KR101428777B1 - Manufacturing method of hot-melt type foam sheet and hot-melt type foam sheet thereby - Google Patents

Abstract

In the present invention, provided is a method for preparing a hot melt type foamed sheet, comprising (a) a material mixing step of mixing a hot melt resin with a melting point of 60-150°C and a foaming agent; (b) a hot melt type foamed sheet foaming step of foaming and extruding the mixed material; and (c) a molding step of molding the hot melt type foamed sheet. The present invention also provides a hot melt type foamed sheet prepared thereby.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a hot-melt type foam sheet and a hot-melt type foam sheet,

The present invention relates to a method for producing a hot melt type foam sheet and a hot melt type foam sheet produced thereby.

The demand for synthetic resin sheets in the form of foam is steadily increasing depending on the need for weight reduction, impact resistance, cushioning, ease of three-dimensional molding and the like of synthetic resin sheet products. Such a foamed synthetic resin sheet is not used alone, but a printed or patterned sheet is further formed on the surface, or a fabric or a non-foamed film is adhered to the lower layer. Adhesives using a hot-melt adhesive or an organic solvent are generally used for the adhesion.

However, in recent years, the use of toxic organic compounds (organic solvents) has been gradually restricted due to environmental regulations. Further, the use of the hot-melt adhesive separately causes a decrease in the productivity of the product and an increase in the production cost because of the complicated procedure. Therefore, there is a demand for a method capable of solving the above problems.

Korean Patent No. 10-1192784

The present invention has been conceived to solve the problems of the prior art as described above, and it is an object of the present invention to provide a hot melt type foam sheet capable of easily attaching a fabric or a non-foam sheet to a foam sheet without an additional adhesive by giving an adhesive force to the foam sheet itself And a hot melt type foam sheet produced thereby.

The present invention

(a) a raw material mixing step of mixing a raw material including a hot-melt resin having a melting point of 60 ° C to 150 ° C and a foaming agent;

(b) a step of forming a hot-melt type foam sheet for foaming and extruding the mixed raw material; And

(c) a step of forming the hot-melt type foam sheet; and (c) a step of forming the hot-melt type foam sheet.

Further, the present invention provides a hot-melt type foam sheet produced by the above-described production method.

In addition,

A method for producing a multilayer sheet using an extruder having two or more layers,

In one or more extruders

A hot-melt type foamed sheet layer is formed by foaming and extruding a mixed raw material including a hot-melt resin having a melting point of 60 ° C to 150 ° C and a foaming agent, and is coalesced with a sheet extruded by another extruder, ≪ / RTI >

The present invention also provides a multilayer sheet produced by the above production method.

The method of producing a hot-melt type foam sheet of the present invention provides a hot-melt type foam sheet capable of easily attaching a fabric or a non-foam sheet to a foam sheet without imparting an adhesive by imparting an adhesive force to the foam sheet itself. That is, at the time of forming the hot melt type foam sheet, the fabric or the non-foam sheet can be directly bonded to the hot melt type foam sheet, or the hot melt type foam sheet can be manufactured,

Therefore, the present invention contributes greatly to the productivity of the foam sheet and the production cost reduction owing to the reduction of the manufacturing process and the reduction of the raw material cost.

1 and 3 are schematic views of a horizontal extrusion type hot melt type foam sheet production apparatus.
2 and 4 are schematic views of a down-extrusion hot-melt type foam sheet producing apparatus.
Fig. 5 shows electron micrographs of the foam sheet produced in Examples 1, 2 and 3. Fig.
6 shows a photograph of a specimen for an adhesion test.
7 shows the results of the adhesion test.

The present invention

(a) a raw material mixing step of mixing a raw material including a hot-melt resin having a melting point of 60 ° C to 150 ° C and a foaming agent;

(b) a step of forming a hot-melt type foam sheet for foaming and extruding the mixed raw material; And

(c) a step of forming the hot-melt type foam sheet; and (c) a step of forming the hot-melt type foam sheet.

In the (a) raw material mixing step, components including 90 to 99.9% by weight of the hot-melt resin and 0.1 to 10% by weight of the blowing agent may be mixed based on the total solid weight of the raw material.

In the (a) raw material mixing step, 0.1 to 5% by weight of an adhesive reinforcing agent may be added based on the total solid weight of the raw material in order to reinforce the adhesive force, thereby mixing the raw materials.

As the hot-melt resin, there may be used a hot-melt resin such as Copolyamide hot melt resin (PA), Copolyester hot melt resin, SIS block copolymer hot melt resin, and amorphous polypropylene (APP) A TPO-based hot-melt resin, a thermoplastic polyurethane hot-melt resin, etc. These may be used singly or in combination of two or more. These may be used in the form of pellets mixed with a blowing agent.

Among the applicable hot melt resins, the thermoplastic polyurethane hot melt resin is preferably a linear polymer and preferably has a weight average molecular weight in the range of 90,000 to 450,000.

The polyurethane hot-melt resin which can be used as the hot-melt resin in the step (a) may include 80 to 90% by weight of a polyol having a weight average molecular weight of 500 to 3,000 and a diisocyanate compound % ≪ / RTI >

The polyol content of the general thermoplastic polyurethane resin is usually 50 to 70% by weight. Unlike the TPU resin for general film and sheet, the TPU resin for hot melt has a functional group (NCO group , OH group), the content of the polyol is 80 to 90% by weight in the feed ratio of the polyol, the diisocyanate compound and the chain extender, which are used as the main raw materials, Is used and the polymer in a polymerized state is mainly composed of a soft segment and is designed to have a low melting point. However, a special manufacturing method is used in which a rigid segment is imparted by using a high crystalline polyol to design an adhesive.

The polyol is generally used in this field and includes a method of using one type of polyol alone and a method of mixing two or more kinds of polyols having different molecular weights to control the melting point and the adhesive force by the additional effect of the reaction And the kind thereof is not particularly limited, and examples thereof include polyester glycol, polyether glycol, polycarbonate glycol, polyethylene glycol, polypropylene glycol, amine terminated polyether, polytrimethylene ether glycol, poly At least one polyol selected from the group consisting of trimethylene ether ester glycol, polytrimethylene-co-ethylene ether glycol, polytetramethylene ether glycol, and mixtures thereof may be used.

In particular, when using polyester glycol, it is possible to improve the rigidity, oil resistance and chemical resistance of the hot melt type foam sheet; When polyether glycol is used, the low temperature properties, resilience, antimicrobial resistance and hydrolysis resistance of the hot melt type foam sheet can be improved; When polycarbonate glycol is used, rigidity and heat resistance of the hot melt type foam sheet can be improved, and at least one polyol selected from the group consisting of polyester glycol, polyether glycol, polycarbonate glycol and mixtures thereof is used Whereby a hot-melt type foam sheet of excellent quality can be obtained.

The diisocyanate compound is generally used in this field, and its kind is not particularly limited. Examples thereof include diisocyanate, methylene diphenyl diisocyanate (MDI), polymeric methylene diphenyl diisocyanate polymeric methylene diphenyl diisocyanate, toluene diisocyanate (TDI), hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, phenylene diisocyanate, dimethyl diphenyl diisocyanate but are not limited to, dimethyl diphenyl diisocyanate, tetramethylene diisocyanate, isoholon diisocyanate, naphthalene diisocyanate, triphenyl methane tr iisocyanate), and mixtures thereof.

The polyurethane hot-melt resin may further comprise 4 to 10% by weight of a chain extender based on the total weight of the polyurethane hot-melt resin solids. Examples of the chain extender include diol group-containing compounds such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 2-methylpentanediol, , 1,6-hexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, neopentyl glycol, etc. These may be used alone or in combination of two or more.

The adhesion promoter may be selected from the group consisting of Turpentine phenolic resin (e.g., NEOLITE KC-4001 from Kangnam Chemical), phenoxy resin (e.g., PKHH from INCHEM), Refining from Heavy Raw-Pyrolysis Gasoline (For example, HIKOTACK P series of KOLON emulsions and the like), hydrogenated DCPD (e.g., SUKOREZ SU series of KOLON emulsions), and rosin. Or two or more species.

If the amount is less than 0.1% by weight, the adhesive strength of the hot-melt type foam sheet becomes insufficient. If it exceeds 5% by weight, the adhesive strength of the adhesive agent The extrusion becomes difficult and the physical properties of the foamed resin may be deteriorated.

The adhesive reinforcing agent can be prepared by mixing a polyol and adding it to a raw material polymerization line or adding it at the rear end of a reactor cylinder of a raw material polymerization line by adding a liquid or powder adhesive reinforcing agent.

The blowing agent may be in the form of a microcapsule containing a hydrocarbon in a polymer shell made of AN-copolymer (acrylonitrile copolymer), PVDC or the like. In this case, the microcapsules may preferably have an average diameter of 5 to 50 [micro] m.

The foaming agent may be contained in an amount of 0.1 to 10% by weight based on the total solid weight of the starting material.

The raw material may further include additives commonly used in a synthetic resin foam sheet. For example, it may further include additives such as thermoplastic elastomers, pigments, surfactants, fillers and the like.

Such additives are generally used in the art, and the specific kinds and contents thereof are not particularly limited, but may be more preferably 0.1 to 30 parts by weight based on 100 parts by weight of the raw materials.

The thermoplastic elastomer may be at least one selected from the group consisting of styrene butadiene styrene (SBS), ethylene vinyl acetate (EVA), thermoplastic rubber (TR), and mixtures thereof.

In the (a) raw material mixing step, one or more selected from a flame retardant and an antistatic agent may be further mixed as the raw material in order to impart flame retardancy or antistatic property to the sheet.

The forming step (c) may include: (b) cooling the hot-melt type foam sheet in a non-cooled state produced in the forming step of the foam sheet while passing the foam sheet between the touch roll and the cooling roll.

The forming step (c) includes: (b) a step of forming a hot-melt foamed sheet in a non-cooled state, which is produced in the step of forming a foamed sheet, together with a synthetic resin, And then cooling while passing through the rolls, pressing them together, and coalescing and forming.

The fabric may be a nonwoven fabric or the like and the synthetic resin in the form of a film may be one or more kinds selected from the group consisting of EVA, TPR, TPO, TPE, TPU, polyester, polyamide, have.

A pattern for molding can be engraved on the surface of the cooling roll.

(C) a step of winding the hot-melt type foam sheet formed after the forming step into a roll form (e) in the manufacturing method of the hot-melt type foam sheet.

In addition,

The present invention relates to a hot-melt type foam sheet produced by the above-described production method.

The hot-melt type foam sheet may be various types of sheets including a hot-melt type foam sheet. For example, the hot-melt type foam sheet includes a hot-melt type foam sheet itself, a form in which another sheet is attached to one side or both sides of the hot-melt type foam sheet. The other sheet may be a fabric sheet or a polymer sheet.

In addition,

A method for producing a multilayer sheet using an extruder having two or more layers,

In one or more extruders

A hot-melt type foamed sheet layer is formed by foaming and extruding a mixed raw material including a hot-melt resin having a melting point of 60 ° C to 150 ° C and a foaming agent, and is coalesced with a sheet extruded by another extruder, And a method for producing the same.

The raw material may be further mixed with an adhesive reinforcing agent.

All contents described in the production method of the hot melt type foam sheet can be equally applied to a method of producing a multilayer sheet.

The extruded sheet in the other layer extruder may be selected from the group consisting of EVA, TPR, TPO, TPE, TPU, polyester, polyamide, and rubber-based polymers.

The present invention also relates to

To a multilayer sheet produced by the above-described production method.

The multi-layer sheet may be a sheet of various types including a hot-melt type foam sheet. For example, the hot-melt type foam sheet includes a form in which another sheet is attached to one side or both sides of the hot-melt type foam sheet.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings exemplified by the embodiments of the present invention. In the following description, well-known functions or constructions are not described in detail since they would obscure the invention in unnecessary detail.

In the present invention, (b) extrusion of the step of forming a hot melt type foam sheet can be performed by a method commonly used in the art, and the method is not particularly limited, but more specifically, a calender line or a T- 3). ≪ / RTI >

In particular, as shown in Figs. 1 and 2, it can be performed using a T-shaped die 3 of a horizontal extrusion type or a downward extrusion type. The step (b) of forming the hot melt type foam sheet may be carried out by extruding the mixed raw materials onto the substrate film (Figs. 3 and 4 and 8) continuously fed.

In the present invention, as shown in Figs. 1 and 2, the (c) forming step is a step of forming the foamed and uncooled hot melt foam sheet 6 on the surface of the touch roll 5 and the cooling roll 4 Forming mold can be formed), and cooling the mold while molding.

As shown in FIGS. 3 and 4, the forming step (c) may be carried out by using a fabric or film synthetic resin 8 continuously fed from a separate Un-winder, Shaped foam sheet 6 is passed between the touch roll 5 and the cooling roll 4 while being compressed and molded.

The forming step (c) may be performed by cooling the cooling roll 4 to a temperature range of 0 to 150 ° C. More preferably from 5 to 80 < 0 > C.

In the forming step (c), the hot-melt type foam sheet 6 in an uncooled state is passed between the cooling roll 4 and the touch roll 5 facing each other, and the cooling roll 4 and the touch roll 5, The thickness of the hot melt type foam sheet 6 can be adjusted by adjusting the rotation speed. At this time, the cooling roll 4 can easily cause the surface pattern of the rollers to be etched on the foam sheet, and at the same time, cooling for winding can be performed simultaneously.

The thickness of the hot melt type foam sheet 6 is 50 to 3,000? Lt; / RTI >

The hot melt type foam sheet 6 after the (b) molding step is re-winded and can be used as a hot melt type foam sheet itself, and can be used for various purposes by re-lapping with other substrates.

Hereinafter, the present invention will be described in more detail by way of examples. However, the following examples are intended to further illustrate the present invention, and the scope of the present invention is not limited by the following examples. The following examples can be appropriately modified and changed by those skilled in the art within the scope of the present invention.

Example  One: Hot-melt type  Preparation of foam sheet and physical property test

A hot-melt type foam sheet was produced using a thermoplastic polyurethane hot-melt resin and a foam master batch.

 The raw material for use was mixed with 100 parts by weight of a thermoplastic polyurethane hot-melt resin having a melting point of 110 占 폚 of Sheensoon Co., Ltd. in the ratio of 3 parts by weight of the foam masterbatch of Lubrizol.

The mixed raw materials were fed into a T-die extruder and extruded continuously. The temperature conditions of the extruder were 130 ° C to 160 ° C for the cylinder, 170 ° C for the adapter and 170 ° C for the die.

The specific gravity of the produced hot melt-type foam sheet was 0.75, and the adhesive strength to the fabric was as shown in Table 1 below.

Specimen thickness - foamed sheet: 1.0 mm, fabric / polystyrene microfiber: 0.5 mm; Specimen width: 25 mm, Pressure: 50 kgf / cm ²

division 140 ℃ 15 sec 150 ℃ 15 seconds 160 ℃ 15 sec Peel strength (kgf / cm) 1.33 3.15 3.94

As a result of the test, the specific gravity reached 0.75, and the adhesive force was maintained at a temperature of 150 ° C or so, which was higher than the target value.

Example  2: Hot-melt type  Preparation of foam sheet and physical property test

A hot-melt type foam sheet was produced using a thermoplastic polyurethane hot-melt resin, a tackifier, and a foam masterbatch.

 1 part by weight of Turpentine phenolic resin of Kangnam Chemical Co., Ltd. was added to 100 parts by weight of a thermoplastic polyurethane hot-melt resin having a melting point of 110 占 폚 of Sheensoon Co., Ltd. of Taiwan, Were mixed at a ratio of 3 parts by weight.

The mixed raw materials were fed into a T-die extruder and extruded continuously. The temperature conditions of the extruder were 130 ° C to 160 ° C for the cylinder, 170 ° C for the adapter and 170 ° C for the die.

The specific gravity of the produced hot melt type foam sheet was 0.75 and the adhesive strength to the fabric was as shown in Table 2 below.

Specimen thickness - foamed sheet: 1.0 mm, fabric / polystyrene microfiber: 0.5 mm; Specimen width: 25 mm, Pressure: 50 kgf / cm ²

division 140 ℃ 15 sec 150 ℃ 15 seconds 160 ℃ 15 sec Peel strength (kgf / cm) 3.29 3.77 4.25

As a result of the test, the specific gravity reached 0.75 and reached the target value, and the adhesive strength was more than the target value even at the heat pressing temperature of about 140 ° C.

Comparative Example  One.

For comparison of the adhesive strength with the hot-melt type foam sheet of the present invention, a foam sheet was prepared using a general thermoplastic polyurethane resin and a foam masterbatch.

 The target adhesive strength of the produced foam sheet is not less than 2.5 kgf / cm, which is commonly used in the shoe industry, and has a specific gravity of 0.7 to 0.85.

 The raw materials used were a mixture of 100 g of a general-purpose TPU resin of 85 A hardness polyester type manufactured by Dong Sung High Chem Co., Ltd., 3 g of foam masterbatch of Lubrizol, and 3 g of fluorescent color masterbatch.

The mixed raw materials were fed into a T-die extruder and extruded continuously. The temperature condition of the extruder was set at 150-180 ° C for the cylinder part, 190 ° C for the adapter part and 185 ° C for the adapter part.

The specific gravity of the foamed sheet produced was 0.85 and the adhesive strength to the fabric was as shown in Table 3.

Specimen thickness - foamed sheet: 1.0 mm, fabric / polystyrene microfiber: 0.5 mm; Specimen width: 25 mm, Pressure: 50 kgf / cm ²

division 140 ℃ 15 sec 150 ℃ 15 seconds 160 ℃ 15 sec Peel strength (kgf / cm) 0.27 0.20 1.24

As a result of the test, the specific gravity reached 0.85, but the adhesive strength was low at a high temperature of about 160 ° C., and it was found that sufficient adhesion could not be obtained without forming a separate adhesive or hot melt film layer.

1: Cylinder 2: Adapter
3: T-shaped dice 4: Cooling roll
5: touch roll 6: hot melt type foam sheet
7: Unwinder 8: base film

Claims (15)

(a) 90 to 99.8% by weight of a hot-melt resin having a melting point of 60 to 150 캜 based on the total solid weight of the raw material; One or two or more types of adhesives selected from the group consisting of turpentine phenolic resin, phenoxy resin, aromatic petroleum resin (C9), hydrogenated DCPD (Dicyclopentadien), and rosin 0.1 to 5% by weight of a reinforcing agent; And 0.1 to 10% by weight of a blowing agent;
(b) a step of forming a hot-melt type foam sheet for foaming and extruding the mixed raw material; And
(c) a step of forming the hot-melt type foam sheet. The method according to claim 1,
In the (a) raw material mixing step, the hot-melt resin is selected from the group consisting of Copolyamide hot melt resin (PA), Copolyester hot melt resin, SIS block copolymer hot melt resin, and thermoplastic poly Urethane hot melt resin, and a urethane hot melt resin. delete delete delete The method of claim 2,
Wherein the thermoplastic polyurethane hot melt resin comprises 80 to 90% by weight of a polyol having a weight average molecular weight of 500 to 3,000 and 10 to 20% by weight of a diisocyanate compound based on the total weight of the resin on a solid basis. Gt; The method according to claim 1,
Wherein the raw material is further mixed with at least one selected from a flame retardant and an antistatic agent in the raw material mixing step (a). The method according to claim 1,
The step (c) includes the steps of: (b) pressing the hot-melt type foam sheet in a non-cooled state produced in the step of forming the foam sheet while passing the foam sheet between the touch roll and the cooling roll, A method for producing a hot melt type foam sheet. The method according to claim 1,
The forming step (c) includes the steps of: (b) forming a hot-melt type foam sheet in a non-cooled state produced in the step of forming a foam sheet, together with a synthetic resin, And then cooling the same while adhering and forming. 2. A method for producing a hot-melt type foamed sheet according to claim 1, The method according to claim 8 or 9,
Wherein the surface of the cooling roll is engraved with a pattern for molding. A hot-melt type foam sheet produced by the method of any one of claims 1, 2, and 6 to 9. A method for producing a multilayer sheet using an extruder having two or more layers,
90 to 99.8% by weight of a hot melt resin having a melting point of 60 to 150 캜 based on the total solid weight of the raw material in an extruder having one or more layers; One or two or more types of adhesives selected from the group consisting of turpentine phenolic resin, phenoxy resin, aromatic petroleum resin (C9), hydrogenated DCPD (Dicyclopentadien), and rosin 0.1 to 5% by weight of a reinforcing agent; And 0.1 to 10% by weight of a foaming agent is foamed and extruded to form a hot-melt type foam sheet layer, and the sheet is extruded from another layer of an extruder to be cemented with the extruded sheet. delete The method of claim 12,
Wherein the extruded sheet in the other layer extruder is formed of one or more kinds selected from the group consisting of EVA, TPR, TPO, TPE, TPU, polyester, polyamide, and rubber- ≪ / RTI > A multilayer sheet produced by the method of any one of claims 12 and 14.

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