheet and wetly coagulating to form the porous layer.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a flameproof printing sheet and a method for producing the sheet. In particular, the present invention relates to a printing sheet that can be printed by a printing method such as a thermal transfer method or an inkjet method, and uses a flameproof cloth as a base material, and a method for manufacturing the same.

[0002]

2. Description of the Related Art Heretofore, it has been known to form a porous layer by wet-coagulating a polyurethane resin on a substrate made of fibers. The smoothness of the printed surface is important for use as a printing sheet, but when a cloth is used as the substrate, the smoothness is strongly affected by the unevenness of the cloth, and therefore the thickness of the porous layer is important. However, the polyurethane resin has high flammability, and therefore, the flameproof performance of the printing sheet decreases as the thickness increases. On the other hand, as a means for imparting flameproofness to a fabric, it is well known to apply a flameproofing agent by absorbing dust. However, this method cannot give sufficient flameproofness to the printed sheet for the above reason. Further, a method of adding a flameproofing agent to a polyurethane resin solution to impart flameproofness is known. However, in this method, the flame retardant added causes a change in shape of the porous layer, making it difficult to obtain sufficient smoothness.

[0003]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a printing sheet having a fabric as a base material and having a porous layer of a polyurethane resin on the base material, without sacrificing the smoothness of the printing. It is to provide a printing sheet having flame resistance.

[0004]

As a result of intensive studies by the present inventors, it was found that the above-mentioned problems can be industrially advantageously achieved by the present invention having the following constitution.

1. A flameproof printing sheet comprising a porous layer which is coated with a resin solution containing a polyurethane resin and which is subjected to wet coagulation to provide a printed surface, a base fabric and a resin layer containing a flameproofing agent.

2. 2. The sheet according to 1 above, which comprises a flameproofing agent-containing resin layer on the side opposite to the porous layer which gives the printed side of the base fabric.

3. The sheet according to 1 or 2 above, wherein the flameproofing agent content is in the range of 5 to 50% by weight based on the flameproof printing sheet.

4. The sheet according to any one of 1 to 3 above, wherein the base fabric is a polyester fiber fabric.

5. The sheet according to any one of 1 to 4 above, wherein the thickness of the porous layer is 10 to 500 μm.

6. Flame resistance including applying a resin solution containing a flameproofing agent to at least one side of a base fabric by a coating method, coating a resin solution containing a polyurethane resin on at least one side thereof, and wet-coagulating to form a porous layer. A method for manufacturing a printing sheet.

That is, the greatest feature of the present invention is to provide a printing sheet having sufficient flameproofness and excellent surface smoothness without affecting the porous layer forming the printing surface, and a method for producing the same. In point.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Base fabrics useful in the present invention include synthetic fibers such as polyester and nylon, semi-synthetic fibers such as diacetate and triacetate, regenerated fibers such as rayon, and natural fibers such as cotton, silk and wool. It may be a fabric made of fibers, or may be a mixed fiber product or a woven product of two or more kinds of these fibers. Further, the form may be any form such as woven fabric, knitted fabric, and non-woven fabric. Among them, polyester fiber cloth, particularly polyester woven cloth is preferable from the viewpoints of processability, dimensional stability, smoothness and good texture. Also,
In order to prevent the impregnation of the resin solution and improve the surface smoothness, the base fabric may be previously subjected to treatment with a water repellent agent or crushing with a calendar treatment. Further, a flameproofing agent may be previously added to the base fabric by an exhaust method such as padding or dip dyeing.

The printing surface of the printing sheet of the present invention is
It is a film surface of a porous layer formed by coating a resin solution containing a polyurethane resin on at least one surface of a base fabric or a base fabric having a resin layer containing a flameproofing agent, and wet-coagulating it. The method using wet coagulation is advantageous because it forms a porous layer and is less likely to be affected by the irregularities of the fiber base material even if the resin solid content is relatively small, and excellent surface smoothness is easily obtained.

The solvent used for preparing the resin solution is not particularly limited as long as it can be used in the wet coagulation method, but dimethylformamide (DMF) is generally preferably used.

The composition of the polyurethane resin in the present invention may be a polyester type, a polyether type, a polycarbonate type or the like, or a mixture thereof, and is not particularly limited, but from the viewpoint of foamability and cost. Are preferably polyester-based and polyester-ether-based.

Further, in order to obtain a porous film for obtaining more excellent surface smoothness, the polyurethane resin is a mixture of two or more kinds of polyurethane resins, at least one of which has a 100% modulus of 300 Kg or more. The above polyurethane resin is preferably blended so that the proportion thereof in the total polyurethane resin is 10 to 70% by mass, more preferably 20 to 50% by mass. Polyurethane resin with a high modulus of 100% modulus of 300 kg or more has a very fast coagulation rate during wet coagulation, and therefore the surface smoothness of the polyurethane resin solution immediately before coagulation is maintained as it is after coagulation, and a surface property suitable for printing is obtained. I think it will give. When the amount of the high modulus polyurethane resin is less than 10% by mass, sufficient surface coagulation may not be obtained, and excellent surface smoothness may not be achieved. If it exceeds 70% by mass, the modulus of the entire resin becomes too high, and the surface smoothness may decrease due to molding shrinkage. In addition, the texture may become hard, which is not preferable. As described above, the surface smoothness immediately after solidification mainly depends on the solidification characteristics of the high modulus polyurethane resin, but the modulus of the entire system should be such that molding shrinkage is difficult. Therefore, the blending ratio of the high modulus polyurethane resin is preferably 70% by mass or less, and the 100% modulus of at least one of the other polyurethane resins mixed with the high modulus polyurethane resin is 1% or less.
It is preferably 00 kg or less.

If necessary, other additives such as a crosslinking agent and a pigment may be added to the polyurethane resin solution. Fine powder or the like may be added for the purpose of improving the washing durability of printing. The fine powder is not particularly limited, but examples of the porous fine powder include porous silica, activated carbon, zeolite and the like, and the average particle diameter thereof is preferably 300 μm or less. Porous silica is particularly preferable. Further, as fine powders, two or more kinds may be used in combination, but in order to avoid processing stability and complexity during solution preparation, it is preferable to use only one kind having good dispersibility in DMF. preferable.

As a method for applying the resin solution to the fiber base material, various coating methods such as knife coating, knife over roll coating and reverse roll coating can be used. The coating amount of the resin solution is not particularly limited, but it is preferable to apply the resin solution so that the film thickness of the porous layer is in the range of 10 to 500 μm from the viewpoint of surface smoothness or cost, and 500
If it exceeds μm, the flame resistance may decrease.

As a method of imparting flameproofness, it is important to impart a sufficient amount of flameproofing agent without affecting the formation of the porous layer to be the printed surface. In order to achieve this object, it is not sufficient to add a flameproofing agent to the cloth by a dust absorption method, and addition of the flameproofing agent to the porous layer unavoidably affects its surface smoothness. Therefore, in the present invention, it is necessary to apply a resin containing a flameproofing agent to at least one surface of the fabric separately from the formation of the porous layer.

The method of applying the flameproofing agent-containing resin may be a padding method, a coating method, a laminating method, a gravure transfer method or the like, and is not particularly limited, but when the printing surface is only one side of the sheet, The method of applying the flameproofing agent-containing resin by coating on the surface of the substrate cloth, which is the back side of the printed surface, is preferable because it is simple and easily provides a sufficient amount of the flameproofing agent. More specifically, after applying a flameproofing agent-containing resin solution to one side of the base fabric by a coating method, a resin solution containing a polyurethane resin is coated on the side opposite to the coating side of the base fabric, and the wet process is performed. It may be solidified to form a porous layer.

Of course, the flameproofing agent-containing resin solution may be applied to both surfaces of the base fabric to form the flameproofing agent-containing resin layer.

Further, as a preferred example in the case where the printing surface is on both sides of the sheet, after applying the flameproofing agent-containing resin on both sides of the base fabric before forming the printing surface by the padding method,
The method of forming the porous layer to be the printed surface is useful because it hardly causes a difference between the printed surface and the printed surface.

The flameproofing agent may be a halogen-based one, a phosphoric acid-based one or the like, and is not particularly limited, but a halogen-based flameproofing agent is preferable from the viewpoint of flameproofness. The resin used for applying the flameproofing agent is also not particularly limited, but an aqueous or solvent-based resin solution is preferable from the viewpoint of easy handling when adding the flameproofing agent.

Further, as the general-purpose resin, an acrylic resin, a polyurethane resin, a polyamide resin, a polyester resin and the like can be mentioned, but the polyurethane resin is preferable from the viewpoint of adhesiveness and easiness of adjusting the texture.

As the film forming method, various film forming methods such as a dry method and a wet method can be used and are not particularly limited.

Needless to say, other additives may be added to the flameproofing agent-containing resin layer depending on the intended use. For example, the addition of a cross-linking agent is effective for applications requiring washing durability. Furthermore, application of such a flameproofing agent-containing resin to a printing sheet is useful in that it also contributes to prevention of fraying and curling of the base fabric.

The amount of the flameproofing agent-containing resin applied to the printing sheet is not particularly limited as long as it satisfies the flameproof performance, but the amount of the flameproofing agent preferably accounts for the weight of the printing sheet. It is preferable to apply it so that the ratio is in the range of 5-50%. If it is less than 5%, it becomes difficult to obtain flameproof performance, and if it exceeds 50%, it is not preferable from the viewpoint of deterioration in adhesiveness to a cloth and cost.

The printing sheet of the present invention can be printed on the surface of the porous layer. As a printing method,
For example, a thermal transfer method, an inkjet method, a handwriting method, a screen printing method, a gravure printing method, or the like can be adopted, and the method is not particularly limited. The printing ink is also not particularly limited, and may be appropriately selected and used depending on the purpose of use, such as oiliness or wateriness. Needless to say, it is possible to perform arbitrary printing including characters such as prints, pictures and bar code patterns, figures and symbols.

[0029]

EXAMPLES The present invention will be further described below with reference to examples of the present invention and comparative examples, but the present invention is not limited to these examples. In addition, "part" shows a mass part in an example.

Example 1 Polyester taffeta using a yarn of 83 decitex / 36 filaments (density: 100 yarns / 2.54c)
m, 90 wefts / 2.54 cm) was scoured by a usual method and heat set. Next, a water-repellent treatment liquid having the composition shown in the following formulation 1 was padded at a squeezing rate of 80%, dried with hot air at 120 ° C., and then heat-treated at 160 ° C. for 30 seconds.

Prescription 1 Asahi Guard AG710 (Asahi Glass Co., Ltd. fluorine-based water repellent) 4 parts Water 96 parts Continuing, using a calendering machine with a mirror-finished roll, a temperature of 180 ° C. Pressure 30kg
/ Cm ² , and the speed was 20 m / min, and calendering was performed to obtain a base fabric for coating.

Next, a polyurethane resin solution having the composition shown in the following Formulation 2 was applied to the surface of the base cloth opposite to the calendered surface by knife coating at an application amount of 50 g / m ² and water at 20 ° C. The polyurethane coating solution was wet-coagulated by immersing it in a coagulation bath for 3 minutes, then washed with warm water of 60 ° C. for 10 minutes, and cylinder-dried at 120 ° C. to obtain a backside coated cloth.

Formulation 2 Polyester polyurethane (DMF solution of resin solid content 30%) 100 parts DMF 40 parts Flame retardant 200 parts (Halogen flame retardant, decabromodiphenyl ether: antimony trioxide = 8: 1 mixture (weight ratio ), Solid content 80% DMF solution) Then, using a knife over roll coater, a polyurethane resin solution having the composition shown in Formula 3 below is applied to the surface (calendering surface) opposite to the coating surface of the back coating cloth. Coated with a coating amount of 120 g / m ² ,
The polyurethane resin coating liquid is wet-coagulated by immersing it in a water coagulation bath at 20 ° C for 3 minutes, and then hot water at 60 ° C is used for 10 minutes.
After washing with water for 1 minute and drying the cylinder at 120 ℃, 160 ℃
Heat treatment for 3 minutes at a thickness of 40 μm for the porous layer,
A printing sheet having a flameproofing agent content of 27% by mass relative to the mass of the printing sheet was prepared.

Formulation 3 Crisbon MP899 30 parts (Dainippon Ink and Chemicals, Inc. polyester polyurethane, 100% module 570 Kg / cm ² , DMF solution of resin solid content 30%) Polyester 70 parts (100% modulus 40 Kg / Cm ² , DMF solution with resin solid content of 30%) DMF 40 parts Sylysia # 740 (Fuji Silysia Chemical Ltd. porous silica) 5 parts White pigment (titanium oxide type) 5 parts Comparative Example 1 83 decitex / 36 filaments Polyester taffeta using yarn (Density: 100 warps / 2.54c
m, 90 wefts / 2.54 cm) was scoured by a usual method and heat-set, and then padded with a water repellent treatment solution having the same composition of the prescription 1 used in Example 1 at a squeezing rate of 80%.
After drying with hot air at 20 ° C., heat treatment was further performed at 160 ° C. for 30 seconds.

Subsequently, a calendering machine having a mirror-finished roll was applied to the water-repellent treated cloth at a temperature of 180 ° C.
Calendar processing was performed under the conditions of a pressure of 30 Kg / cm ² and a speed of 20 m / min to obtain a base fabric for coating.

Then, a polyurethane resin solution having the same composition as that of the formulation 3 used in Example 1 was applied to the calendered surface of the above base fabric with a knife over roll coater for 120 seconds.
Apply at a coating amount of g / m ² and apply 3 in a 20 ° C water coagulation bath.
Wet for a minute to wet and solidify the polyurethane resin coating liquid,
Then, it was washed with warm water of 60 ° C. for 10 minutes, dried at 120 ° C. in a cylinder, and then heat-treated at 160 ° C. for 3 minutes to prepare a printing sheet.

Comparative Example 2 Polyester taffeta using a yarn of 83 decitex / 36 filaments (density: 100 yarns / 2.54c)
m, 90 wefts / 2.54 cm) was scoured by a usual method and heat-set, and then the composition shown in the following prescription 4 was applied to the composition at 135 ° C.
In a hot water bath, the flameproofing agent was exhausted for 60 minutes, washed with an alkali, and then dried with hot air at 120 ° C to subject the base fabric to the flameproofing agent treatment.

Formulation 4 Flameproofing agent (hexabromocyclododecane dispersion type, solid content 45%) 4 parts Water 96 parts Next, a water repellent treatment liquid having the same composition of Formulation 1 used in Example 1 was squeezed to 80%. After padding with and dried in hot air at 120 ° C., heat treatment was further performed at 160 ° C. for 30 seconds.

Subsequently, a calendering machine having a mirror surface roll was used for the water-repellent treated cloth at a temperature of 180 ° C.
Calendar processing was performed under the conditions of a pressure of 30 Kg / cm ² and a speed of 20 m / min to obtain a base fabric for coating.

Then, the same formulation 3 as used in Example 1 was prepared.
The composition of the polyurethane resin solution, the calendar of the base fabric
120g on the treated surface by knife over roll coater
/ M ² And apply in a water coagulation bath at 20 ° C for 3 minutes.
For 6 hours to wet solidify the polyurethane coating solution, then
Rinse with warm water of 0 ℃ for 10 minutes, then cylinder at 120 ℃
-After drying, heat-treat at 160 ℃ for 3 minutes for printing
Created a sheet.

Comparative Example 3 A printing sheet was prepared in the same manner as in Comparative Example 1 except that Formula 3 described in Comparative Example 1 was changed to Formula 5 below.

Formulation 5 Crisbon MP899 30 parts (Dainippon Ink and Chemicals, Inc. polyester polyurethane, 100% module 570 Kg / cm ² , DMF solution of resin solid content 30%) Polyester polyurethane 70 parts (100% modulus 40 Kg / Cm ² , DMF solution of resin solid content 30%) DMF 40 parts Sylysia # 740 (Fuji Silysia Chemical Ltd. porous silica) 5 parts White pigment (titanium oxide-based) 5 parts Flame retardant 200 parts (halogen-based protection) Flame retardant, decabromodiphenyl ether: antimony trioxide = 8: 1 mixture (weight ratio), DMF solution having a solid content of 80%) The printing sheets obtained in the above Examples and Comparative Examples were subjected to the following test method. An evaluation test was conducted.

Printability The printing sheets obtained in Examples and Comparative Examples were printed by a thermal transfer method to obtain a printing sheet, and the printed state was visually observed, and excellent (good appearance), good (printed thin but legible) The evaluation was made in three grades: poor (unreadable).

Smoothness The smoothness of the printed surface was measured using an Oken type air permeability smoothness tester (manufactured by Asahi Seiko Co., Ltd.).

The flame resistance of FMWSS 302 was evaluated, and those having a flame retardance of 100 mm / min or less were regarded as acceptable.

The results of these evaluation tests are shown in Table 1.

[0047]

[Table 1]

[0048]

According to the present invention, it has excellent surface smoothness, can print delicately and clearly in a thermal transfer system and various printing systems, and has an excellent flameproof property.
It is possible to obtain a printing sheet that can be used in applications where flameproof performance is required.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 2C056 FC06                 4L033 AA07 AB05 AC05 AC15 BA14                       CA51 CA52

Claims (6)

[Claims] 1. A flameproof printing sheet comprising a porous layer which is coated with a resin solution containing a polyurethane resin and which is wet-coagulated to provide a printing surface, a base fabric and a flameproofing agent-containing resin layer. 2. The sheet according to claim 1, further comprising a flameproofing agent-containing resin layer on the surface opposite to the porous layer which gives the printed surface of the base fabric. 3. The sheet according to claim 1, wherein the flameproofing agent content is in the range of 5 to 50% by weight based on the flameproof printing sheet. 4. The base fabric is a polyester fiber fabric,
The sheet according to claim 1. 5. The sheet according to claim 1, wherein the porous layer has a thickness of 10 to 500 μm. 6. A porous layer is formed by applying a flameproofing agent-containing resin solution on at least one side of a base fabric by a coating method, coating the resin solution containing a polyurethane resin on at least one side, and wet-coagulating the solution. A method for producing a flameproof printing sheet containing: