KR101631688B1 - Thin Film Polyurethanes Foam Tape Laminate having UV-curable Adhesive Layer and Manufacturing Method Thereof - Google Patents

Thin Film Polyurethanes Foam Tape Laminate having UV-curable Adhesive Layer and Manufacturing Method Thereof Download PDF

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KR101631688B1
KR101631688B1 KR1020150110751A KR20150110751A KR101631688B1 KR 101631688 B1 KR101631688 B1 KR 101631688B1 KR 1020150110751 A KR1020150110751 A KR 1020150110751A KR 20150110751 A KR20150110751 A KR 20150110751A KR 101631688 B1 KR101631688 B1 KR 101631688B1
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polyol
film layer
weight
parts
polyurethane foam
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KR1020150110751A
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이상호
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주식회사 에스제이폼웍스
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    • C09J7/0296—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C09J7/0282—
    • C09J2205/10—

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
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Abstract

The adhesive thin film polyurethane foam laminate according to the present invention comprises a base film layer, a polyurethane foam thin film layer formed on the base film layer using a foam composition comprising polyol A, polyol B, polyol C and isocyanate, Wherein the polyol A is a polyol-based triol or diol having a molecular weight of 2000 to 4000 and containing 20 to 40 functional groups, and the polyol A is an ethylene oxide And the polyol C is a caprolactone series having a molecular weight of from 400 to 800, and a functional group having a molecular weight of 400 to 800. The polyol B is a polyol having a molecular weight of 400 to 800 and a functional group of 200 to 400, Or a triol system or a diol system containing 200 to 400 units.

Figure R1020150110751

Description

TECHNICAL FIELD [0001] The present invention relates to a thin film polyurethane foam tape laminate and a method of manufacturing the same,

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thin film polyurethane foam tape laminate which can be applied as a cushioning material and a sealing material used in an electronic device such as a smart phone and a method of manufacturing the same, A moisture absorbent agent is added to the foam composition to suppress the chemical foaming reaction due to the residual moisture contained in the foam composition and instead, the cell structure formed in the foam laminate by the chemical foaming reaction in the prior art is replaced with a low- It is possible to form a very thin polyurethane foam laminate at a low density by replacing the hollow microspheres with a micro hollow sphere, and the molded foam laminate can be produced by any one of reverse gravure, gravure and microgravure having 100 to 250 necks directly Solvent-free or solvent-free UV curable adhesives by coating the adhesive layer Due to the property it relates to the separate adhesive application or a double-sided pressure-sensitive adhesive films that can easily be attached to the required portion without using such as a film of polyurethane foam tape laminated body and a method of manufacturing the same.

In general, electronic devices using displays such as smart phones and tablet PCs use cushioning materials and sealing materials made of synthetic resin for the purpose of shock absorption, waterproofing, and dustproofing. In recent years, these electronic devices have gradually become smaller, slimmer (Specifically, a thin film having a thickness of 200 μm or less, a density of 0.25 to 0.40 g / cm 3 at a level of 0.25 to 0.40 g / cm 3) capable of maintaining a sufficient buffering and sealing function even when the thickness of the buffer material / , And a 25% compression force deflection (CFD) value of from 0.18 to 0.36 kgf / cm 2), and a cross-sectional or double-sided adhesive strength of 600 to 1500 gf / inch.

Olefin-based or acrylic-based materials are mainly used as raw materials for the cushioning material / sealing material used in such electronic devices. However, in the case of these materials, not only the thickness strain at the quality inspection temperature (70 to 80 ° C) There has been a problem in that the thickness strain is very high when laminating or laminating the fabric itself. Recently, a curable polyurethane material having a smaller thickness strain than the above materials has been attracting attention as disclosed in the following [1].

The cushioning polyurethane cushioning material and sealant are prepared by a method of forming a bubble cell inside a foam laminate by using carbon dioxide generated by the reaction of isocyanate with water contained in the foam composition as disclosed in detail in Document 1 (That is, the density becomes lower as the thickness becomes thicker) depending on the molding thickness.

However, the technique according to the following [1] is advantageous in that it has a low density of about 0.10 to 0.25 g / cm 3 when compared with the previously developed cushioning polyurethane material and the sealing material. However, The thickness of the cushioning material and the sealing material required in recent years can not be satisfied and the gap between the parts of the electronic device can not be effectively filled.

In order to solve this problem, when a conventional curing-type polyurethane manufacturing method is applied to form a desired thickness of 150 to 200 탆, the density of the foam laminate increases to a level of 0.7 to 0.8 g / cm 3 (25% CFD value of 1 kgf / cm 2 or more), the cell structure formed inside the foam laminate is scarce, so that the function as a cushioning material and a sealing material can hardly be performed.

In addition, the following [Document 1] discloses that when the artificial skin film is laminated and cured, the foam is swollen 2 to 4 times due to chemical foaming in the foam layer, so that the thickness of the foam composition is preferably set to 50 to 80 탆 (Roll coater, comma coater, knife coater), it is difficult to coat the foamed composition on the base film with a thickness of 80 탆 or less, and further, the coating thickness of the foamed composition is 30 to 50 It is not suitable for a method of producing a polyurethane foam laminate having a molding thickness of 100 to 150 탆 which can be obtained by applying the polyurethane foam layer at a level of 탆.

This problem is caused by the use of water contained in the foam composition as a chemical foaming agent as described in [1] below, and therefore, by solving such a problem, it is possible to maintain a thin thickness required in recently- A new method for forming a cured polyurethane foam laminate having physical properties capable of providing a buffering and sealing function is desperately required.

Further, in the case of the technique according to the following [Document 1], a separate base material and / or an inorganic material type double-sided adhesive film or the like should be used in order to attach the polyurethane material to a site requiring buffering or airtightness. In this case, The problem of non-adhesion to the foam due to non-uniformity of the adhesive force, tearing of the foam, and the like, resulting in a decrease in productivity and an increase in production cost due to an excessive defect rate .

[Patent Document 1] Korean Patent No. 10-1149013 (Bulletin of May 24, 2012)

An object of the present invention is to provide a polyurethane foam laminate which is formed in a tape form by forming an adhesive layer on the polyurethane foam laminate itself so that it can be easily adhered to a site requiring buffering or airtightness without using a separate adhesive or a double- A urethane foam tape laminate and a process for producing the same.

Another object of the present invention is to provide a method for producing a foamed polyurethane foam tape laminate, which comprises adding a water absorbent to a foamed composition to form a foamed laminate constituting the thin film polyurethane foam tape laminate to inhibit a chemical foaming reaction by residual moisture contained in the foamed composition, Instead, in the prior art, by replacing the cell structure formed inside the foam laminate by the chemical foaming reaction with a hollow hollow sphere having a small intercellular cohesion phenomenon, a thin polyurethane foam laminate capable of forming a very thin polyurethane foam laminate at a low density A foam tape laminate and a method of manufacturing the same.

Another object of the present invention is to provide a thin film polyurethane foam tape laminate having physical properties suitable for use as a sealing material and a cushioning material for electronic devices using a display such as a smart phone and a tablet PC, The foam tape laminate has a thickness of 100 to 200 탆, a density of 0.25 to 0.40 g / cm 3, a 25% CFD of 0.18 to 0.36 kgf / cm 2, an average cell size of 40 to 60 탆, and a surface adhesive force of 600 to 1500 gf / inch .

A polyurethane foam thin film layer formed on an upper surface of the base film layer using a foam composition comprising a base film layer, a polyol A, a polyol B, a polyol C and an isocyanate, and a polyurethane foam thin film layer formed on the polyurethane foam thin film layer Wherein the polyol A is a polyester-based triol-based or diol-based polyol having a molecular weight of 2,000 to 4,000 and containing 20 to 40 functional groups, and contains 15 to 25% of ethylene oxide , And the polyol B is a polyester-based polyol having a molecular weight of 400 to 800 and containing 200 to 400 functional groups, and the polyol C is a caprolactone series having a molecular weight of 400 to 800 and a functional group of 200 to 400 Or a diol-based triol system.

The adhesive layer is formed by a coating method of at least one of reverse gravure, gravure, and microgravure as a solventless UV curable adhesive layer. The thin film polyurethane foam tape laminate has a thickness of 100 to 200 탆. The polyurethane The foam thin film layer portion has a density of 0.25 to 0.40 g / cm 3, a 25% CFD of 0.18 to 0.36 kgf / cm 2, and an average cell size of 40 to 60 μm.

The method for producing a thin film polyurethane foam laminate having a UV coating adhesive layer according to the present invention is characterized in that a mixture containing polyol A, polyol B, polyol C and isocyanate is mechanically foamed by a gas for conditioning, A second step of applying the foam composition to a top surface of the first base film layer to a predetermined thickness, a second base film layer on the surface of the applied foam composition, A third step of forming a polyurethane foam thin film layer on the first base film layer and a fourth step of releasing the second base film layer and forming an adhesive layer on the surface of the cured polyurethane foam thin film layer, Is a polyester-based triol or diol system having a molecular weight of 2,000 to 4,000 and 20 to 40 functional groups, an ethylene oxide content of 15 to 25%, and the polyol B is a poly The polyol C is a caprolactone series having a molecular weight of 400 to 800 and containing 200 to 400 functional groups and having a molecular weight of 400 to 800 and a functional group of 200 to 400, Or diol-based.

The polyol is mixed in a ratio of 40 to 60 parts by weight, 15 to 35 parts by weight and 15 to 35 parts by weight of polyol A, polyol B and polyol C, respectively, and the isocyanate is contained in an amount of 25 to 40 wt. By weight.

The mixture of the first step may further comprise a water absorbent for removing moisture which is a chemical blowing agent contained in the foam composition, and a hollow hollow sphere for providing a foam cell in the foam composition.

The water absorbent is added as a zeolite in a proportion of 0.5 to 5 parts by weight based on 100 parts by weight of the polyol. The micro hollow spheres are artificial bubbles having a cell size of 20 to 80 μm and a specific gravity of 0.02 to 0.20 g / And 0.1 to 2 parts by weight per 100 parts by weight of the polyol.

The method may further include a fifth step of bonding the release paper to the adhesive layer formed in the fourth step.

In addition, in the fourth step, the adhesive layer is formed by coating UV-curable adhesives with a solvent-free UV curing system by any coating method such as reverse gravure, gravure or microgravure and then irradiating UV light. The adhesive layer has a thickness of 5 to 100 μm , And an adhesive strength of 600 to 1500 gf / inch.

The thin film polyurethane foam tape laminate according to the present invention is formed so that the adhesive layer is formed on the upper side of the polyurethane foam thin film layer so that the laminate itself has adhesiveness. Therefore, even when a separate adhesive application or double- There is an advantage that it can be easily attached to a part where airtightness is required.

Also, the thin film polyurethane foam tape laminate according to the present invention and the method for manufacturing the same can suppress the chemical foaming reaction by residual moisture by adding zeolite to the foam composition as a water absorbent to adsorb the residual moisture contained in the foam composition, It is possible to form an adhesive polyurethane foam laminate having a very thin thickness at a low density by adding a micro hollow spherical body with little aggregation.

In addition, according to the present invention, a thin film polyurethane foam tape laminate which can be used as a sealing material and a shock absorber for sealing or sealing impacts of highly integrated parts in an electronic device using a display, such as a smart phone, The thin film polyurethane foam tape laminate has a thickness of 100 to 200 μm, a density of 0.25 to 0.40 g / cm 3, a 25% CFD of 0.18 to 0.36 kgf / cm 2, an average cell size of 40 to 60 μm, 600 to 1500 gf / inch.

1 is a cross-sectional view showing the structure of a thin film polyurethane foam tape laminate according to the present invention,
2 is a process drawing showing a method for producing a thin film polyurethane foam tape laminate according to the present invention, and
3 is a schematic view for explaining the structure of an apparatus for producing a thin film polyurethane foam tape laminate according to the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.

While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings and will herein be described in detail. It should be understood, however, that the invention is not intended to be limited to the particular embodiments, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.

1, the thin film polyurethane foam tape laminate manufactured according to the present invention comprises a first base film layer 21, a polyurethane foam thin film layer 31 formed on the top surface of the first base film layer 21, , And an adhesive layer (81) coated on the surface of the polyurethane foam thin film layer (31).

Here, the "adhesive layer " used throughout this specification and claims includes not only conventional adhesive properties but also sticky or viscous properties.

The thin film polyurethane foam tape laminate according to the present invention is obtained by mechanically foaming a foam composition (that is, a raw material composition for forming a polyurethane foam laminate) constituted as described below, ) To a predetermined thickness and then thermally cured.

Herein, the term "mechanical foaming" as used throughout this specification and claims means that the mixture of the foamed composition is stirred by using a mechanical stirrer or the like (mixer head is mixed with polyol, isocyanate, (Process) It means that air bubbles (or bubbles) are generated in the foam composition.

In the case of the present invention, the foamed composition comprises polyol and isocyanate, which are raw materials for synthesizing polyurethane, and other additives such as surfactants, catalysts, carbon-based pigments, water absorbents, and micro hollow spheres.

The polyol may be a mixture of a polyester series and a caprolactone series. In this embodiment, the polyol A, the polyol B, and the polyol C are mixed.

At this time, the polyol A is polyester-based, has a molecular weight of 2000 to 4000, and has a triol or diol system containing 20 to 40 functional groups, an ethylene oxide content of 15 to 25%, a polyol B, And the polyol C is a caprolactone polyol series having a molecular weight of 400 to 800 and a triol type or diol type containing 200 to 400 functional groups do.

The polyol is used in a ratio of 40 to 60 parts by weight of polyol A, 15 to 35 parts by weight of polyol B and 15 to 35 parts by weight of polyol C. In the case of this embodiment to be described later, 50 parts by weight of polyol A, And 25 parts by weight of polyol C were mixed and used.

The above-mentioned isocyanate (MDI) may be at least one of aromatic, alicyclic and aliphatic, and may be a bifunctional isocyanate having two isocyanate groups in one molecule, three or more isocyanate groups in one molecule, A trifunctional or higher isocyanate having a hydroxyl group, or a combination thereof.

The isocyanate may be used either alone or in combination with a certain ratio depending on the product characteristics (hardness, density, reactivity), such as Polymeric MDI, Monomeric MDI and Modified MDI. 90 to 110. < / RTI >

The isocyanate is preferably used in a ratio of 25 to 40 parts by weight based on 100 parts by weight of the polyol. In this embodiment, the isocyanate is used in a ratio of 35 parts by weight based on 100 parts by weight of the polyol.

If necessary, a crosslinking agent may be further added during the polyurethane synthesis. If the crosslinking agent is not mixed, it is preferable to add the crosslinking agent because the crosslinking density becomes poor and the heat resistance of the polyurethane foam lowers.

The crosslinking agent may be 1,4BD (1,4 butanediol), TEG (triethylene glycol), TPG (tripropylene glycol), DEG (diethylene glycol), and the like. It is preferable to use TEG which is free from freezing point and has good workability and can improve physical properties.

The amount of the cross-linking agent is preferably 2 to 7 parts by weight based on 100 parts by weight of the polyol, and 5 parts by weight with respect to 100 parts by weight of the polyol in the present invention.

On the other hand, the foam stabilizer is a nonionic surfactant such as polydimethylsiloxane or polyoxyalkylene for stabilizing the bubble cell. By using the nonionic surfactant as a foam stabilizer, A suitable bubble cell structure can be formed inside the polyurethane foam.

The foam stabilizer is preferably added in an amount of 1 to 3 parts by weight based on 100 parts by weight of the polyol. In the following examples, the foam stabilizer is added in an amount of 2 parts by weight based on 100 parts by weight of the polyol.

The catalyst may be at least one selected from the group consisting of an amine catalyst and a metal catalyst (organometallic compound catalyst, nickel acetate). Examples of the amine catalyst include monoamine compounds, diamine compounds, triamine compounds, polyamine compounds, Compound, an alcohol amine compound, and an ether amine compound.

 When the amine catalyst is used in combination with the metal catalyst (nickel acetate), the amine catalyst is used in an amount of 0.03 parts by weight based on 100 parts by weight of the polyol, and the metal catalyst (nickel acetate) is used in an amount of 1.5 parts by weight based on 100 parts by weight of the polyol. Is preferably added.

In addition, the carbon-based pigment is for coloring the polyurethane foam laminate and is preferably added in a proportion of 0.5 parts by weight based on 100 parts by weight of the polyol.

On the other hand, the water absorbent functions to inhibit the chemical foaming reaction by moisture remaining in the foam composition, which is constituted as described above, to restrict the expansion of the foam laminate, and the moisture absorbed in the polyol producing or packaging step About 0.05 to 0.08 part by weight based on parts by weight) or moisture naturally produced in the raw material mixture.

In the prior art, since the bubble cell is formed in the polyurethane foam laminate by using water (water) contained in the foam composition as a chemical foaming agent, in order to maintain a low density, as described in [1] In order to solve this problem, in the present embodiment, the moisture contained in the foamed composition is previously removed by using the water absorbent as described above, thereby suppressing unnecessary chemical foaming, thereby preventing the polyurethane foam laminate And it is a technical feature that the thickness of the sieve is extremely thinly formed to 200 탆 or less which is the latest required level.

To this end, zeolite was used as the water absorbent in this embodiment. Specifically, a synthetic molecular sieve (Molyceracibe) was used as a synthetic zeolite produced by Linde Corporation in the United States.

The molybdenum carbide is prepared and mixed in the form of powder, and has high adsorption power against liquid water or vapor. In addition, the molybdenum carbide powder has 3A, 4A, and 5A depending on the pore size, and is useful for adsorbing specific molecules with a constant pore size. Since the catalyst has high catalytic properties and most of the pores have a fine pore structure, Or high adsorption power in a low temperature environment.

It is preferable that the water absorbent (that is, the molybdenum powder in this embodiment) is added in an amount of 0.5 to 5 parts by weight based on 100 parts by weight of the polyol. In the case of the present invention described below, By weight.

On the other hand, when the moisture contained in the foamed composition is removed, the thickness of the foamed laminate can satisfy the required level of 200 μm or less. However, since the content of the foamed cells contained in the foamed laminate is small, So that a function as a cushioning material and a sealing material can not be performed.

Therefore, in the present invention, in order to replace the bubble cell structure by the chemical foaming according to the prior art, the micro hollow spheres and the gas for conditioning are added to the foamed composition, so that the polyurethane foam laminate satisfies the recently required thickness level of 200 μm or less Density property of 0.25 to 0.40 g / cm < 3 > which can provide a sufficient buffering function and a sealing function.

In this case, the micro hollow spheres are micro sized hollow micro spheres having a hollow center, with a cell size of 20 to 80 탆 and a specific gravity of 0.02 to 0.20 g / cm 3, preferably a density of 0.04 g / Lt; RTI ID = 0.0 > um. ≪ / RTI >

The micro hollow spheres are made of plastic, glass or the like, and acrylic copolymer, glass acrylic copolymer and polyvinylidene chloride are synthesized and used.

As described above, by adding the hollow hollow spheres to the inside of the foamed composition, not only the density of the foamed laminate can be maintained at a low density, but also the artificially processed hollow spheres having very small size tend to cling to each other, That is, the surface smoothness of the polyurethane foam foam can be stabilized due to the characteristics of the micro hollow spheres having little intercellular aggregation phenomenon.

That is, in the case where bubbles are formed only depending on a later-described gas (nitrogen) for conditioning, a foaming composition in gas-liquid mixing is applied to the first base film layer 21 in a coating state, When the phenomenon that the foamed composition of the foamed structure is partially retained occurs, strong cohesion between the foamed cells due to the foamed gas causes a large-sized bubble to be formed, thereby deteriorating the overall surface smoothness of the foamed laminated body.

However, when the micro hollow spheres are added as in the present invention, even if the foamed composition of the vapor-liquid mixture is partially retained by the coater blade during the transfer process, the microporous sphere aggregation phenomenon remarkably drops due to the characteristics of the micro hollow spheres, The cell size is stable and the bubble cell is small and uniformly generated, so that the surface smoothness of the foam laminate can be increased.

In the case where micro hollow spheres are added without forming bubbles through chemical foaming by water contained in the foamed composition as in the present invention, the average size of the cells can be stably and uniformly maintained at a level of 40 to 60 탆, Since the ratio of the open cells in the foam laminate increases, it can be used effectively as a waterproof foam having excellent waterproof function.

In addition, the above-mentioned shaping gas is mixed with a foaming composition in the mechanical foaming step to form a bubble cell inside the foam laminate, and a gas (nitrogen in this embodiment, for example) which does not adversely affect the reaction between the polyol and isocyanate, Is preferably used.

At this time, it is preferable that the gas for conditioning is contained so that the blending ratio in the polyurethane raw material is such that the volume ratio is 30 to 75% with respect to the total volume of the foamed composition.

The process for producing the thin film polyurethane foam tape laminate according to the present invention using the foamed composition as described above and the schematic configuration of the device used therefor will be described with reference to FIGS. 2 and 3. FIG.

First, the process for producing a thin film polyurethane foam tape laminate according to the present invention comprises the steps of: (S10) producing a foam composition for gas-liquid mixing; (S20) applying the foam composition to a first base film layer 21; (S30, S40) of forming a polyurethane foam thin film layer (31) on the upper surface of the first base film layer (21) by a thermosetting process in a state where a second base film layer is adhered to a coating surface of the foam composition, (S50, S60) of winding the finished product after the adhesive layer 81 is formed on the upper surface of the polyurethane foam thin film layer 31 by releasing the film layer.

As shown in FIG. 3, the apparatus for producing a thin film polyurethane foam tape laminate used in the present invention for carrying out the above-described manufacturing process includes a mixer 10, an ejector 13, a first winding roll 20, A pick-up roll 30, a thermosetting portion 50, an adhesive layer coating portion 70, an adhesive layer UV curing portion 80, and a first recovery roll 90.

The apparatus for producing a polyurethane foam laminate according to the present invention is characterized in that the second base film layer 41 is laminated (or adhered) as an artificial skin film on the foamed composition of the gas-liquid mixture which enters the thermosetting step, and after the heat- And a second take-up roll 40 and a second take-up roll 60 for releasing the second take-up roll.

If necessary, the polyurethane foam laminate manufacturing apparatus may further include a thickness adjusting member 14 disposed behind the discharger 13 to limit the thickness of the foamed composition of the gas-liquid mixture applied on the first base film layer 21 It may be additionally installed.

When the raw material for producing the thin film polyurethane foam tape laminate according to the present invention is put into the mixer 10, mechanical blending is performed together with mixing of the materials in the mixer 10, Raw material composition).

The foamed composition thus prepared is supplied to a discharger 13 to be described later. To this end, a connecting pipe 11 is provided between the mixer 10 and the discharger 13, A control valve 12 is provided.

Accordingly, a proper amount of the foamed composition that has undergone the mechanical foaming process in the mixer 10 as it operates the opening of the control valve 12 is supplied to the discharger 13, which will be described later, through the connecting pipe 11, The specific gravity of the foam composition in the vapor-liquid mixed state is approximately 0.25 to 0.40 g / ml.

 The discharger 13 discharges the foamed composition in the gas-liquid mixed state supplied from the mixer 10 onto the first base film layer 21 which is fed at a constant speed by the first take-up roll 20 and the pickup roll 30 And performs a function of coating.

The discharger 13 may be constructed using a conventional discharging device such as a nozzle as in the prior art. However, in the embodiment of the present invention, it is possible to prevent a part of the foamed composition from staying at the front end of the coater, And the discharger 13 is configured as a slot die so as to adjust the thickness of the coating liquid applied on the first base film layer 21 to a desired level.

On the other hand, the second base film layer 41 supplied from the second wind-up roll 40 is transported at a predetermined distance from the first base film layer 21 and recovered to the second recovery roll 60, In order to prevent the bubbles contained in the polyurethane foam thin film layer 31 from being released during the process of forming the polyurethane foam thin film layer 31 by thermally curing the foam composition applied to the base film layer 21, (Or the surface of the polyurethane foam thin film layer after the thermal curing process).

The first base film layer 21 and the second base film layer 41 may be formed of a material selected from the group consisting of polyethylene terephthalate (PET), black polyethylene terephthalate (PET) for shading, teflon belt, polyethylene terephthalate (PET) And acrylic adhesive cross-section tapes may be used as a material of the base film.

In this embodiment, a release type polyethylene terephthalate was used as a material of the second base film layer 41 in order to make the surface of the polyurethane foam laminate flat during release.

The foamed composition of the vapor-liquid mixture discharged from the discharger 13 and coated on the first base film layer 21 is cured in the process of passing through the thermosetting part 50 to form the polyurethane foam thin film layer 31.

At this time, the thermosetting part 50 is divided into three process sections independently by the first to third heating parts 51 to 53. First, the first heating part 51 is connected to the preheating section free heating zone. The temperature range of this zone is 60 ~ 80 ℃. The second heating section 52 is a concentrated hardening section, and the temperature range is 100 to 130 ° C.

The surface of the polyurethane foam thin film layer 31 hardened through the first and second heating portions 51 and 52 may be unevenly formed when the temperature suddenly rises at a high temperature. To solve this problem, the third heating unit 53 lowers the high-temperature atmosphere, and the temperature range of the third heating unit 53 is 60 to 80 ° C.

At this time, the second base film layer 41 attached to the polyurethane foam thin film layer 31 is released after passing through the thermosetting part 50. The released base material film layer 41 is transferred to the second recovery roll 60 Respectively.

In order to impart adhesiveness to the polyurethane foam laminate, an adhesive layer is formed on the surface of the polyurethane foam thin film layer 31 cured by the thermosetting part 50. For this purpose, The surface of the polyurethane foam thin film layer 31 is coated with a UV curable adhesive capable of being cured by ultraviolet irradiation to form an adhesive layer.

In this case, the UV curable adhesive is coated on the surface of the polyurethane foam thin film layer 31 using at least one coating method of microgravure, reverse gravure having 100 to 250 necks, or gravure, And the adhesive layer is formed by curing. As the UV irradiation, for example, Hg, Mtl (Fe) UV LAMP having a UV Intensity of 2.5 m / min-700 mj or more can be used.

The UV curing type adhesive may be a solvent type or a solventless type. Examples of the UV curing type adhesive include a UV-curable type adhesive such as a styrene-butadiene copolymer latex and a styrene-isoprene block copolymer, an ultraviolet curing type acrylic adhesive, And an ultraviolet hardening type adhesive.

As a specific example, the ultraviolet curable adhesive may be an acrylonitrile butadiene copolymer, an acrylonitrile butadiene styrene copolymer, an acrylonitrile butadiene methyl methacrylate, an n-butyl acrylate copolymer, a modified rubber, a modified acrylic rubber, a polyurethane Rubber, hydrogenated acrylonitrile butadiene copolymer, hydrogenated acrylonitrile butadiene styrene copolymer, hydrogenated acrylonitrile butadiene methyl methacrylate copolymer, acrylonitrile butadiene methyl methacrylate silicone copolymer, hydrogenated acrylonitrile butadiene methyl methacrylate But the present invention is not limited thereto. Other known materials may be used within the range of performing the same function.

When coating (or coating) of the ultraviolet curable adhesive is completed on the upper part of the polyurethane foam thin film layer 31 as described above, the UV curable part 80 of the adhesive layer is irradiated with ultraviolet light having a very short wavelength to form the polyurethane foam thin film layer 31 And the adhesive layer 81 is laminated on the surface of the polyurethane foam thin film layer while passing through the adhesive layer UV curing portion 80. Thereafter, the polyurethane foam laminate in which the adhesive layer 81 is laminated is recovered to the first recovery roll 90.

The first base film layer 21 thus produced can be formed to a thickness of 15 占 퐉, the adhesive layer 81 to a thickness of 5 to 100 占 퐉 and the polyurethane foam thin film layer 31 to a thickness of 80 to 180 占 퐉, and the polyurethane foam laminate Has a total thickness of 100 to 200 占 퐉, a density of 0.25 to 0.40 g / cm3, a 25% CFD of 0.18 to 0.36 kgf / cm2, and an average cell size of 40 to 60 占 퐉.

Also, it is preferable that the adhesive layer 81 is formed to have an adhesive strength of about 600 to 1500 gf / inch (which is a concept including adhesive force).

Although not described in the present embodiment, after the completion of the step S50 (that is, after the formation of the adhesive layer is completed), before the step S60 is performed, the adhesive layer 81 ) May be further subjected to a step of laminating a release film on the top of the release film.

At this time, the release film to be used may be PE (polyethylene) or a release PET (polyethylene terephthalate) material.

Although the adhesive layer 81 is formed by UV coating in this embodiment, it may be formed by any other known method of forming an adhesive layer on the thin film if necessary.

In order to evaluate the physical properties of the polyurethane foam laminate according to the present invention prepared by the above-mentioned method, the physical properties of the six examples prepared according to the present invention and the comparative examples prepared according to the prior art were compared, The results are shown in Table 1.

Commonly applied test conditions for the six comparative examples and the four comparative examples applied to the comparative test site and the test conditions individually applied for each are as follows.

For the sake of convenience of explanation, the above-described physical property comparison test was excluded from the influence of the formation of the adhesive layer.

≪ Conditions Commonly Applied to Examples and Comparative Examples >

- Polyol A: Polyol-based triol or diol having a molecular weight of 2000 to 4000 and 20 to 40 functional groups, with an ethylene oxide content of 15 to 25% and a content of 50 parts by weight.

- Polyol B: Triol type or diol type having a molecular weight of 400 to 800 and containing 200 to 400 functional groups and being added in a proportion of 30 parts by weight based on 100 parts by weight of polyol.

-Polyol C: Triol or Diol series having a molecular weight of 400 to 800 as a caprolactone series and containing 200 to 400 functional groups and being added in a proportion of 25 parts by weight based on 100 parts by weight of polyol.

- Isocyanate: Polymeric MDI was used and added at a ratio of 40 parts by weight to 100 parts by weight of the polyol.

Polishing agent: Polydimethylsiloxane was used and added in a proportion of 2 parts by weight based on 100 parts by weight of the polyol.

- Catalyst: An amine catalyst (0.03 parts by weight based on 100 parts by weight of polyol) and nickel acetate (1.5 parts by weight based on 100 parts by weight of polyol) were mixed.

- Carbon series pigments: 0.5 parts by weight based on 100 parts by weight of polyol.

(Example 1)

, 0.05 part by weight based on 100 parts by weight of the polyol, 3 parts by weight based on 100 parts by weight of the polyol of zeolite (molybdenum carbide powder), and 100 parts by weight of the micro hollow spheres based on 100 parts by weight of the polyol , The coating thickness of the gas-liquid mixture applied by the discharger 13 is 80 占 퐉, the mixing nitrogen content is 60% in the polyurethane raw material, the second base film layer 41 is made of artificial skin film To form and cure a polyurethane foam laminate, followed by forming a UV-curable adhesive coating film having a thickness of 5 mu m.

(Example 2)

A polyurethane foam laminate was produced under the same conditions as in Example 1 except that the coating thickness of the gas-liquid mixture applied by the discharger 13 was set at 100 탆, and then the UV-curable adhesive coating film was formed to a thickness of 10 탆 box.

(Example 3)

A polyurethane foam laminate was produced under the same conditions as in Example 1 except that the coating thickness of the gas-liquid mixture applied by the discharger 13 was 100 탆 and the mixing ratio of nitrogen for the coating was 65% The adhesive agent coating film is formed to a thickness of 15 탆.

(Example 4)

A polyurethane foam laminate was produced under the same conditions as in Example 1 except that the coating thickness of the gas-liquid mixture applied by the discharger 13 was 120 탆 and the mixing ratio of nitrogen for the coating was 65% The adhesive agent coating film is formed to a thickness of 20 占 퐉.

(Example 5)

A polyurethane foam laminate was produced under the same conditions as in Example 1 except that the coating thickness of the gas-liquid mixture applied by the discharger 13 was 150 탆 and the mixing ratio of nitrogen for deposition was 67%.

(Example 6)

A polyurethane foam laminate was produced under the same conditions as in Example 1 except that the coating thickness of the gas-liquid mixture applied by the discharger 13 was 200 탆 and the mixing ratio of nitrogen for the coating was 75%.

(Comparative Example 1)

Zeolite and micro hollow spheres were not used in the conditions of Example 1 and the residual moisture content of the foam composition was 0.05 parts by weight based on 100 parts by weight of the polyol and the coating thickness of the gas-liquid mixture applied by the discharger 13 And the second base film layer 41 as the artificial skin film, the polyurethane foam laminate is produced.

(Comparative Example 2)

The polyurethane foam laminate was produced under the same conditions as in Comparative Example 1 except that the residual moisture content of the foam composition was 0.3 parts by weight based on 100 parts by weight of the polyol.

(Comparative Example 3)

A polyurethane foam laminate was prepared under the same conditions as in Comparative Example 1 except that the micro hollow spheres were added at a ratio of 0.5 part by weight per 100 parts by weight of the polyol and the coating thickness of the gas-liquid mixture applied by the discharger 13 was 150 占 퐉, Nitrogen for the preparation of the polyurethane foam laminate was prepared without using the second base film layer 41 as the artificial skin film in the mixing ratio of 50% to the polyurethane raw material.

(Comparative Example 4)

A polyurethane foam laminate was produced under the same conditions as in Comparative Example 1 except that the coating thickness of the gas-liquid mixture applied by the discharger 13 was 150 占 퐉, the mixing ratio of the polyurethane raw material to the polyurethane raw material was 30% A polyurethane foam laminate was produced without using the second base film layer 41 as a film.

The term " surface health bubble "as used in Table 1 means small bubbles blowing up to the surface of the foam immediately after inflated to the maximum extent in the free foam, and the thin film polyurethane foam laminate The evaluation of physical properties is as follows.

- Density (g / cm3): measured according to the method of ASTM D3574.

- 25% CFD: measured by a universal material testing machine according to the method of ASTM D3574.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 The coating thickness (mu m) applied to the first base film layer 80 100 100 120 150 200 200 200 150 150 Nitrogen mixture ratio
(volume;%) 60 60 65 65 67 75 75 75 50 30 Moisture content
(Parts by weight) 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.3 0.05 0.05 Zeolite (parts by weight) 3 3 3 3 3 3 0 0 0 0 Micro hollow spheres (parts by weight) 0.3 0.3 0.3 0.3 0.3 0.3 0 0 0.5 0 The second base film layer (artificial skin film) ○ ○ ○ ○ ○ ○ ○ ○ × × Polyurethane foam thickness after curing (탆) 80 100 100 120 150 200 300 400 150 150 Density (g / cm3) 0.42 0.42 0.36 0.36 0.32 0.24 0.18 0.12 0.5 0.7 blowing magnification ± 5% One One One One One One 1.5 2 One One 25% C.F.D (kgf / cm2) 0.25 0.25 0.18 0.18 0.15 0.1 0.05 0.05 0.6 One Compression set (%) <5 <5 <5 <5 <5 <5 <10 <10 <5 <5 Average cell size (탆) 40 50 50 50 60 60 80 ~
150 80 ~
150 50 100 Surface health bubble inhibition ◎ ◎ ◎ ◎ ◎ ◎ ○ ○ ◎ △ Thickness of adhesive layer ( μm) 5 10 15 20 Adhesive strength (gf / inch) 500 600 900 1400

As shown in Table 1, the polyurethane foam laminate according to each of Examples 1 to 6 of the present invention all had the physical properties (thickness of 200 μm or less, 0.25 A low density of the order of 0.40 g / cm 3, and a low 25% CFD value of the order of 0.18 to 0.36 kgf / cm 2).

Specifically, in the case of Examples 1 to 6 according to the present invention, the thicknesses of 80 to 200 탆, the density of 0.24 to 0.42 g / cm 3, the 25% CFD of 0.1 to 0.25 kgf / cm 2 and the cell average size of 40 to 60 탆 And in the case of Examples 1 to 4, the adhesive strength is 500 to 1400 gf / inch when the thickness of the UV cured adhesive is 5 to 25 탆.

The thin-film polyurethane foam tape laminate according to the present invention has a remarkably thin thickness when compared with the prior art, and has a sufficient shock-absorbing function, a sealing function, and a physical property capable of providing adhesiveness, Able to know.

On the other hand, in the case of Comparative Examples 1 to 4 according to the prior art, when the density is low, the thickness is thick and when the thickness is thin, the density is high. As a result, the physical properties required as cushioning materials and sealing materials It can not be done.

In the case of the first to sixth embodiments of the present invention in which the water contained in the foam composition is removed by the water absorbent to suppress chemical foaming by water, All satisfied the required thickness.

Particularly, in comparison between Example 6 and Comparative Example 1 in which the same coating thickness is 200 占 퐉 and the nitrogen mixing ratio is 75%, Example 6 shows that the thickness of the polyurethane foam after curing is 200 占 퐉, In Comparative Example 1, the thickness after curing was 300 μm, which was significantly thicker than that in Example 6.

From these results, it can be directly known that when the water absorbent is used as in the present invention, the thickness of the foam laminate can be significantly reduced.

The results of Comparative Example 1 and Comparative Example 2, in which the other conditions except moisture content were the same, showed that the greater the amount of moisture contained in the foam composition, the thicker the foam laminate was formed, It can once again be confirmed that the technical features of the present invention, in which the water absorbent is applied to reduce the thickness of the water absorbent, is very reasonable.

Further, it can be understood that when the micro hollow spheres are applied as in the present invention, a thin foam laminate can be realized at a low density.

Next, the influence of the micro hollow spheres, which is another technical feature applied to the present invention, will be described. Examples 1 to 6 of the present invention in which water contained in the foam composition is removed by water absorbent to suppress chemical foaming by water In the case of Example 6, both the density and the 25% CFD were found to satisfy the required level as a whole, and it can be seen that the micro hollow spheres according to the present invention can effectively replace the chemical foaming effect according to the prior art.

In comparison with the results of Comparative Example 3 and Comparative Example 4 in which artificial skin membranes were not commonly used, the density was 0.5 g / cm 3 and 0.7 g / cm 3, respectively, because chemical foaming by water did not occur. % CFD of 0.6 kgf / cm 2 and 1 kgf / cm 2, respectively. However, in Comparative Example 3 in which micro hollow spheres were used, the suppression effect of the surface health bubble was very effective.

From these results, it was confirmed that the micro hollow spheres used in the present invention can provide not only an effect of realizing lower density of the foam laminate but also an effect of preventing the occurrence of surface health bubbles as described above.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is clearly understood that the same is by way of illustration and example only and is not to be taken as limitations. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

10: Mixer 11: Connector
12: Control valve 13: Discharger
20: first winding roll 21: first base film layer
30: pick-up roll 31: polyurethane foam thin film layer
40: second winding roll 41: second base film layer
50: thermosetting part 51: first heating part
52: second heating section 53: third heating section
60: second recovered roll 70: adhesive layer coating part
80: adhesive layer UV hardening part 90: first recovered roll

Claims (8)

A base film layer;
A polyurethane foam thin film layer formed on the upper surface of the base film layer using a foam composition comprising polyol A, polyol B, polyol C and isocyanate; And
And an adhesive layer formed on the upper surface of the polyurethane foam thin film layer,
The polyol A is polyester-based, has a molecular weight of 2000 to 4000, and is a triol or diol system containing 20 to 40 functional groups, and contains 15 to 25% of ethylene oxide,
The polyol B is a polyester-based triol type or diol type having a molecular weight of 400 to 800 and containing 200 to 400 functional groups,
Wherein the polyol C is a caprolactone series having a molecular weight of 400 to 800 and a triol type or diol type containing 200 to 400 functional groups. The method according to claim 1,
The adhesive layer is a UV-curable adhesive layer of a solventless type and is formed by a coating method of at least one of reverse gravure, gravure, or microgravure,
Wherein the polyurethane foam thin film layer portion has a density of 0.25 to 0.40 g / cm 3, a compression force deflection (CFD) of 25% to 0.18 to 0.36 kgf / cm 2, a cell average size of 40 To 60 m. &Lt; / RTI &gt; A first step of mechanically foaming a mixture containing a polyol A, a polyol B, a polyol C and an isocyanate with a gas for conditioning to produce a foam composition of a gas-liquid mixture;
A second step of applying the foamed composition to the upper surface of the first base film layer to a predetermined thickness;
A third step of attaching a second base film layer to the surface of the applied foamed composition and forming a polyurethane foam thin film layer on the upper surface of the first base film layer by a thermal curing process; And
And a fourth step of releasing the second base film layer and forming an adhesive layer on the surface of the cured polyurethane foam thin film layer,
The polyol A is polyester-based, has a molecular weight of 2000 to 4000, and is a triol or diol system containing 20 to 40 functional groups, and contains 15 to 25% of ethylene oxide,
The polyol B is a polyester-based triol type or diol type having a molecular weight of 400 to 800 and containing 200 to 400 functional groups,
Wherein the polyol C is a caprolactone series having a molecular weight of 400 to 800 and a triol type or diol type containing 200 to 400 functional groups. The method of claim 3,
The polyol is mixed at a ratio of 40 to 60 parts by weight, 15 to 35 parts by weight and 15 to 35 parts by weight, respectively, of polyol A, polyol B and polyol C,
Wherein the isocyanate is mixed at a ratio of 25 to 40 parts by weight based on 100 parts by weight of the polyol. The method of claim 3,
Wherein the mixture of the first step further comprises a water absorbent for removing moisture which is a chemical blowing agent contained in the foam composition, and a hollow microsphere. 6. The method of claim 5,
The water absorbent is added as a zeolite in a proportion of 0.5 to 5 parts by weight based on 100 parts by weight of the polyol,
Wherein the micro hollow spheres have a cell size of 20 to 80 탆 and a specific gravity of 0.02 to 0.20 g / cm 3 and are added in a ratio of 0.1 to 2 parts by weight to 100 parts by weight of the polyol . 7. The method according to any one of claims 3 to 6,
Further comprising a fifth step of laminating the releasing paper to the adhesive layer formed in the fourth step. &Lt; Desc / Clms Page number 20 &gt; 8. The method of claim 7,
In the fourth step, the adhesive layer is formed by coating a solventless UV curable adhesive with a coating method of at least one of reverse gravure, gravure, and microgravure, and then irradiating UV,
Wherein the adhesive layer has a thickness of 5 to 100 占 퐉 and an adhesive strength of 600 to 1500 gf / inch.
KR1020150110751A 2015-08-05 2015-08-05 Thin Film Polyurethanes Foam Tape Laminate having UV-curable Adhesive Layer and Manufacturing Method Thereof KR101631688B1 (en)

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KR101847147B1 (en) * 2017-01-25 2018-04-09 주식회사 에스제이폼웍스 Flexible buffer film for oled containing polyurethane foams and method of manufacturing the same
KR20210052351A (en) * 2019-10-30 2021-05-10 주식회사 에스제이폼웍스 Waterproof polyurethane foam

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KR20100107328A (en) * 2009-03-25 2010-10-05 (주)다락 Microsphere dispersed waterborne polyurethane and process for preparing the same
KR100944507B1 (en) * 2009-10-21 2010-03-03 권영구 Manufacturing method for low density polyurethane foam sheet having sealing, shock absorbing and slow rebound properties
KR20120076904A (en) * 2010-12-30 2012-07-10 주식회사 이파엘지종합특수방수 Structure for insulation-waterproof using nonsolvent urethane foam and method for the same
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KR101847147B1 (en) * 2017-01-25 2018-04-09 주식회사 에스제이폼웍스 Flexible buffer film for oled containing polyurethane foams and method of manufacturing the same
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KR102556255B1 (en) 2019-10-30 2023-07-17 주식회사 에스제이폼웍스 Waterproof polyurethane foam

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