JP2010254920A - Adhesive - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyurethane-based adhesive with a predetermined composition, which is applicable to various kinds of products as an adhesive. <P>SOLUTION: The adhesive includes: a polycarbonate diol-based urethane resin with a number-average molecular weight of 10,000-100,000; a polyisocyanate-based curing agent composed of hexamethylene diisocyanate (15.0-27.0% of the NCO content) with a weight ratio of 3:10-15:10; and one or more selected from methyl ethyl ketone, toluene, isopropyl alcohol, cyclohexanone, and 2-ethoxyethyl acetate of 50-75 wt.% of the total amount, as a solvent. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a urethane-based adhesive. More specifically, it can be suitably used as a reactive adhesive, has excellent properties such as adhesion and creep resistance, and is widely used as an adhesive for various adherends such as leather products, synthetic resin products, textile products, and woodwork products. It can be used effectively for various applications.

  Adhesives include natural adhesives such as natural rubber and starch, and synthetic adhesives such as acrylic, α-olefin, urethane, ethylene-vinyl acetate, epoxy, silicone, and cyanoacrylate. Can be classified. These adhesives are variously selected and used depending on the purpose, compatibility with the adherend, usage mode, and the like.

  Among these, urethane resins are widely used as base polymers for hot melts or adhesives. For example, in an invention relating to an adhesive (Patent Document 1) mainly composed of a hexamethylene diisocyanate polyisocyanate compound, focusing on the uretdione structure, which is a lower molecular weight structure than the isocyanurate structure, lowering the molecular weight and lowering the viscosity. In some cases, the effect of reducing volatile organic compounds (VOC) can be obtained.

  Further, in the invention relating to the fast-curing polyurethane coating composition (Patent Document 2), it comprises a mixture of 100 parts by weight of polyol, 1 to 30 parts by weight of cyclodextrin, 0.01 to 5.0 parts by weight of catalyst and organic polyisocyanate, Even if a catalyst is used, the pot life is long and the effect of increasing the curing time is obtained. Furthermore, in the invention relating to the laminated heat transfer marking sheet (Patent Document 3), a heat-sensitive adhesive layer mainly composed of a polyurethane resin or a polyester resin and a transparent resin layer mainly composed of a polyurethane resin are laminated. In addition, it can be easily transferred to a product molded into a complicated shape by heating, and a colored pattern having a good finish after transfer and excellent wear resistance and weather resistance can be formed by transfer.

  On the other hand, in the invention relating to the adhesive sheet for shoes (Patent Document 4), a polyester obtained by reacting 0.9 to 1.1 equivalents of a diisocyanate compound with 1 equivalent of a terminal hydroxyl group-containing polyester product having a hydroxyl value of at least 100 or less. To the urethane resin, 0.5 to 20 parts by weight of a trifunctional or higher functional isocyanate compound as a crosslinking agent was added to 100 parts by weight of the polyester urethane resin to form a sheet. As a result, the use of an organic solvent can be reduced, and the application work of the adhesive and the primer, which is a troublesome work in the shoe process, can be simplified. In addition, in the invention related to the thermosensitive adhesive composition for board (Patent Document 5), the particle board, the hard fiber are formed by the organic polyisocyanate adhesive composition containing the organic acid salt catalyst of the cyclic amine compound and the organic polyisocyanate compound. In the formation of various boards such as boards, it is possible to achieve both curability and pot life, and to obtain a board with excellent physical properties and high physical properties. Alternatively, in the invention related to the non-contact IC tag (Patent Document 6), one surface of the IC tag can be easily attached to a product by using any one of urethane-based and acrylic-based adhesive layers as an adhesive layer. is there.

  Further, in the invention relating to the polyurethane aqueous dispersion system adhesive composition (Patent Document 7), a polyurethane water dispersion obtained by containing a certain amount of a diol segment having a carboxyl group and converting the carboxyl group to a lithium salt A polyurethane water-based adhesive having excellent emulsification stability and excellent heat resistance, water resistance and light resistance is obtained by mixing with a curing agent.

  In addition to the proposals exemplified above, inventions using urethane-based resins as adhesives are very diverse, and their uses are increasingly expanding. However, it is necessary to use a combination of specific components depending on the respective adhesive application, adherend, target function, etc., and it is difficult to obtain sufficiently satisfactory adhesion durability for use as a so-called universal type adhesive. is the current situation.

JP-A-5-32759 JP-A-6-329982 JP-A-9-248996 Japanese Patent Laid-Open No. 10-192004 Japanese Patent Laid-Open No. 11-35918 JP 2000-251046 A JP 2004-18672 A

  As described above, the polyurethane resin is useful as a highly versatile adhesive, but it seems that there is still room for improvement as a so-called universal type adhesive. Therefore, an object of the present invention is to propose a polyurethane adhesive having a specific composition that can be bonded to a wide variety of products.

  As a result of intensive studies to solve the above-mentioned problems and achieve the intended purpose, the present invention is to extremely increase the amount of the curing agent used in the conventional urethane adhesive in a small amount. Has found that it is possible to provide polyurethane adhesives that can adhere to a wide variety of products.

  That is, the present invention provides a polycarbonate diol type urethane resin having a number average molecular weight of 10,000 to 100,000 and a polyisocyanate type curing agent composed of hexamethylene diisocyanate (NCO content of 15.0 to 27.0%). The present invention relates to an adhesive comprising a weight ratio of ˜15: 10 and containing at least one selected from methyl ethyl ketone, toluene, isopropyl alcohol, cyclohexanone and 2-ethoxyethyl acetate as a solvent. Is.

  The polycarbonate diol urethane resin used in the present invention preferably has a number average molecular weight of 10,000 to 100,000, more preferably 15,000 to 50,000. This is because if the molecular weight is less than 10,000, the solvent resistance of the resulting adhesive and the adhesion to the adherend tend to decrease, and if it exceeds 100,000, the viscosity of the adhesive increases and the operability is poor.

  The polyisocyanate curing agent used in the present invention has an isocyanate (NCO) content of 15.0 to 27.0%. The curing agent is prepared by reacting trimethylolpropane with diisocyanate such as tolylene diisocyanate or 1,6-hexane diisocyanate, and preferably has a number average molecular weight of about 500 to 1,000. The curing agent reacts with the hydroxyl group of the urethane resin to cure the adhesive. In the present invention, the weight ratio of the urethane resin: curing agent is mixed in the range of 3:10 to 15:10. It is a feature. Usually, these ratios are equimolar or slightly higher in curing agent, specifically 1: 1 to 1: 1.1 in terms of molar ratio.

  However, assuming that the weight ratio of 3:10 is used in the present invention and the urethane resin has a molecular weight of 10,000 and the curing agent has a molecular weight of 500, the molar ratio is 1: 66.6. It will be. Thus, by increasing the ratio of the curing agent, in the present invention, the adhesion to a very wide range of adherends could be improved. Probably, it is thought that the adhesive force is enhanced by reacting with the hydroxyl group present on the surface of the adherend, but the mechanism has not been elucidated.

  And in this invention, the mixture of the said urethane resin and a hardening | curing agent contains 50 to 75weight% of the whole with 1 or more types selected from methyl ethyl ketone, toluene, isopropyl alcohol, cyclohexanone, and 2-ethoxyethyl acetate as a solvent. It is. This is because the presence of the solvent keeps the adhesive in a liquid state and can maintain the state until it is applied to a desired adherend.

  The adhesive can be stored and circulated in a tube-type container such as polyethylene or polypropylene (for example, a container in which sauce or soy sauce accompanying a lunch box or the like is stored).

  In the present invention, a polycarbonate diol urethane resin having a number average molecular weight of 10,000 to 100,000 and a polyisocyanate curing agent composed of hexamethylene diisocyanate (NCO content of 15.0 to 27.0%) are 3:10. The adhesive can be suitably used for bonding the colored sheet formed by curing at a weight ratio of ˜3: 50 and the adherend. The urethane resin and the curing agent constituting the colored sheet have the same chemical structure and molecular weight as the adhesive of the present invention, but the ratio of the curing agent is extremely higher than the above ratio. This is because the crosslink density of the colored sheet can be increased thereby suppressing the volatilization of the dye as the colorant.

  It is preferable to use a sublimable dye for coloring the colored sheet. This is because the dyeing method is very simple and can express various shapes, patterns, and colors.

  The adhesive of the present invention is preferably used, for example, for bonding an IC tag to an adherend. As a conventional method of fixing an IC tag, an IC tag storage portion is formed in advance on an adherend, and is fixed so as to be inserted therein, or placed in a cloth bag and sewn with an adherend. It was. If the adhesive of the present invention is used, the IC tag can be bonded to the adherend as it is, and if the adherend is flexible (for example, a doormat or a blanket), the heat resistant urethane is wrapped around the IC tag. It is preferable to coat using a sheet such as.

  In addition, the adhesive of the present invention can be used for bonding an embroidered fabric (such as a patch) to an adherend. At this time, the hot melt adhesive layer or polyester made of a thermoplastic polyurethane resin is used instead of directly bonding the fabric and the adhesive so that the adhesive does not penetrate into the fabric and the adhesive strength with the adherend is not lowered. It is desirable that the adhesive layer of the present invention is used to prevent excessive entry of the adhesive of the present invention by heating and pressing the adhesive layer, and to bond the hot melt adhesive layer or the polyester adhesive layer to the adherend. A hot melt layer or a polyester adhesive layer may be formed on the entire surface of the cloth, or may be formed on a part of the cloth.

  Furthermore, a conventionally used mark fabric may be used instead of the embroidered fabric. A conventional mark fabric is, for example, a laminate of a color heat-resistant urethane layer and a hot-melt layer on a pet film. Usually, after processing into a desired shape with a cutting plotter or the like, it is applied to an adherend such as a textile product. On the other hand, a hot melt layer is brought into contact and is adhered by heating and pressing from above the pet film. Originally, the hot melt layer penetrates and adheres between the fibers of the fiber product by melting, but by using the adhesive of the present invention, even for products that are difficult to heat to high temperatures. It can be easily bonded.

  The material of the adhesion surface of the adherend is not particularly limited by using the adhesive of the present invention, and leather (for example, bags, leather shoes, etc.), natural rubber, nitrile-butadiene rubber (for example, doormat) Etc.), styrene-butadiene rubber, chloroprene rubber, isoprene rubber, butadiene rubber, urethane rubber (for example, a tire), acrylic rubber, and soft polyvinyl chloride.

  Since the adhesive of the present invention can be easily produced from a readily available and inexpensive raw material without going through a complicated route, the cost can be reduced. Further, since the adhesive of the present invention can be applied to a wide variety of products, it is very useful as a universal type adhesive.

Hereinafter, the adhesive of the present invention will be described in more detail.
The polycarbonate diol urethane resin of the present invention is usually obtained by reacting polycarbonate polyol and diisocyanate. Examples of the polycarbonate polyol include those obtained by a dealcoholization reaction between a polyhydric alcohol and diethylene carbonate, dimethyl carbonate, diethyl carbonate, diphenyl carbonate, or the like. Examples of the polyhydric alcohol include ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6- Hexanediol, 1,6-hexamethylenediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,8-octanediol, 1,9-nonanediol, diethylene glycol, 1,4-cyclohexanedimethanol, Examples include hydroquinone diethylol ether.

  Diisocyanates include tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, tolidine diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, tetramethylxylylene diisocyanate, trimethylhexamethylene diisocyanate, etc. Is mentioned.

  The number average molecular weight of the urethane resin of the present invention obtained by the reaction between the polyol and diisocyanate is determined as a molecular weight in terms of polystyrene by gel permeation chromatography (GPC) analysis. As described above, in the present invention, it is in the range of 10,000 to 100,000, preferably 15,000 to 50,000. This is because if the molecular weight is less than 10,000, the solvent resistance of the resulting adhesive and the adhesion to the adherend tend to decrease, and if it exceeds 100,000, the viscosity of the adhesive increases and the operability is poor. Specifically, it can be obtained by using a product name such as “Nipporan 5115”, “Nipporan 5120”, “Nipporan 5196”, “Nipporan 5199”, “Nipporan 5230” manufactured by Nippon Polyurethane Industry Co., Ltd. and used in the present invention. it can.

  In the adhesive of the present invention, a polyisocyanate curing agent (NCO content: 15.0 to 27.0%) is added to the urethane resin. The curing agent is obtained by reacting trimethylolpropane with diisocyanate such as tolylene diisocyanate or 1,6-hexane diisocyanate, and preferably has a number average molecular weight of about 500 to 1,000. The curing agent reacts with the hydroxyl group of the urethane resin to cure the adhesive, and specifically, “Coronate HX”, “Coronate HXR”, “Coronate HXLV”, “Coronate HK” manufactured by Nippon Polyurethane Industry Co., Ltd. ”,“ Coronate HX-T ”,“ Coronate 2096 ”.

  In the present invention, the weight ratio of the urethane resin: curing agent is in the range of 3: 10-15: 10, preferably 4: 10-9: 10. Usually, since the urethane bond by the reaction at the time of crosslinking reacts with the isocyanate group and the hydroxyl group in a ratio of 1: 1, the isocyanate group is overwhelmingly blended as exemplified above in the weight ratio of the present invention. . Therefore, it is considered that the isocyanate group of the curing agent of the present invention not only reacts with the diol urethane resin but also reacts with the hydroxyl group present on the surface of the target adherend to form a strong bond. The mechanism between the adhesive and the adhesive surface of the adherend is as follows: (A) Bonding by the force (van der Waals force) between the adhesive surface and adhesive molecules; (B) Between the adhesive surface and adhesive molecules There are three types of chemical bonding: (C) mechanical bonding by the adhesive entering into a fine hole or groove on the bonding surface and solidifying. In the present invention, any of the above mechanisms is acting, and it is considered that the contribution of (B) is particularly large.

  Further, the adhesive of the present invention contains 50 to 75% by weight as a solvent of at least one selected from methyl ethyl ketone, toluene, isopropyl alcohol, cyclohexanone and 2-ethoxyethyl acetate. These solvents can be used alone or in combination, and are used to keep the urethane resin and the curing agent in a liquid state that is easy to apply. In order to improve the adhesive force with the adherend, the solvent also has an effect of roughening the adherend surface of the adherend in a good sense (corresponding to (C) of the mechanism). Among the solvents, methyl ethyl ketone and 2-ethoxyethyl acetate are more preferably used.

  The adhesive of the present invention can be stored and distributed in containers such as polyethylene and polypropylene. This is because these containers can be squeezed, easily apply the adhesive to a desired position of the adherend, and are excellent in operability. Moreover, an existing container may be used as it is according to a desired capacity from a small amount container (several ml), and a general-purpose product can be used without developing a new dedicated container.

  Next, the use etc. suitable about the adhesive agent of this invention are described. INDUSTRIAL APPLICABILITY The present invention can be used as an adhesive for applying a mark to an adherend for decoration or identification. As an example of the mark, a polycarbonate diol urethane resin having a number average molecular weight of 10,000 to 100,000 and a polyisocyanate curing agent composed of hexamethylene diisocyanate (NCO content 15.0 to 27.0%) are 3:10 Examples thereof include a colored sheet formed by curing at a weight ratio of 3:50.

  Since the urethane resin and the curing agent constituting the colored sheet are not different from those already described, only the different portions will be described here. The colored sheet is greatly different from the previous adhesive in the weight ratio of each component, and the ratio of the curing agent is set high. The purpose is to prevent the volatilization of the dye printed on the colored sheet and to give the sheet an appropriate strength for easy handling.

  As a method for producing a colored sheet, for example, a urethane resin and a curing agent are measured at a predetermined weight ratio, and a solvent for making the mixture uniform is added and mixed so as to be 40% to 75% of the total weight. . This is thinly stretched on the surface of the silicon-coated glass cloth sheet, and the release paper is placed on top of each other. The whole is put into a dryer, and the release paper is peeled off by volatilizing the solvent. Is done. A paper with a desired pattern, color, letter, figure, etc., preliminarily applied with a sublimation dye is superimposed on this, and the sublimation dye is transferred by heating and pressurizing with a press to obtain a preferred colored sheet of the present invention. .

The solvent used in the production method is the same as that used for the adhesive, and one or more selected from methyl ethyl ketone, toluene, isopropyl alcohol, cyclohexanone, and 2-ethoxyethyl acetate can be used. Moreover, the heating by a press machine is about 150-250 degreeC, a pressure is about 100-200 kg / cm < ² >, and time is the range for several seconds-several minutes. Since the colored sheet thus obtained is a thin film, it is well adapted not only to an adherend having a flat surface but also to an adherend having a curved surface (for example, various balls and shoes such as soccer balls and volleyballs). Furthermore, since the colored sheet is stacked after the adhesive of the present invention is applied, the solvent in the adhesive penetrates into the colored sheet, so that it can be easily adapted to an adherend having irregularities and curved surfaces in shape.

  In addition, since the ratio of the curing agent contained in the colored sheet is large, by increasing the crosslink density, the movement of the polymer that forms the sheet is suppressed, and the gap between the polymer chains is narrowed to prevent dye bleeding. It can be done.

  Next, an example in which an IC tag is bonded to an adherend (for example, an entrance mat, a floor mat, a tire, a lab coat, etc.) will be described. The IC tag is attached for the purpose of manufacturing management, shipping and distribution management, or maintenance management. Conventionally, most of the conventional IC tags are physically attached by screws or sewing. This is because it is difficult to incorporate the IC tag and the adherend from the beginning because the product is obtained through separate manufacturing processes, and there is a problem in durability even if the IC tag is fixed with an adhesive. Because there was.

  In the present invention, when the IC tag is fixed, heat-resistant urethane is used to cover the IC tag, and not only the IC tag is directly adhered and held, but also the external force acts on the IC tag by covering with the heat-resistant urethane. Besides the reduction, the IC tag can be securely held by the bonding force between the heat-resistant urethane and the adhesive of the present invention.

  Furthermore, the adhesive of the present invention can be applied to an adherend (for example, clothing, a hat, a fabric product) through a hot melt adhesive layer or a polyester adhesive layer made of a thermoplastic polyurethane resin on a part or the entire surface of an embroidered fabric. Can be used to glue, back, gloves, helmet, protector, etc.).

  Conventionally, for fixing embroidery patches, etc., a thermoplastic polyurethane resin is used as an adhesive, and the thermoplastic polyurethane resin melted by heating is bonded by the anchor effect of the resin solidified during cooling by entering the embroidery patch and clothing. Was. However, this method has a problem that since the embroidery portion has a thickness, the heat conductivity is poor and the adhesive is not sufficiently melted. For this reason, the adhesion by the molten resin is auxiliary, and it is common to sew around the embroidery.

  In addition, because of the need to sew around the embroidery, for example, an item such as an enamel bag, temporarily remove the part necessary for embroidery from the bag body, add the embroidery, and then return to the bag body again. It was necessary to provide a mechanism for connection. Further, as a problem of the prior art, when the embroidery portion is applied to a hand-held band portion instead of the bag body, a method has been adopted in which embroidery is directly formed on the band. In such a method, in addition to the difficulty of embroidery formation due to the thickness of the band, the embroidery thread pierced from one surface of the band to the other surface tends to be unsightly.

  In the present invention, because of the chemical reaction by the adhesive, the complicated mechanism and embroidery formation as described above are not required, and the adhesive strength can be very high. The point regarding this adhesion is through a hot melt layer or a polyester adhesive layer. Adhesion is possible by simply using only the adhesive of the present invention, but the adhesive solution is easily absorbed by the embroidery fabric and may not be used effectively for adhesion to the adherend. The same can be said on the adherend side. Especially when the adherend is easy to absorb liquids such as textiles, a hot melt adhesive layer or polyester adhesive layer is formed with a thermoplastic polyurethane resin as a pretreatment at the desired position where the embroidery patch is to be applied. It is good to keep.

  In addition to the embroidered fabric, the adhesive of the present invention is used to bond a so-called mark fabric to an adherend (for example, clothing, a hat, a fabric product, a bag, a glove, a helmet, a protector, etc.). Can do. As the mark fabric, a conventionally known material is composed of a woven fabric or film (colored heat-resistant urethane, etc.) mark base body, and a thermoplastic polyurethane disposed on one side of the mark base body. Some have a hot melt adhesive layer. Conventionally, the mark base body is preliminarily colored, designs, and the like, and the mark is attached by heating from the mark base body side with an iron or the like while pressing the hot melt adhesive layer against the surface of the clothing. There is also a type in which a protective layer such as a pet film is provided on the surface of the mark base body opposite to the side where the hot melt layer is present in order to protect the mark fabric during heating.

  In addition, some mark fabrics employ a white heat-resistant urethane layer so that a desired color, figure, or pattern can be formed on the mark base body. That is, a hot-melt adhesive layer made of a thermoplastic polyurethane resin or the like is laminated on a protective film such as a pet film, and a white heat-resistant urethane layer is laminated thereon. The above-mentioned pattern is transferred by superimposing a sheet with a pattern with a sublimation dye and pressurizing and heating. Usually, when adhering to an adherend, it is cut into a desired shape, and then the pet film is peeled off, the hot melt layer is aligned with the desired position of the adherend, and the hot melt layer is melted by pressing and heating. Enters the fiber structure of the adherend and adheres by the anchor effect as described above.

  These mark fabrics can be adhered to the adherend by the adhesive of the present invention in the same manner as in the case of embroidered fabrics. Compared to the conventional case, there is an effect that the adherend can be bonded without being limited to the fiber product (regardless of the entry of the hot melt layer). For example, using only the mark fabric could not be used for adhesion to soccer balls or leather shoes, but if the adhesive of the present invention is used, it is easy to use without requiring a special device. Can be glued. In addition, since it has been necessary to heat the hot melt layer at a high temperature in the past, it is possible to fix the mark to products (for example, high-grade bags and handbags) that must avoid such a high temperature. However, it was possible to apply a mark with the adhesive of the present invention.

  The specific use of the adherend and the adhesive has been described above. However, the present invention is not limited to the specific examples, and the material of the adhesive surface of the adherend is leather, natural rubber, nitrile. The adhesive of the present invention can be used as long as it is formed of one selected from butadiene rubber, styrene-butadiene rubber, chloroprene rubber, isoprene rubber, butadiene rubber, urethane rubber, acrylic rubber, and soft polyvinyl chloride. it can.

  In order to clarify the present invention more specifically, some examples according to the present invention are shown below.

-Invention Examples 1 to 5 and Comparative Examples 1 to 2
Table 1 shows a ratio of a polycarbonate diol urethane resin having a number average molecular weight of about 20,000 and a polyisocyanate curing agent composed of hexamethylene diisocyanate (number average molecular weight is about 700; NCO content is about 21.0%). Blended. Moreover, the same table | surface shows the example which prepared the adhesive agent of this invention using methyl ethyl ketone or 2-ethoxyethyl acetate as a solvent. The composition in Table 1 is shown in parts by weight.

  Using the adhesives prepared at the respective ratios shown in Table 1, a mark fabric was affixed to a soccer ball as shown in FIG. 1, and the adhesive strength, durability, and the like were examined. The bonding method at this time is that the adhesive 10 is applied to a desired position of the soccer ball, the mark fabric 20 colored with a sublimation dye and processed into a desired shape is pasted, and the temperature is 100 ° C. to 130 ° C. Heating was applied for 1 to 3 minutes while applying pressure so that the mark dough became familiar with the coated surface.

  As a result, when the adhesives of Examples 1 to 5 of the present invention were used, the adhesive was so strong that the mark could not be erased unless the adhesive was integrated with the mark fabric and removed with a cutter or the like. Among them, the adhesives of Examples 1 to 3 of the present invention exhibited flexibility equivalent to the flexibility of the surface of other balls. On the other hand, in the case of the adhesive of Comparative Example 1, the bonded portion is too hard and easily cracked, and in the case of the adhesive of Comparative Example 2, the adhesive strength is weak and the mark fabric can be easily formed with a nail. It was the extent which can be peeled off.

  FIG. 2 shows a situation in which the same adhesion test as described above was performed on a baseball ball using the adhesives prepared at the respective ratios shown in Table 1 above. It was the same.

  Polycarbonate diol type urethane resin having a number average molecular weight of about 20,000 and a polyisocyanate type curing agent composed of hexamethylene diisocyanate (number average molecular weight is about 700; NCO content is about 21.0%) in the ratios shown in Table 2. Blended. The table shows an example of preparing a colored sheet base material using methyl ethyl ketone or 2-ethoxyethyl acetate as a solvent. The compositions in Table 2 are shown in parts by weight.

When the base material prepared in each ratio shown in Table 2 is coated on a glass-coated sheet coated with silicon, the release paper is stacked, the whole is placed in a dryer, the solvent is evaporated, and the release paper is peeled off. A sheet having a thickness of 15 to 40 μm was formed. A paper having a desired pattern, color, letter, figure, etc. previously applied with a sublimation dye is superimposed on this, and heated at a temperature of 200 ° C. with a press machine, and pressurized at 150 kg / cm ² for about 60 seconds, A colored sheet to which the sublimation dye was transferred was obtained.

  Using the adhesives prepared at the respective ratios shown in Table 1, the colored sheet was attached to a soccer ball as shown in FIG. 1, and the adhesive strength, durability, and the like were examined. The adhesion method at this time is the same as described above, and the adhesive 10 is applied to a desired position of the soccer ball, the colored sheet is attached, and the colored sheet is adapted to the coated surface at a temperature of 100 ° C. to 130 ° C. And heated for 1 to 3 minutes.

  As a result, when the adhesives of Examples 1 to 5 of the present invention were used, the adhesive was so strong that the pattern could not be erased unless the adhesive was integrated with the colored sheet and removed with a cutter or the like. Among them, the adhesives of Examples 1 to 3 of the present invention exhibited flexibility equivalent to the flexibility of the surface of other balls. On the other hand, in the case of the adhesive of Comparative Example 1, the bonded portion is too hard and easily cracked, and in the case of the adhesive of Comparative Example 2, the adhesive strength is weak and the colored sheet is easily peeled off with a nail. I was able to do it.

  FIG. 3 shows a state in which the embroidery material 30 is bonded to a garment (T-shirt) through a hot melt layer 40 made of a thermoplastic polyurethane resin. First, a thermoplastic polyurethane resin having a thickness of 100 μm was heated and pressed with a press on one side of the embroidered fabric to form a hot melt layer. Next, the adhesive shown in Invention Example 2 was applied to the garment, and the embroidery fabric on which the hot melt layer was formed was adhered. When bonding, the film was heated at about 80 ° C. for about 1 minute. As a result, it was possible to adhere to the clothing under extremely mild conditions without increasing the temperature to a high temperature as in the past (if only hot melt adhesion is required, heating to around 200 ° C. is necessary for resin melting).

  FIG. 4 shows a state in which an embroidered fabric 50 having a polyester adhesive layer formed to a thickness of about 30 μm is adhered to an adherend (handbag) with the adhesive shown in Example 2 of the present invention. For such products, it is difficult to perform hot melt bonding by high-temperature heating, and a desired mark or the like can be imparted by chemically using an adhesive as in the present invention.

FIG. 5 shows a state where the IC tag 60 is covered with the heat-resistant urethane 70 and adhered to the back surface of the adherend (entrance mat) with the adhesive shown in Example 2 of the present invention. The bonding method is as follows. First, the adhesive of Invention Example 2 is applied to a desired position on the doormat. Next, an adhesive is applied to the heat-resistant urethane in the same manner as described above, and after the IC tag is attached, it is bonded to the applied position of the front door mat. Thus, the heat-resistant urethane and the doormat can be temporarily bonded with an adhesive with the IC tag interposed therebetween. Adhesion can be achieved even if left as it is, but for example, the adhesion can be completed at an early stage by heating at 100 to 140 ° C. for 2 to 5 minutes while applying a pressure of 200 to 500 g / cm ² .

  In the above example, it is also possible to use a method in which a thermoplastic urethane layer is provided on the surface of the heat-resistant urethane 70 and the adhesive is applied to the thermoplastic urethane layer. In this case, the thermoplastic urethane layer is melted and the IC tag can be bonded more firmly.

  FIG. 6 shows a state in which the embroidered fabric 30 is bonded to the “cap collar” via the hot melt layer 40 made of thermoplastic polyurethane resin. The adhering method was the same as in Example 4, and a hot-melt layer was formed by heating and pressing a 100 μm-thick thermoplastic polyurethane resin on one side of the embroidered fabric with a press. Next, the adhesive shown in Example 2 of the present invention was applied to the brim 80 of the hat, and the embroidery fabric on which the hot melt layer was formed was adhered. When bonding, the film was heated at about 80 ° C. for about 1 minute. As a result, it was possible to bond to the adherend under extremely mild conditions without increasing the temperature (if only hot-melt bonding is required, heating to around 200 ° C. is necessary for melting the resin).

  Conventionally, when embroidery is applied to a brim of a hat or the like, it is performed by directly sewing, and a method by hot melt bonding has not been adopted. The reason is that the core material (thick paper, polymer sheet, etc.) that constitutes the collar is vulnerable to heat, and therefore a method using high-temperature hot-melt bonding (heating at about 200 ° C. as described above) is not applicable. It is. In the present invention, as described above, the heating conditions are mild, and embroidery with high adhesive strength can be applied.

  The adhesive of the present invention is a polyurethane-based adhesive having a specific composition that can be prepared from an easily available and inexpensive raw material and has a strong adhesive force. Therefore, a very wide variety of products (such as various sports equipment such as soccer balls and baseball balls, shoes, bags, clothing, doormats, etc.) can be marked and decorated with simple means. I can do it.

FIG. 1 shows an example in which the adhesive of the present invention is applied to a soccer ball. FIG. 2 shows an example in which the adhesive of the present invention is applied to a baseball ball. FIG. 3 shows an example in which the adhesive of the present invention is applied to clothing. FIG. 4 shows an example in which the adhesive of the present invention is summarized in a handbag. FIG. 5 shows an example in which the adhesive of the present invention is applied to the doormat. FIG. 6 shows an example in which the adhesive of the present invention is applied to a hat.

10 Adhesive 20 Mark fabric 30 Embroidered fabric 40 Hot melt layer 50 Embroidered fabric (having polyester adhesive layer)
60 IC tag 70 Heat-resistant urethane 80 Hat collar

Claims (7)

A polycarbonate diol urethane resin having a number average molecular weight of 10,000 to 100,000,
A polyisocyanate-based curing agent composed of hexamethylene diisocyanate (NCO content: 15.0 to 27.0%),
In a weight ratio of 3: 10-15: 10,
An adhesive comprising 50 to 75% by weight of a total of one or more selected from methyl ethyl ketone, toluene, isopropyl alcohol, cyclohexanone, and 2-ethoxyethyl acetate as a solvent. Weight of 3:10 to 3:50 is a polycarbonate diol urethane resin having a number average molecular weight of 10,000 to 100,000 and a polyisocyanate curing agent (NCO content 15.0 to 27.0%) made of hexamethylene diisocyanate. A colored sheet formed by curing at a ratio;
The adherend,
The adhesive according to claim 1 for bonding.
  The adhesive according to claim 2, wherein the colored sheet is a colored sheet colored with a sublimable dye. Heat-resistant urethane covering the IC tag,
The adherend,
The adhesive according to claim 1 for bonding. Through a hot melt adhesive layer or polyester adhesive layer made of a thermoplastic polyurethane resin on part or the entire surface of the embroidered fabric,
The adhesive according to claim 1 for adhering to an adherend.   The adhesive according to claim 1 for adhering the mark fabric and the adherend.   The adhesion surface material of the adherend is a kind selected from leather, natural rubber, nitrile-butadiene rubber, styrene-butadiene rubber, chloroprene rubber, isoprene rubber, butadiene rubber, urethane rubber, acrylic rubber, and soft polyvinyl chloride. The adhesive according to claim 2, wherein the adhesive is formed.

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