JP4868778B2 - In-mold label - Google Patents

Description

The present invention relates to an in-mold molding label that has an antenna and an IC chip that can transmit and receive data in a non-contact manner in a laminated structure and can read and write data.
The in-mold molding label obtained by the present invention can be printed or printed on the surface, and there is a security concern that an internal IC chip or antenna (hereinafter referred to as an IC module) can be seen through. Furthermore, when the label is attached to the thermoplastic resin container, the internal IC module is not damaged by the heat and pressure of the molten thermoplastic resin.
Furthermore, since the label for in-mold molding is excellent in strength, water resistance, and adhesive strength, the labeled thermoplastic resin container can be used in water both indoors and outdoors, frozen food containers, industrial products, It can be used for various chemical containers, manufacturing process management applications, logistics management applications, returnable boxes, etc.

In recent years, cards that include IC modules and transmit / receive data without contact via an external reader or writer have become widespread. An IC label that has an adhesive layer for the same purpose and is attached to and used on an adherend has also been proposed (see, for example, Patent Documents 1, 2, and 3).
As one aspect of the label, the label is set so as to be in contact with the mold wall surface in advance, and a molten thermoplastic resin is injection molded into the mold, or a molten thermoplastic resin parison is guided and hollow molded. Alternatively, an in-mold molding label that can produce a resin-molded article with a label by vacuum molding or pressure molding a molten thermoplastic resin sheet is known (see, for example, Patent Documents 4 and 5).

Such an in-mold molding label has a high adhesive strength, excellent water resistance and durability, and a glass transition point of the pressure-sensitive adhesive, compared to a pressure-sensitive adhesive label. This is advantageous in that stable adhesive strength can be maintained even in a lower temperature environment. Moreover, since it cannot be reattached after sticking, it is advantageous at the point which can prevent fraud, such as camouflage and falsification.
Utilizing the characteristics of the IC module that can send and receive repetitive data, the IC label is made of a thermoplastic resin film and used as an in-mold molding label that is affixed to a resin molded product by an in-mold molding method. The obtained resin molded products can be used in water, indoors or outdoors, in harsh environments such as frozen food containers, industrial products, various chemical containers, manufacturing process management applications, logistics management applications, returnable boxes, etc. Can be suitably used, and fraud such as disguise and falsification due to label replacement can be prevented.

Patent Document 6 proposes a resin extrusion molded product in which an IC module is set as it is in a fixed position in a mold, and a hot melt resin is extruded into the mold to enclose the IC module. As described above, the IC module undergoes a heating process in the process of manufacturing a product in which the IC module is enclosed in a resin molded product. Conventionally, the IC module is required to mold a thermoplastic resin molded product. It is said that it has heat resistance that can withstand at any temperature. These were very bulky and expensive for circuit protection.
However, small IC modules developed in recent years do not need to apply high heat to the junction between the IC chip and the antenna, and it is not necessary to use a heat-resistant polyimide film for the base film that constitutes the IC module. Inexpensive polyester film and polyethylene film have come to be used for the purpose of cost reduction. In addition, there is concern that the miniaturization of the IC chip itself will lead to a decrease in resistance to thermal stress accompanying a decrease in heat capacity, and in the future, even in the manufacturing process of the same resin extrusion molded product, the heat history of the IC module will be reduced. If not fully considered, it is estimated that problems such as product yield deterioration will occur.

Patent Document 7 describes a non-contact data carrier label that can be used for in-mold molding. However, even in Patent Document 7, the IC module directly touches the heat-melted resin at the time of in-mold molding. Similarly to the above, the IC module is damaged by a sudden temperature change, or the antenna part is deformed by the extrusion pressure of the molten resin. Inadequate from the viewpoint of protecting the IC module under the technical background of in-mold molding.
Since IC chips are extremely sensitive to static electricity and may be damaged by the charging of the label material during label molding, printing and printing, and in-mold molding, countermeasures against static electricity are also important.

Japanese Patent Laid-Open No. 11-134460 Japanese Patent Application Laid-Open No. 11-231782 JP 2002-074303 A Japanese Patent Laid-Open No. 02-084319 Japanese Patent Laid-Open No. 09-207166 Japanese Patent Application Laid-Open No. 08-056799 JP 2002-049905 A

  That is, in the present invention, in-mold molding that includes an IC module that can solve production problems with the challenge of protecting the IC module from heat, pressure, and static electricity during label molding, printing, printing, and in-mold molding. An object of the present invention is to provide a label for use and a thermoplastic resin container with the label.

As a result of repeated studies on an in-mold molding label containing an IC module suitable for in-mold molding, the present inventors sealed and fixed the IC module between at least two thermoplastic resin films. Has found that the above problem can be solved.
That is, in this invention, the label for in-mold shaping | molding which has the following structures, and this thermoplastic resin container with a label are provided.

"1" a label for in-mold forming to be used in in-mold molding, possess film layer the in-mold molding label has pores in the heat-sealable layer (1a) and a layer in the (1b), A thermoplastic resin film (1) having a thermal conductivity of 0.01 to 0.5 W / m · K and a printable thermoplastic resin film (2), and the thermoplastic resin film (1) and the thermoplastic resin An in-mold molding label comprising an antenna and an IC chip for transmitting and receiving data without contact with the film (2).
"2" heat-mold label according to porosity of Ru 1-60% der the "1" obtained from the following equation thermoplastic resin film (1).
Porosity (%) = [(ρ ₀ −ρ) / ρ ₀ ] × 100
(Where ρ ₀ is the true density of the film and ρ is the density of the film.)
<< 3 >> The in-mold molding label according to the above << 2 >>, in which the film layer (1b) is stretched in at least a uniaxial direction.

<< 4 >> The label for in-mold molding according to any one of the above << 1 >> to << 3 >>, wherein the thermoplastic resin film (1) and the thermoplastic resin film (2) have a thermal shrinkage of 0 to 5%.
<< 5 >> Any of the above << 1 >> to << 4 >> in which at least one of the thermoplastic resin film (1), the thermoplastic resin film (2), and the in-mold molding label has an opacity of 70 to 100% A label for in-mold molding according to crab.
<< 6 >> An adhesive layer (3) is provided between the thermoplastic resin film (1) and the thermoplastic resin film (2), and the adhesive layer (3) is a pressure-sensitive adhesive and a curable resin adhesive. The label for in-mold molding according to any one of the above << 1 >> to << 5 >>, which contains at least one of UV curable adhesive and electron beam curable adhesive.
<< 7 >> The label for in-mold molding according to any one of the above << 1 >> to << 6 >>, wherein the adhesive strength between the thermoplastic resin film (1) and the thermoplastic resin film (2) is 300 gf / 25 mm or more. .

<8> The above, wherein at least one of the thermoplastic resin film (1) and the thermoplastic resin film (2) has a light transmittance of a wavelength of 380 nm of 60% or more, and the adhesive layer (3) comprises an ultraviolet curable adhesive. The label for in-mold molding according to << 6 >> or << 7 >>.
<9> The in-mold molding label according to any one of the above <1> to <8>, wherein the thermoplastic resin film (2) includes a printable layer (2a) on at least one side.
<< 10 >> The label for in-mold molding according to the above << 9 >>, wherein information including a barcode or a two-dimensional barcode is printed and printed on the printable layer (2a).
<< 11 >> The in-mold molding label according to any one of the above << 1 >> to << 10 >>, wherein the thermoplastic resin film (2) includes a concealing layer (2b) on at least one side.

<12> The in-mold molding label according to the above item <11>, wherein the concealing layer (2b) includes at least one of a metal thin film, a white pigment coat, white solid printing, and black solid printing.
<< 13 >> The label for in-mold molding according to any one of the above << 1 >> to << 12 >>, wherein at least one of the thermoplastic resin film (1) and the thermoplastic resin film (2) contains a crystalline polyolefin-based resin.
<14> The label for in-mold molding according to the above <13>, wherein the crystalline polyolefin-based resin is a propylene-based resin.
<< 15 >> Any one of the above << 1 >> to << 14 >>, wherein at least one of the thermoplastic resin film (1) and the thermoplastic resin film (2) contains at least one of an inorganic fine powder and an organic filler. Label for in-mold molding.

<< 16 >> The label for in-mold molding according to any one of the above << 1 >> to << 15 >>, wherein the heat sealable layer (1a) is made of a heat sealable resin containing an ethylene-based resin having a melting point of 50 to 130 ° C.
<< 17 >> The heat-sealable layer (1a) is provided by applying and drying an aqueous coating liquid containing a heat-sealable resin dispersion having a phase transition temperature of 50 to 140 ° C. on the thermoplastic resin film (1). The in-mold molding label according to any one of the above << 1 >> to << 16 >>.
<< 18 >> The in-mold molding label according to any one of the above << 1 >> to << 17 >>, wherein the antenna and the IC chip that transmit and receive data without contact have a function of any one of an RFID, a smart tag, and an active tag.

<< 19 >> The in-mold molding label according to any one of the above << 1 >> to << 18 >>, which has antistatic performance on at least one surface.
<< 20 >> A thermoplastic resin container in which the in-mold molding label according to the above << 1 >> to << 19 >> is integrally attached at the time of molding in a mold.
<21> The thermoplastic resin container according to <20>, wherein the adhesive strength between the thermoplastic resin container and the in-mold molding label is 300 gf / 25 mm or more.
<< 22 >> The thermoplastic resin container according to the above << 20 >> or << 21 >>, which is molded in a mold by at least one molding means of injection molding, hollow molding, differential pressure molding, and foam molding.

The in-mold label of the present invention has a function as an IC label, is excellent in strength, water resistance, and adhesive strength, and can be printed or printed on the surface. It is possible to prevent fraud such as tampering. There is no security concern that the internal IC chip and antenna can be seen through, and the internal IC chip and antenna are not damaged by processing when the label is attached to a thermoplastic resin container. .
The labeled thermoplastic resin container can be used in water both indoors and outdoors, and is suitably used for frozen food containers, industrial products, various chemical containers, manufacturing process management applications, logistics management applications, returnable boxes, etc. It is possible.

The in-mold forming label and the labeled thermoplastic resin container of the present invention will be described in detail below. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
The in-mold molding label of the present invention comprises a thermoplastic resin film (1) having a heat-sealable layer (1a) and a printable thermoplastic resin film (2), and the thermoplastic resin film (1) and the heat It has an antenna and IC chip for transmitting and receiving data in a non-contact manner with the plastic resin film (2).

  In the present invention, the thermoplastic resin film (1) having the heat-sealable layer (1a) is in direct contact with the molten resin forming the thermoplastic resin container during in-mold molding, and the heat-sealable layer (1a) is activated to form a resin film. While (1) is firmly adhered to the container, the antenna and the IC chip are prevented from directly touching the molten resin and have a function of protecting them from heat and stress damage. The thermoplastic resin film (2) covers the antenna and IC chip so that they are not exposed to the outside, and gives water resistance and durability, and can print and print information such as barcodes on at least one side as a label. Therefore, convenience and design can be improved. Usually, the thermoplastic resin film (2) is opaque so that the antenna and IC chip inside the label cannot be seen through.

The thermoplastic resin film (1) has a film layer (1b) having pores in the layer, and the porosity determined from the following formula of the thermoplastic resin film (1) is 1 to 60%. Is preferable, 10 to 50% is more preferable, and 20 to 45% is particularly preferable.
Porosity (%) = [(ρ ₀ −ρ) / ρ ₀ ] × 100
(Where ρ ₀ is the true density of the film and ρ is the density of the film.)
The thermal conductivity of the thermoplastic resin film (1) is preferably 0.01 to 0.5 W / m · K, more preferably 0.05 to 0.15 W / m · K, and 0.08. It is especially preferable that it is -0.12W / m * K.
By providing the film layer (1b) having pores, the cushioning property and heat insulating property of the thermoplastic resin film (1) are improved, and the antenna and the IC chip are more reliably protected. Moreover, it becomes possible to hold | maintain the temperature of activation of a heat-sealable layer (1a) effectively at the time of adhesion | attachment of the label for in-mold shaping | molding.

If the porosity is less than 1%, the heat insulation is insufficient, and if the porosity exceeds 60%, an appearance defect such as a hull caused by collapse of the pores occurs during in-mold molding. Cheap. A thermoplastic resin film having a thermal conductivity of less than 0.01 W / m · K is generally difficult to obtain, and if it exceeds 0.5 W / m · K, the heat insulating property is insufficient.
The film layer (1b) is preferably stretched at least in a uniaxial direction. Stretching will be described in detail later, but it is possible to impart pores to the film layer (1b) by stretching and easily adjust the porosity. Furthermore, the stretch uniformity of the thermoplastic resin contained in the film layer (1b) can impart thickness uniformity, rigidity and the like suitable for post-processing including printing and labels.

  The thermal shrinkage of the thermoplastic resin film (1) and the thermoplastic resin film (2) constituting the in-mold molding label of the present invention is preferably 0 to 5%, and preferably 0 to 4%. Is more preferable. When the thermal contraction rate of the label exceeds 5%, the label is likely to be deformed by the heat of the molten resin when the label is attached to the thermoplastic resin container, and the appearance is likely to deteriorate. In particular, in the case of an in-mold molding label comprising a laminated structure of at least two thermoplastic resin films as in the present invention, mold shrinkage of a thermoplastic resin container after in-mold molding, film (1), film (2) Due to the difference in thermal history, the thermoplastic resin film (2) that becomes the label surface is likely to float, and appearance defects due to blisters (bulges) are likely to occur. Further, there is a concern about deformation of the antenna portion fixed to the shrinkage of the label. Therefore, the thermoplastic resin film (1) and the thermoplastic resin film (2) constituting the in-mold molding label of the present invention have the smallest heat shrinkage, are firmly bonded and fixed, and have higher rigidity. good.

  It is preferable that at least one of the thermoplastic resin film (1), the thermoplastic resin film (2), and the in-mold molding label has an opacity of 70 to 100%, more preferably 80 to 100%. 90 to 100% is particularly preferable. In particular, by setting the opacity of the thermoplastic resin film (2) to 70% or more, there is no security concern that the internal IC chip or antenna can be seen through, and the appearance is handled like a normal label. be able to. In addition, by setting the opacity of either the thermoplastic resin film (1) or the in-mold molding label to 70% or more, the ground of the thermoplastic resin container is not seen through, and is decorated on the label. The design property of printing and the reading rate of barcode printing can be improved.

As a specific method for sealing and fixing the antenna and the IC chip between the thermoplastic resin film (1) and the thermoplastic resin film (2), the thermoplastic resin film (1) and the thermoplastic resin film ( It is preferable to have an adhesive layer (3) between 2).
The adhesive layer (3) preferably contains at least one of a pressure sensitive adhesive, a curable resin adhesive, an ultraviolet curable adhesive, and an electron beam curable adhesive. In order to increase the water resistance, durability and security of the in-mold molding label, the higher the adhesive strength between the thermoplastic resin film (1) and the thermoplastic resin film (2), the better, specifically 300 gf / 25 mm or more, more preferably 300 to 8000 gf / 25 mm, and particularly preferably 500 to 7000 f / 25 mm. When the adhesive strength between the film (1) and the film (2) is less than 300 gf / 25 mm, peeling becomes easy, the thermoplastic resin film (2) that becomes the label surface is easily lifted, and the appearance is deteriorated due to blisters or the like. Is likely to occur.

  At least one of the thermoplastic resin film (1) and the thermoplastic resin film (2) has a light transmittance of a wavelength of 380 nm of 60% or more, and an ultraviolet curable adhesive is used for the adhesive layer (3). When the film (1) and the film (2) are bonded while being irradiated with ultraviolet rays, a strong adhesive force can be obtained in a short processing time, and the film (1) and the film (2) do not shift after curing. Particularly preferred. The thermoplastic resin film (2) preferably has a printable layer (2a) on at least one side. The printability layer (2a) is provided in order to properly perform various printing and printer printing when the present invention is used as a label. Accordingly, not only information such as barcodes and two-dimensional barcodes on the printable layer (2a), but also, for example, product names, manufacturer names, and sales company names related to thermoplastic resin containers with labels attached thereto. , Information on how to use the product, notes, characters, trademarks, logos, patterns, etc. can be printed and printed.

The thermoplastic resin film (2) preferably has a concealing layer (2b) on at least one side. As the concealing layer (2b), at least one of a metal thin film, a white pigment coat, a white solid printing, and a black solid printing can be selected. The concealing layer (2b) improves the opacity of the thermoplastic resin film (2). By providing this, there is no security concern that the internal IC chip or antenna can be seen through. It can be handled like a label.
The metal thin film provided on the thermoplastic resin film (2) to the extent that it does not obstruct or interfere with the data transmission / reception by the IC module contributes to improving the design of the label by providing a metal-like appearance. Also, white pigment coating, white solid printing, etc. contribute to the improvement of the barcode reading rate.

<Thermoplastic resin films (1) and (2)>
The thermoplastic resin film (1) and the thermoplastic resin film (2) constituting the in-mold molding label of the present invention are made of ethylene such as high-density polyethylene, medium-density polyethylene, and low-density polyethylene as the thermoplastic resin used therefor. Resin, or propylene resin, polyolefin resin such as polymethyl-1-pentene, ethylene-cyclic olefin copolymer, polyethylene terephthalate or copolymer thereof, thermoplastic polyester resin such as polyethylene naphthalate, aliphatic polyester, Polyamide resins such as nylon-6, nylon-6,6, nylon-6,10, nylon-6,12, etc., polyvinyl chloride, polycarbonate, atactic polystyrene, syndiotactic polystyrene, ABS resin, ionomer, polyphenyle It can be exemplified thermoplastic resins sulfides. These resins can be used in combination of two or more.

Among these, from the viewpoints of processing suitability, moldability, strength, flexibility, water resistance, chemical resistance, and weather resistance, it is preferable that at least one of the films contains a polyolefin resin. Is more preferable, and it is particularly preferable to include a propylene-based resin having a low thermal conductivity.
Examples of such propylene resins include propylene homopolymers exhibiting isotactic or syndiotactic stereoregularity, propylene, ethylene, 1-butene, 1-hexene, 1-heptene, and 4-methyl-1-pentene. And a copolymer with an α-olefin. These copolymers may be binary, ternary or quaternary, and may be random copolymers or block copolymers.

Moreover, an inorganic fine powder, an organic filler, etc. can be suitably mix | blended with said thermoplastic resin. At least one of the thermoplastic resin film (1) and the thermoplastic resin film (2) contains at least one of an inorganic fine powder and an organic filler, and these are cored in the film when stretched. A large number of fine pores can be provided, which is preferable because it contributes to a decrease in the thermal conductivity of the label and an improvement in opacity.
The kind of inorganic fine powder or organic filler is not particularly limited. Examples of the inorganic fine powder include heavy calcium carbonate, light calcium carbonate, calcined clay, talc, barium sulfate, diatomaceous earth, magnesium oxide, zinc oxide, titanium oxide, and silicon oxide. Among them, heavy calcium carbonate, calcined clay, and talc are preferable because they are inexpensive and have good moldability.

Examples of the organic filler include polyethylene terephthalate, polybutylene terephthalate, polyamide, polycarbonate, polyethylene naphthalate, polystyrene, melamine resin, polyethylene sulfite, polyimide, polyethyl ether ketone, polyphenylene sulfite, cyclic olefin homopolymer, and cyclic olefin. Examples thereof include copolymers with ethylene. Among them, it is preferable to use an incompatible organic filler having a melting point higher than that of the thermoplastic resin used for the film.
One kind of the inorganic fine powder or organic filler may be used alone, or two or more kinds may be selected and used in combination. When two or more types are used in combination, an inorganic fine powder and an organic filler may be mixed and used.
Further, if necessary, a dispersant, an antioxidant, a compatibilizer, an ultraviolet stabilizer, an antiblocking agent, a permanent antistatic agent, and the like can be added to the thermoplastic resin.

The thermoplastic resin film (1) and the thermoplastic resin film (2) of the present invention may be a single layer or multiple layers. In the case of multiple layers, the base layer and a structure in which surface layers are arranged on one side or both sides thereof, each layer may be made of the same thermoplastic resin, or may be made of different types of thermoplastic resins. Moreover, when mix | blending inorganic fine powder or an organic filler with these, those types and compounding quantities may be the same and may differ.
It is preferable that the thermoplastic resin film (1) and the thermoplastic resin film (2) include at least a layer that is stretched in a uniaxial direction. When extending | stretching a several layer, you may extend | stretch separately before laminating | stacking each layer, and you may extend | stretch the whole, after laminating | stacking. Further, the stretched layer may be further stretched after lamination.
Although various known methods can be used for stretching, as a specific example, the stretching temperature is higher than the glass transition point when the thermoplastic resin used is an amorphous resin, and in the case of a crystalline resin. It can be carried out in a temperature range suitable for each thermoplastic resin, from the glass transition point of the non-crystalline part to the melting point of the crystalline part, and longitudinal stretching utilizing the peripheral speed difference of the roll group, and transverse using a tenter oven Examples thereof include stretching, rolling, simultaneous biaxial stretching using a combination of a tenter oven and a linear motor, or a combination thereof.

The draw ratio is not particularly limited, and is appropriately selected depending on the purpose and the characteristics of the thermoplastic resin used. For example, when a propylene homopolymer or a copolymer thereof is used as a thermoplastic resin, it is about 1.2 to 12 times, preferably 2 to 10 times when stretched in one direction. In some cases, the area magnification is 1.5 to 60 times, preferably 10 to 50 times. When using other thermoplastic resins, it is 1.2 to 10 times, preferably 2 to 5 times when stretched in one direction, and preferably 1.5 to 20 times by area magnification in the case of biaxial stretching. Is 4 to 12 times. Furthermore, heat treatment at a high temperature is performed as necessary.
The thicknesses of the thermoplastic resin film (1) and the thermoplastic resin film (2) are appropriately determined according to the material used, the application target of the label, the purpose of use, the use environment, the storage environment, and the like. The thickness of the thermoplastic resin film (1) is preferably 5 to 500 μm, and more preferably 10 to 300 μm. Moreover, it is preferable that it is 20-500 micrometers, and, as for the thickness of a thermoplastic resin film (2), it is more preferable that it is 40-300 micrometers.

<Heat sealable layer (1a)>
As the heat-sealable resin constituting the heat-sealable layer (1a) used for the in-mold molding label of the present invention, a known resin can be selected, and the label is attached by heating during in-mold molding. The type is not particularly limited as long as it has a function of sticking to a resin material constituting the container.
Examples of preferred resins, low density or medium density polyethylene having a density of 0.900~0.935g / cm ^3, density of 0.880~0.940g / cm ³ linear low-density polyethylene, ethylene-acetic acid Vinyl copolymer, ethylene / acrylic acid copolymer, ethylene / alkyl acrylate copolymer, ethylene / methacrylic acid alkyl ester copolymer (alkyl group having 1 to 8 carbon atoms), ethylene / methacrylic acid copolymer An ethylene-based resin having a melting point of 50 to 130 ° C. such as a coalesced metal salt (Zn, Al, Li, K, Na, etc.) can be given.

  Among these, high pressure polyethylene having a density of 10 to 60% and a number average molecular weight of 10,000 to 40,000, or linear linear polyethylene is preferable. Among these, from the viewpoint of adhesion to a resin container, 40 to 98% by weight of ethylene and 60 to 2% by weight of an α-olefin having 3 to 30 carbon atoms are converted into a metallocene catalyst (particularly a metallocene / alumoxane catalyst or, for example, International Publication 92/92). A linear on-line polyethylene obtained by copolymerization using a metallocene compound as disclosed in the pamphlet of No. 0723, a metallocene catalyst comprising a compound that reacts with a metallocene compound to form a stable anion. Particularly preferred. These ethylene resins may be used alone or in a combination of two or more. When the ethylene resin is used by mixing with other resins such as polypropylene, a form mainly containing the ethylene resin (50% by weight or more) is preferable.

As a method for providing the heat-sealable resin on the thermoplastic resin film (1) to form the heat-sealable layer (1a), the above-mentioned resin layer constituting the thermoplastic resin film (1) inside the multilayer die is used. A co-extrusion method in which a molten resin (for example, film layer (1b)) and a molten resin of the heat-sealable resin adhesive are laminated and extruded into a film shape, and the molten resin of the heat-sealable resin adhesive is formed into a film form from a T-die Extrusion lamination method for extruding and laminating on the resin layer, a method of laminating the heat-sealable resin in a solvent such as toluene, ethyl cellosolve and the like after applying to the resin layer and drying Can be mentioned.
In this case, the thickness of the heat-sealable layer (1a) is preferably 1 to 100 μm, and more preferably 2 to 20 μm. The heat-sealable layer needs to be melted by the heat of the molten resin that is a raw material of the container, and the container and the label need to be fused together. In order to obtain sufficient adhesive strength, the thickness of the heat-sealable layer is preferably 1 μm or more. Moreover, if it is 100 micrometers or less, a label will be hard to curl and the setting to a shaping die will be comparatively easy at the time of in-mold shaping | molding.

The heat-sealable layer (1a) is formed with an embossed pattern on the surface by a known method, so that air enters between the label for in-mold molding and the container (the blistering phenomenon). ) Can be prevented.
A known resin additive can be arbitrarily added to the heat-sealable layer (1a) as long as the performance required for heat-seal is not impaired. Examples of such additives include dyes, nucleating agents, plasticizers, mold release agents, antioxidants, antiblocking agents, flame retardants, ultraviolet absorbers, ultraviolet stabilizers, and antistatic agents.
In addition, as the heat-sealable resin constituting the heat-sealable layer (1a) used for the in-mold molding label of the present invention, a water-based heat-sealable resin suitable for the in-mold molding label is appropriately selected and used. You can also. According to this method, the adhesive strength of the label can be improved regardless of the type of thermoplastic resin forming the container. In particular, selecting a heat-sealable resin provided by coating and drying an aqueous coating liquid containing a heat-sealable resin dispersion having a phase transition temperature of 50 to 140 ° C. on the thermoplastic resin film (1). Is preferred.

The aqueous heat sealable resin is preferably a resin dispersion having heat sealability (thermal activity) suitable for in-mold molding. Examples of the dispersion of the resin having heat sealability include those obtained by emulsion polymerization, those obtained by suspension polymerization, and those that are mechanically pulverized by an extruder or the like and dispersed in an aqueous solvent. What formed the heat-sealable layer, leaving the particle form of the dispersion, can prevent blistering of labels for in-mold molding and blocking of labels.
Examples of preferable water-based heat-sealable resins include acrylic polymers, vinyl acetate polymers, styrene polymers, vinyl chloride polymers, vinylidene chloride polymers, ethylene resins including polyethylene, polyurethane, polyester, epoxy Resin, petroleum resin, rosin ester, silicone resin, alkyd resin, polybutadiene, butadiene copolymer, polybutene, butyl rubber, polypropylene, polychloroprene, polyisoprene and the like can be used.
Among these, acrylic polymers, vinyl acetate polymers, and styrene polymers are preferable, and among them, ethylene / acrylic acid copolymers, ethylene / methacrylic acid copolymers, ethylene / acrylic acid ester copolymers, acrylic acid. Ester polymers, ethylene / vinyl acetate copolymers, and styrene / butadiene copolymers are more preferred.

  The phase transition temperature of these resin dispersions is preferably in the range of 50 to 140 ° C., more preferably 55 to 130 ° C., from the viewpoint of in-mold molding suitability. When the phase transition temperature exceeds 140 ° C., the low-temperature heat sealability tends to deteriorate and the adhesive strength of the label tends to decrease. In addition, when the phase transition temperature is less than 50 ° C., it is difficult to form a heat-sealable layer while leaving the particle shape of the dispersion, and when dried at a high temperature, the particle shape does not remain and the heat-sealable resin is labeled. Since the surface is covered in a smooth state, blistering tends to occur during in-mold molding, and blocking tends to occur during printing or label processing. For this reason, if the drying after the dispersion liquid coating is carried out at a temperature lower than the phase transition temperature, the productivity tends to decrease. Furthermore, there is a problem that the heat-sealable layer of the label is sticky even at room temperature, or the labels are likely to block each other during label storage in summer.

Coating methods for these resin dispersions include comma method, roll method, rod method, curtain method, gravure method, blade method, air knife method, size press method, wire bar method, slide hopper method, reverse gravure method, etc. The general coating method is used. Moreover, the method of coating combining these general coating methods suitably is also used.
The drying method after coating is performed by a known means, but in the drying process, it must be dried under conditions that do not exceed the phase transition temperature of the heat-sealable resin dispersion to be used.
Dry coating amount of this heat-sealable layer (1a) is usually preferably 0.05~30g / m ^2, more preferably 0.1 to 20 g / m ^2, further is 0.2 to 10 g / m ² preferable. When the dry coating amount is less than 0.05 g / m ^2, there is a tendency that sufficient adhesive strength with the container cannot be obtained during in-mold molding. When the dry coating amount exceeds 30 g / m ² , the adhesive strength is sufficient, but the coating surface tends to be smooth and blistering tends to occur. Further, when the coating amount is increased, the coating cannot be completed in a single process, and a plurality of repeated coatings are required, resulting in an increase in production cost.

Furthermore, the heat-sealable layer (1a) after coating and drying may cover 30 to 100%, preferably 40 to 90%, more preferably 50 to 80% of the surface of the thermoplastic resin film (1). Suitable for in-mold molding. If it is less than 30%, the adhesive strength with the container tends to decrease during in-mold molding.
The heat-sealable layer (1a) made of a dispersion of a water-based heat-sealable resin is used to improve the adhesion with the above-described resin layer (for example, the film layer (1b)) constituting the thermoplastic resin film (1). It is preferable to add various binder resins, an anti-blocking agent for preventing blocking when processed into a label, a slip agent and an antistatic agent for improving the paper supply / discharge suitability at the time of printing.
Furthermore, a dispersant, a thickener, an antifoaming agent, an antiseptic, an ultraviolet absorber, an ultraviolet stabilizer, an antioxidant, a surfactant, a dye, a pigment, an antistatic agent, etc. may be added as necessary. Can do.

<Printable layer (2a)>
The printable thermoplastic resin film (2) is subjected to a surface treatment on at least one side to form a printable layer (2a) in order to improve printability by various printing methods and printability by various printing methods. Is preferred. As such a printable layer (2a), a surface modified layer, a pigment coat layer for improving print quality, a heat-sensitive recording layer, a laser print receiving layer, a thermal transfer receiving layer, an ink jet receiving layer, and the like may be various as required. Can be used.
Moreover, it is preferable that the label for in-mold molding of the present invention has antistatic performance on at least one side as a countermeasure against static electricity. Specifically, an antistatic agent may be added to the above-described heat-sealable layer (1a), and the printable layer (2a) contains an antistatic agent as described later and also has antistatic performance. Also good.

<Surface modification layer>
It is preferable to perform a surface treatment on at least the surface side of the thermoplastic resin film (2) to form a surface modified layer. The surface treatment method is a combination of a surface oxidation treatment and a surface treatment agent. As the surface oxidation treatment, corona discharge treatment, flame treatment, plasma treatment, glow discharge treatment, ozone treatment or the like generally used for films is used alone or in combination. Of these, corona treatment and frame treatment are preferred, and in the case of corona treatment, the treatment amount is 600 to 12,000 J / m ² (10 to 200 W · min / m ² ), preferably 1,200 to 9,000 J. / M ² (20 to 150 W · min / m ² ), in the case of frame processing, 8,000 to 200,000 J / m ² , preferably 20,000 to 100,000 J / m ² is used.

[Surface treatment agent]
The surface treatment agent in the former stage is mainly selected from the following primers and antistatic polymers, and is a single or a mixture of two or more components. From the viewpoint of improving ink adhesion during printing and preventing static charge, a preferable surface treatment agent is a primer or a combination of a primer and an antistatic polymer.
Primer: Examples of the primer include polyethyleneimine, polyethyleneimine having 1 to 12 carbon atoms, polyimethyleneimine-based polyimethylene, such as polyimethyleneimine-urea and polyiminepolyamide-polyethylenepolyamide-imineimine adducts and polyaminepolyamide-epichlorohydrin adducts. Acrylics such as polymers, acrylic amide-acrylic ester copolymers, acrylic amide-acrylic ester-methacrylic ester copolymers, polyacrylamide derivatives, oxazoline group-containing acrylic ester polymers and polyacrylic esters Acid ester polymer, water-soluble resin such as polyvinyl pyrrolidone, polyethylene glycol, polyvinyl alcohol, resin, polyvinyl acetate, polyurethane, ethylene-vinyl acetate copolymer, poly salt Water-dispersible resins such as vinylidene chloride, chlorinated polypropylene, and acrylonitrile-butadiene copolymer are used.
Of these, polyethyleneimine polymers, urethane resins, polyacrylates and the like are preferable, polyethyleneimine polymers are more preferable, and polyethyleneimines having a polymerization degree of 20 to 3,000 are more preferable. An ethyleneimine adduct of polyamine polyamide or a modified polyethyleneimine modified with an alkyl halide, alkenyl halide, cycloalkyl halide or benzyl halide having 1 to 24 carbon atoms.

  Antistatic polymer: Examples of the antistatic polymer include polymer types such as cationic, anionic, and amphoteric types. Examples of the cationic type include polymers having a quaternary ammonium salt structure or a phosphonium salt structure, and nitrogen-containing acrylic polymers. , A quaternary ammonium salt-containing nitrogen-containing acrylic or methacrylic polymer, and anionic styrene-maleic anhydride copolymer or alkali metal salt thereof, ethylene-acrylic acid copolymer alkali metal salt or ethylene -Alkali metal salts of methacrylic acid copolymers and amphoteric systems include acrylic or methacrylic polymers having a betaine nitrogen, especially acrylic or methacrylic polymers having a quaternary ammonium salt structure nitrogen. Is preferred.

The molecular weight of the antistatic polymer can be set to any level depending on the polymerization conditions such as the polymerization temperature, the type and amount of the polymerization initiator, the amount of solvent used, and the chain transfer agent. In general, the molecular weight of the obtained polymer is 1,000 to 1,000,000, but the range of 1,000 to 500,000 is preferred. The surface treatment agent in the former stage of the present invention may contain the following optional components as necessary.
Optional component 1: Crosslinking agent By adding a crosslinking agent, the coating strength and water resistance can be further improved. Examples of the crosslinking agent include epoxy compounds such as glycidyl ether and glycidyl ester, water-dispersed resins such as epoxy resins, isocyanates, oxazolines, formalins, and hydrazides. The addition amount of the crosslinking agent is usually in the range of 100 parts by weight or less with respect to 100 parts by weight of the active ingredient excluding the solvent for the surface modifier.

Optional component 2: Alkali metal salt or alkaline earth metal salt An alkali metal salt or alkaline earth metal salt is added to the surface modifier, and these salts include water-soluble inorganic salts such as sodium carbonate and carbonic acid. Sodium hydrogen, potassium carbonate, sodium sulfite, other alkaline salts, sodium chloride, sodium sulfate, sodium nitrate, sodium tripolyphosphate, sodium pyrophosphate, ammonium alum and the like can be mentioned. The amount of the optional component is usually 50 parts by weight or less with respect to 100 parts by weight of the active ingredient excluding the surface modifier solvent.
Optional component 3: The surface modifier may further contain a surfactant, an antifoaming agent, a water-soluble or water-dispersible fine powder substance, and other auxiliary agents. The amount of the optional component is usually 20 parts by weight or less based on 100 parts by weight of the active ingredient excluding the solvent for the surface modifier.

[Formation of surface modified layer]
Each component of the surface modifier is used after being dissolved in water or a hydrophilic solvent such as methyl alcohol, ethyl alcohol, isopropyl alcohol, etc., but among these, it is preferably used in the form of an aqueous solution. The solution concentration is usually about 0.1 to 20% by weight, preferably about 0.1 to 10% by weight. The coating method is performed by die method, lip method, roll method, gravure method, spray method, blade method, reverse method, air knife method, size press method, Mayer bar method, etc., smoothing if necessary, drying process After that, excess water and hydrophilic solvent are removed. Coating amount is 0.005~5g / m ² as solid content after drying is preferably 0.01 to 2 g / m ^2.
When the thermoplastic resin film forming the thermoplastic resin film layer (A) is a stretched film, the surface-modified layer may be applied in one or more stages regardless of longitudinal or lateral stretching. I do not care. On the surface of the thermoplastic resin film layer (A), after the above-mentioned surface treatment or after the surface modification layer formation, a writability imparting layer, a print quality improving layer (pigment coat layer) on the surface, if necessary, A thermal transfer receiving layer, a laser print layer, a heat-sensitive recording layer, an ink jet receiving layer and the like can be provided by the same coating method as that for forming the surface modified layer.

<Pigment coat layer>
As the pigment coat layer for improving the printing quality used in the present invention, as described in detail in JP-A-4-77530, JP-A-3-10894, JP-A-2003-127290, etc., Usually, known materials used as a coating agent for coated paper can be used. Thereby, it is possible to obtain a printed matter having good adhesion, drying property, and coloring property of the printing ink. Moreover, the writing property with a pencil is also good.

<Thermosensitive recording layer, laser print receiving layer, thermal transfer receiving layer>
As the heat-sensitive recording layer, laser print receiving layer, and thermal transfer receiving layer for printing used in the present invention, known ones as described in detail in JP-A-9-164768 can be used. By providing these layers, variable information such as barcodes and product names can be suitably printed with a suitable printer, and a high-definition and water-resistant printed matter can be obtained.

<Inkjet receiving layer>
As the ink jet receiving layer for printing used in the present invention, known ones as described in detail in JP-A-9-156208 and the like can be used. By providing these layers, printing with a suitable printer can be suitably performed, and a water-resistant printed matter can be obtained in combination with the water resistance of the resin film or resin container.

<Concealing layer (2b)>
A concealing layer (2b) may be provided on at least one surface of the thermoplastic resin film (2) of the present invention. The concealing layer can be formed by performing white solid printing or black solid printing with a thickness of 1 to 50 μm, preferably 5 to 40 μm, by letterpress printing, offset printing, screen printing, flexographic printing, gravure printing or the like. The pigment coat layer may also serve as a concealing layer. In order to improve the design, the concealing layer is developed by exposing the interference fringes to the metal direct vapor deposition, metal transfer vapor deposition, metal foil transfer, metal powder containing paint coating, pearl pigment containing paint coating, photosensitive resin. It can be formed by a (hologram shaping) method or the like. By providing such a concealing layer, there is an advantage that the designability as a label can be improved, the transparent resin film can be made opaque, and the printable layer (2a) can be provided on both sides thereof. .

<Adhesive layer (3)>
The adhesive layer (3) used for the in-mold molding label of the present invention can be provided between the thermoplastic resin film (1) and the thermoplastic resin film (2), and adheres each film, The antenna and the IC chip can be embedded and fixed. The adhesive used for the adhesive layer (3) preferably contains at least one of a pressure-sensitive adhesive, a curable resin adhesive, an ultraviolet curable adhesive, and an electron beam curable adhesive, and in particular pressure sensitive. It is preferable to use any one of an adhesive, a curable resin adhesive, and an ultraviolet curable adhesive.
Moreover, in order to improve the water resistance, durability, and security of the in-mold molding label, the higher the adhesive strength between the thermoplastic resin film (1) and the thermoplastic resin film (2), the better. Is preferably 300 gf / 25 mm or more, more preferably 300 to 8000 gf / 25 mm, and particularly preferably 500 to 7000 gf / 25 mm. When the adhesive strength between the film (1) and the film (2) is less than 300 gf / 25 mm, it is easy to peel off, and the thermoplastic resin film (2) may fall off from the container, or the appearance may deteriorate due to blistering. It is easy to worry about security issues.

<Pressure sensitive adhesive>
The method of using a pressure sensitive adhesive as the adhesive layer (3) is the simplest method for forming the in-mold label of the present invention. For example, an antenna and an IC chip are installed on a thermoplastic resin film (1) having a heat-sealable layer, and a thermoplastic resin film (2) on which a pressure-sensitive adhesive layer is previously provided is used as a pressure-sensitive adhesive. If the layers are laminated and bonded so as to be in contact with the thermoplastic resin film (1) while embedding the antenna and the IC chip, the label for in-mold molding of the present invention can be obtained.
The type and thickness (coating amount) of the pressure-sensitive adhesive can be variously selected depending on the type of thermoplastic resin film used, the environment in which the label is used, the strength of adhesion, and the like. Can be formed by applying water-based or solvent-based pressure-sensitive adhesives that are generally used and drying, and natural rubber-based, synthetic rubber-based, acrylic-based, silicone-based, etc. can be used. These synthetic polymer-based pressure-sensitive adhesives The agent can be used in a form dispersed in water, such as an organic solvent solution, a dispersion or an emulsion.

The application method of pressure sensitive adhesive is not limited at all, but for example, kiss coating method, die coating method, bar coating method, comma coating method, knife coating method, lip coating method, roll coating method, curtain coating method, gravure coating method, spray Examples thereof include a method of directly applying onto a thermoplastic resin film by a coating method, a blade coating method, a reverse coating method, a reverse gravure method, etc., and a transfer method of transferring a material applied by these methods onto a process paper.
Specific examples of the rubber-based pressure-sensitive adhesive include polyisobutylene rubber, butyl rubber and a mixture thereof, or these rubber-based pressure-sensitive adhesives including abietic acid rosin ester, terpene / phenol copolymer, terpene / indene copolymer The thing which mix | blended tackifiers, such as coalescence, is mentioned. Specific examples of the acrylic pressure-sensitive adhesive include a glass transition point of −20 ° C. such as 2-ethylhexyl acrylate / n-butyl acrylate copolymer and 2-ethylhexyl acrylate / ethyl acrylate / methyl methacrylate copolymer. The following are mentioned. In order to improve the opacity of the label, an adhesive containing a pigment such as titanium white can be used.
The coating amount of the pressure-sensitive adhesive is not particularly limited, but is usually in the range of ^{3 to} 60 g / m ² , preferably 10 to 40 g / m ² in terms of solid content.

<Curing resin adhesive>
The curable resin adhesive that can be used as the adhesive layer (3) is a chemical reaction curable resin adhesive generally classified into a room temperature one-part curable type, a room temperature two-part curable type, etc. It is possible to obtain a strong adhesive strength. Usually, it can be pressure-bonded at room temperature or in a heated state, and in the present application, a thermosetting adhesive can be used as long as it can be cured with little heating. Generally, cyanoacrylate-based, butyral-based, silicone-based, polyurethane-polyester-based, polyester-based, epoxy-based, and other compositions containing polyether polyol / polyisocyanate adhesive and polyester polyol-polyisocyanate adhesive can be used.
Specific examples of the adhesive include, for example, a liquid resin adhesive, for example, a polyurethane resin adhesive, EL-150 (trade name) manufactured by Toyo Morton Co., Ltd., or a mixture of BLS-2080A and BLS-2080B. As the polyester resin adhesive, AD-503 (trade name) manufactured by the same company can be applied. These are coated by the same method as the pressure sensitive adhesive so that the dry coating amount is 0.5 to 25 g / m ^2, and the thermoplastic resin film (1) and the heat are coated by a method called dry lamination or wet lamination. A plastic resin film (2) is laminated.

<UV curable adhesive>
The UV curable adhesive that can be used as the adhesive layer (3) is generally an adhesive that is reactively cured by irradiating ultraviolet rays, and is easier to handle than a chemically reactive curable resin adhesive. The time required for curing is short, and once cured, very strong adhesive strength can be obtained. In the composition of the ultraviolet curable adhesive, urethane-based, polyester-based, and epoxy-based resins are used as prepolymers, and acrylic acid esters are used as monomers. Moreover, a photoinitiator, a photoinitiator, and a silicone resin as needed are used as an additive. In the present invention, a visible light curable adhesive is also considered to be included in this genus.
In this case, the light transmittance in the ultraviolet region (wavelength 380 nm) of at least one of the thermoplastic resin film (1) and the thermoplastic resin film (2) is set to 60% or more, and the adhesive is irradiated with ultraviolet rays from the film layer side. It is preferable to cure the ultraviolet curable adhesive of the layer (3).

<Electron beam curable adhesive>
The electron beam curable adhesive that can be used as the adhesive layer (3) is generally an adhesive that is reactively cured by irradiation with an electron beam, and is easier to handle than a chemically reactive curable resin adhesive. After irradiation, the time required for curing is short, and once cured, very strong adhesive strength can be obtained. When the electron beam curable adhesive is used, it can be suitably used even if the thermoplastic resin film (1) and the thermoplastic resin film (2) are opaque resin films. In the composition of the electron beam curable adhesive, polyamide resin, vinyl resin, urethane resin, polyester resin, epoxy resin or the like is used as a prepolymer, and acrylic acid ester or the like is used as a monomer. In addition, when hardening with an electron beam, additives, such as a photoinitiator, are unnecessary in particular, However, When promoting sclerosis | hardenability, a well-known photoinitiator can be added.
As the coating method of the ultraviolet curable adhesive and the electron beam curable adhesive, the same method as the pressure-sensitive adhesive, or letterpress printing, offset printing, screen printing, flexographic printing, gravure printing and the like can be preferably used.

<Antenna and IC chip>
The antenna and IC chip (IC module) for transmitting and receiving data in a non-contact manner used for the in-mold molding label of the present invention preferably have any function of an RFID tag, a smart tag, and an active tag.
There are many documents related to antennas and IC chips (IC modules) that transmit and receive data without contact. Here, an RFID tag is an IC chip composed of a memory card such as PROM, EPROM, or EEPROM. Codes for identification are recorded in these ROMs, but these codes cannot be altered by factory burning, or can be written in a state that has passed authentication with a circuit that controls access. It is characterized by being able to be downsized, and it is difficult to reproduce including the size, and has copy resistance.

Smart tags are more difficult than RFID to analyze the internal structure of software and hardware and the data stored in them, and generally a CPU card with an IC chip containing a CPU (also called MPU) It consists of Since the card itself has a calculation function, authentication using encryption can be performed between the IC chip and the reader / writer, and the tag itself can determine whether or not the access is valid when reading and writing data. For this reason, it is very difficult for a third party to perform unauthorized access and alteration, and high security can be realized.
An IC module that transmits and receives data without contact cannot supply a voltage for starting a circuit from the outside unlike a contact-type IC module. For this reason, electromagnetic waves (radio waves or magnetic fields) or microwaves from the reader / writer are electrostatically converted into starting voltages to operate the circuit. However, the type of electromagnetic waves used, the distance between the IC module and the reader / writer, the direction, etc. are received. Depending on the condition, there may be a case where a sufficient starting voltage cannot be obtained and the operation becomes unstable. An active tag has a long-life battery or a self-generating function (such as photovoltaic power generation) and can operate stably even when not accessed. On the other hand, the former is sometimes called a passive tag.
In the current technology, the IC module becomes larger as it becomes the latter, and it is difficult to seal between the films. Therefore, in the in-mold molding label of the present invention, it is more preferable to use an RFID or a smart tag as the IC module. It is preferable to use RFID.

  The IC module is provided by forming an IC circuit and a wiring circuit on a circuit board. Board materials for circuit boards are in accordance with purposes, such as rigid types such as general paper phenol, glass epoxy, BT resin, FR4, composite, flexible type such as polyimide film, polyester film, polyethylene film, and composite type of both Is used. The wiring circuit is a method of installing a coiled metal conductor on the substrate material using an adhesive, or by deforming the film by heating and pressing, or a substrate material stretched with a metal such as copper or aluminum. A method of etching and providing a metal part, a method of transferring a metal foil formed of a conductive metal such as silver onto a substrate, and printing and drying by silk screen printing or ink jet printing using a conductive paste paint Then, it can be formed by a method of providing a wiring pattern on the substrate. You may provide this directly on a thermoplastic resin film (1) or a thermoplastic resin film (2).

The IC module is formed by mounting an IC circuit on a substrate on which a wiring circuit is formed by the above method, and electrically connecting the antenna and the IC circuit. For mounting the IC circuit on the substrate, wire bonding, tape automated bonding, chip-on-board or flip-chip mounting is used. For mounting IC circuits and connecting to antennas, normal soldering, use of conductive adhesives, and ultrasonic waves can be used. There is.
An IC chip is a small one having a size of 0.3 to 0.4 mm square and a thickness of 60 μm. This including the antenna can be easily embedded in the above-mentioned adhesive layer (3), and the presence of the IC module cannot be easily confirmed from the appearance of the obtained in-mold molding label. The IC module can be used by being embedded (packaged) with an epoxy resin or the like in order to protect the mounted IC circuit or wiring circuit. In this case, the thickness of the IC module is 150 μm to 1 mm after embedding with an epoxy resin or the like.

<Formation of in-mold molding label>
As a method for forming the label for in-mold molding of the present invention, an IC chip is provided after an adhesive layer (3) is provided on the surface of either the thermoplastic resin film (1) or the thermoplastic resin film (2). And the antenna is mounted on the adhesive, and the other film is laminated and bonded. This is because when both the thermoplastic resin film (1) and the thermoplastic resin film (2) to be used are in a roll form, a dry lamination method is used, and when one is a sheet form, both are in a sheet form. In this case, a hot press lamination method can be preferably used. Further, the sheets may be bonded together manually.
At the time of bonding by the above method, printing and printing on the thermoplastic resin film (2) may be performed before molding of the label for in-mold molding (before bonding) or after molding (after bonding). good.

<Thermoplastic resin container>
The label for in-mold molding of the present invention can be used for various resin containers. For example, it can be used for containers made of high-density polyethylene, polypropylene, polyester, polystyrene, polyvinyl chloride, polycarbonate, and the like, and is particularly suitable for containers made of high-density polyethylene, polypropylene, polyester, and polystyrene. The label for in-mold molding of the present invention is integrally attached at the time of molding the container in the mold to provide a thermoplastic resin container.
In the present invention, the adhesive strength between the thermoplastic resin container and the in-mold molding label is preferably 300 gf / 25 mm or more, more preferably 300 to 8000 gf / 25 mm, and more preferably 500 to 7000 gf / 25 mm. Particularly preferred. When the adhesive strength between the in-mold molding label and the container is less than 300 gf / 25 mm, peeling is easy, and the in-mold molding label falls off from the container, and the function as a label is insufficient.
The thermoplastic resin container of the present invention is manufactured in a mold by at least one of injection molding, hollow molding, differential pressure molding, and foam molding. Among them, it is suitable for injection molding, hollow molding, and differential pressure molding.

The features of the present invention will be described more specifically with reference to the following examples. However, the present invention does not depart from the gist of the present invention in terms of materials, amounts used, ratios, processing methods, processing procedures, etc. shown in these examples. It can be changed as long as possible. Therefore, the scope of the present invention should not be construed as being limited to the specific examples shown below.
In the present invention, each physical property value and its range were measured according to the following method.
Thickness: JIS-P-8118 (1998)
Density: JIS-P-8124 (1998)
Whiteness: JIS-P-8148 (2001)
Porosity: Obtained by the following formula.
Porosity (%) = [(ρ ₀ −ρ) / ρ ₀ ] × 100
(Where ρ ₀ is the true density of the film and ρ is the density of the film.)
Thermal conductivity: Measured by a probe method using a thermal conductivity meter “QTM-D3” (trade name) manufactured by Kyoto Electronics Industry.
Heat shrinkage ratio: A thermoplastic resin film is cut into a square of 100 mm both vertically and horizontally, and after measuring its actual dimensions in a constant temperature and humidity chamber at a temperature of 23 ° C. and a relative humidity of 50%, it is heat-treated in a 120 ° C. ventilated oven for 30 minutes, After taking out, it stood to cool again for 1 hour in a constant temperature and humidity chamber, and the actual dimension was measured and it calculated | required by calculating a dimensional change compared with before oven heat processing.
Opacity: Based on the method described in JIS P-8138, a value obtained by applying a black plate to the back of the sample and measuring the value measured by applying a white plate to the back of the sample was obtained as a percentage.

<Production Example 1>
<Manufacture of thermoplastic resin film (1) having heat-sealable layer (1a)>
Calcium carbonate 15 having an average particle size of 1.5 μm was added to a mixture of 80% by weight of a propylene homopolymer and 5% by weight of high-density polyethylene having a melt flow rate (MFR: 230 ° C., 2.16 kg load) of 0.8 g / 10 min. The composition (1b) blended with wt% is kneaded in an extruder set at a temperature of 270 ° C., then extruded into a sheet shape with a T-die, cooled by a cooling device, and unstretched sheet Got. Next, this unstretched sheet was heated to a temperature of 140 ° C., and then stretched 4 times in the longitudinal direction using the peripheral speed of the roll group to obtain a 4 times longitudinally stretched sheet.
A composition for surface layer (1c) in which 55% by weight of propylene homopolymer having an MFR of 4 g / 10 min and 45% by weight of calcium carbonate having an average particle size of 1.5 μm is mixed is kneaded in an extruder set at 270 ° C. Then, the extruded sheet was laminated on one side of the 4 times longitudinally stretched sheet obtained in the above process.

An ethylene / 1-hexene copolymer (1-hexene) having an MFR of 18 g / 10 min, a density of 0.898 g / cm ³ and a melting point of 90 ° C. obtained by copolymerizing ethylene and 1-hexene using a metallocene catalyst content 22 wt%, crystallinity 30, the number-average molecular weight 23,000) and 70 wt%, MFR is 4g / 10 min, density of 0.92 g / cm ^3, high pressure process of melting point 110 ° C. low density polyethylene 30 wt% The mixture was mixed with a tumbler mixer for 3 minutes, and this was extruded into a strand shape from a die and cut to obtain a heat-sealable layer pellet (1a).
This and the composition (1d) having the same composition as (1c) are melt-kneaded at 250 ° C. using different extruders, supplied to one coextrusion die, and laminated at 230 ° C. in the die. After that, the other side of the 4 × longitudinal stretch sheet obtained in the above step was laminated so that the layer (1a) was on the outside.

This four-layer film was guided to a tenter oven, reheated to 155 ° C., stretched 8 times in the transverse direction, subsequently heat-set at 160 ° C., cooled to 55 ° C., and slit the ear. Further, a corona discharge treatment of 70 W / m ² / min was performed on the surface layer (1c) side. This has a density of 0.80 g / cm ³ and a wall thickness of 100 μm (each layer thickness (1c / 1b / 1d / 1a) = 15/70/10/5 μm) (1c / 1b / 1d / 1a = uniaxial) A thermoplastic resin film (1) having a heat-sealable layer (1a) of stretching / biaxial stretching / uniaxial stretching / uniaxial stretching) was obtained.
This product had a whiteness of 96%, a porosity of 35%, a thermal conductivity of 0.115 W / m · K, a thermal shrinkage of 3.5%, and an opacity of 95%.

<Production Example 2>
<Manufacture of thermoplastic resin film (1) having heat-sealable layer (1a)>
Calcium carbonate 1 having an average particle size of 1.5 μm was added to a mixture of 94% by weight of propylene homopolymer and 5% by weight of high-density polyethylene having a melt flow rate (MFR: 230 ° C., 2.16 kg load) of 0.8 g / 10 min. The composition (1b) blended with wt% is kneaded in an extruder set at a temperature of 270 ° C., then extruded into a sheet shape with a T-die, cooled by a cooling device, and unstretched sheet Got. Next, this unstretched sheet was heated to a temperature of 140 ° C., and then stretched 4 times in the longitudinal direction using the peripheral speed of the roll group to obtain a 4 times longitudinally stretched sheet.
A composition for surface layer (1c) in which 99% by weight of propylene homopolymer having an MFR of 4 g / 10 min and 1% by weight of calcium carbonate having an average particle diameter of 1.5 μm is mixed is kneaded in an extruder set at 270 ° C. Then, the extruded sheet was laminated on one side of the 4 times longitudinally stretched sheet obtained in the above process.

An ethylene / 1-hexene copolymer (1-hexene) having an MFR of 18 g / 10 min, a density of 0.898 g / cm ³ and a melting point of 90 ° C. obtained by copolymerizing ethylene and 1-hexene using a metallocene catalyst content 22 wt%, crystallinity 30, the number-average molecular weight 23,000) and 70 wt%, MFR is 4g / 10 min, density of 0.92 g / cm ^3, high pressure process of melting point 110 ° C. low density polyethylene 30 wt% The mixture was mixed with a tumbler mixer for 3 minutes, and this was extruded into a strand shape from a die and cut to obtain a heat-sealable layer pellet (1a).
This and the composition (1d) having the same composition as (1c) are melt-kneaded at 250 ° C. using different extruders, supplied to one coextrusion die, and laminated at 230 ° C. in the die. After that, the other side of the 4 × longitudinal stretch sheet obtained in the above step was laminated so that the layer (1a) was on the outside.

The four-layer film was introduced into a tenter oven, reheated to 170 ° C., stretched 8 times in the transverse direction, subsequently heat-set at 172 ° C., cooled to 55 ° C., and slits at the ears. Further, a corona discharge treatment of 70 W / m ² / min was performed on the surface layer (1c) side. This has a density of 0.910 g / cm ³ and a thickness of 75 μm (each layer thickness (1c / 1b / 1d / 1a) = 17/41/12/5 μm) (1c / 1b / 1d / 1a = uniaxial) A thermoplastic resin film (1) having a heat-sealable layer (1a) of stretching / biaxial stretching / uniaxial stretching / uniaxial stretching) was obtained.
This product had a whiteness of 89%, a porosity of 1%, a thermal conductivity of 0.135 W / m · K, a thermal shrinkage of 2.3%, and an opacity of 15%.

<Production Example 3>
A composition in which 25% by weight of calcium carbonate having an average particle diameter of 1.5 μm is blended with a mixture of 65% by weight of a propylene homopolymer having a melt flow rate (MFR) of 0.8 g / 10 min and 10% by weight of high-density polyethylene ( A), a composition (B) in which 99% by weight of a propylene homopolymer having a melt flow rate (MFR) of 4 g / 10 min and 1% by weight of titanium dioxide are mixed, and a composition having the same composition as the composition (B) (C) was melt-kneaded at 250 ° C. using three separate extruders. Then, after supplying to one co-pressing die and laminating within a die (B / A / C), it extruded to the sheet form and cooled to about 60 degreeC with the cooling roll, and the laminated | multilayer film was obtained.
This laminated film is reheated to 145 ° C., then stretched 5 times in the machine direction by utilizing the difference in peripheral speed of many roll groups, reheated to about 150 ° C., and 8.5 times in the transverse direction with a tenter. Stretched. Then, after annealing at 160 ° C., cooling to 60 ° C., slitting the ear, and forming a three-layer structure (B / A / C = biaxial stretching / biaxial stretching / biaxial stretching) with a thickness of 100 μm (3 μm / 94 μm / 3 μm), density 0.66 g / cm ³ , whiteness 96%, porosity 40%, thermal conductivity 0.091 W / m · K, thermal shrinkage 2.5%, opacity A 90% biaxially stretched film was obtained.

<Production Example 4>
A composition in which 16% by weight of calcium carbonate having an average particle diameter of 1.5 μm is blended in a mixture of 81% by weight of a propylene homopolymer having a melt flow rate (MFR) of 0.8 g / 10 min and 3% by weight of high density polyethylene ( 1c) was kneaded in an extruder set at a temperature of 270 ° C., then extruded into a sheet, and further cooled by a cooling device to obtain an unstretched sheet. Next, the sheet was heated again to a temperature of 160 ° C., and then stretched 5 times in the machine direction to obtain a 5-fold longitudinally stretched film.
The composition for the surface layer (1d) in which 54% by weight of propylene homopolymer having an MFR of 4 g / 10 min and 46% by weight of calcium carbonate having an average particle size of 1.5 μm was mixed was kneaded in an extruder set at 210 ° C. After that, this was extruded into a sheet shape by a die, and this was laminated on both surfaces of the 5-fold longitudinally stretched sheet obtained in the above step to obtain a laminated film having a three-layer structure. Next, after the laminated film having the three-layer structure is cooled to a temperature of 60 ° C., it is again heated to a temperature of about 160 ° C., stretched 7.5 times in the transverse direction using a tenter, and at a temperature of 165 ° C. Annealing treatment, cooling to a temperature of 60 ° C., slitting the ears, and a thickness of 80 μm (1d / 1c / 1d = 3 layer structure (1d / 1c / 1d = uniaxial stretching / biaxial stretching / uniaxial stretching)) 17 μm / 46 μm / 17 μm) with a density of 1.02 g / cm ³ , whiteness 94%, porosity 29%, thermal conductivity 0.13 W / m · K, thermal shrinkage 1.2%, opacity A 72% laminated stretched film was obtained.

<Production Example 5>
A composition in which 1% by weight of calcium carbonate having an average particle diameter of 1.5 μm is blended with a mixture of 96% by weight of a propylene homopolymer having a melt flow rate (MFR) of 0.8 g / 10 min and 3% by weight of high-density polyethylene. After kneading with an extruder set at a temperature of 270 ° C., the mixture was extruded into a sheet and further cooled by a cooling device to obtain an unstretched sheet. Next, the sheet was heated again to a temperature of 180 ° C., then stretched 5 times in the machine direction, and then annealed at 182 ° C. to obtain a uniaxially stretched film.
The uniaxially stretched film was cooled to a temperature of 60 ° C., and had a thickness of 80 μm, a density of 0.90 g / cm ³ , a porosity of 0.5%, a thermal conductivity of 0.137 W / m · K, and a thermal shrinkage of 1. A uniaxially stretched film of 0% and opacity of 10% was obtained.

<Production Example 6>
<Manufacture of thermoplastic resin film (1) having heat-sealable layer (1a)>
On one side of the biaxially stretched film obtained in Production Example 3, an ethylene / methacrylic acid copolymer (manufactured by Chuo Rika Kogyo Co., Ltd., trade name: Aquatex AC-) having a phase transition temperature of 90 ° C. and an average particle diameter of 0.7 μm 3100) Ethylene / methyl methacrylate copolymer (manufactured by Chuo Rika Kogyo Co., Ltd., trade name: Ricabond ES-90) having 45% by weight and a phase transition temperature of 108 ° C. Is coated with a slot die coater so that the dry coating amount is 4 g / m ² at a line speed of 20 m / min, and dried in an oven with a length of 10 m set at a drying temperature of 80 ° C. A heat-sealable layer (1a) made of a resin was provided to obtain a thermoplastic resin film (1).

<Production Example 7>
<Manufacture of thermoplastic resin film (1) having heat-sealable layer (1a)>
A thermoplastic resin film (1) having a heat-sealable layer (1a) was obtained in the same manner as in Production Example 6 except that the laminated stretched film obtained in Production Example 4 was used.
<Production Example 8>
<Manufacture of thermoplastic resin film (1) having heat-sealable layer (1a)>
A thermoplastic resin film (1) having a heat-sealable layer (1a) was obtained in the same manner as in Production Example 6 except that the uniaxially stretched film obtained in Production Example 5 was used.

<Production Example 9>
<Manufacture of printable thermoplastic resin film (2)>
A composition in which 16% by weight of calcium carbonate having an average particle diameter of 1.5 μm is blended in a mixture of 81% by weight of a propylene homopolymer having a melt flow rate (MFR) of 0.8 g / 10 min and 3% by weight of high density polyethylene ( 2c) was kneaded in an extruder set at a temperature of 270 ° C., then extruded into a sheet, and further cooled by a cooling device to obtain an unstretched sheet. Next, the sheet was heated again to a temperature of 150 ° C., and then stretched 5 times in the machine direction to obtain a 5-fold longitudinally stretched film.

The composition for the surface layer (2d), in which 54% by weight of propylene homopolymer having an MFR of 4 g / 10 min and 46% by weight of calcium carbonate having an average particle size of 1.5 μm was mixed, was kneaded in an extruder set at 210 ° C. After that, this was extruded into a sheet shape by a die, and this was laminated on both surfaces of the 5-fold longitudinally stretched sheet obtained in the above step to obtain a laminated film having a three-layer structure. Next, after cooling the laminated film of this three-layer structure to a temperature of 60 ° C., it is again heated to a temperature of about 155 ° C., stretched 7.5 times in the transverse direction using a tenter, and at a temperature of 165 ° C. Annealing treatment, cooling to a temperature of 60 ° C., slitting the ear part, and a thickness of 60 μm (2d / 2c / 2d = 3d structure (2d / 2c / 2d = uniaxial stretching / biaxial stretching / uniaxial stretching)) A laminated stretched film having a density of 0.79 g / cm ³ , a whiteness of 96%, a porosity of 32%, a heat shrinkage of 1.9%, and an opacity of 87% was obtained using a laminated film of 10 μm / 40 μm / 10 μm).

A surface modified layer was provided as a printable layer (2a) on both surface layers of the obtained laminated stretched film by the following method.
<Surface oxidation treatment>
Corona discharge treatment was performed on both sides of the thermoplastic resin film (2) as follows. The corona discharge treatment machine uses a Kasuga Electric Co., Ltd. corona discharge treatment machine HFS400F, the aluminum electrode and the treater roll use a silicone-coated roll, the gap between the electrode and the roll is 2 mm, the line speed is about 30 m / min, the applied energy Processing was performed at a density of 50 W · min / m ² .
<Formation of surface modified layer>
Thereafter, the surface treatment agent prepared by the following method was applied to both sides of the thermoplastic resin film (2) subjected to corona discharge treatment so that the coating amount after drying with a roll coater was 0.06 g / m ^{2 on} one side. And dried in an oven at a temperature of about 65 ° C. for several tens of seconds to obtain a printable thermoplastic resin film (2). The heat shrinkage and opacity were the same as those of the laminated stretched film.

<Adjustment of surface treatment agent>
Primer production:
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and an introduction tube for nitrogen substitution, 25 of polyethyleneimine “Epomin P-1000 (degree of polymerization 1600)” (manufactured by Nippon Shokubai Co., Ltd., trade name) 100 parts by weight of an aqueous solution, 10 parts of n-butyl chloride and 10 parts of propylene glycol monomethyl ether were added, stirred under a nitrogen stream, and subjected to a denaturation reaction at a temperature of 80 ° C. for 20 hours to give 20% by weight of butyl as a solid content. A primer comprising a modified polyethyleneimine aqueous solution was obtained.

Antistatic polymer production:
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and an introduction tube for nitrogen substitution, 35 parts of dimethylaminoethyl methacrylate, 20 parts of ethyl methacrylate, 20 parts of cyclohexyl methacrylate, 25 parts of stearyl methacrylate, 150 parts of ethyl alcohol and 1 part of azobisisobutyronitrile were added, and a polymerization reaction was performed at a temperature of 80 ° C. for 6 hours under a nitrogen stream. Next, 70 parts of a 60% aqueous solution of 3-chloro-2-hydroxypropyltrimethylammonium chloride was added, and the mixture was further reacted at a temperature of 80 ° C. for 15 hours. As a result, an antistatic polymer comprising 20% by weight of a quaternary ammonium salt copolymer was obtained.
Production of optional component 1:
The following was used as a polyamine polyamide / epichlorohydrin adduct.
“WS-570” (trade name) manufactured by Nippon PMC Co., Ltd., solid content 25% by weight
Blended in water medium so that the solid content of each blended component prepared above is 100 parts of surface treatment agent, 0.5 part of primer, 0.5 part of antistatic polymer, and 0.5 part of optional component 1 The surface treatment agent was prepared by sufficiently stirring.

<Production Example 10>
<Manufacture of printable thermoplastic resin film (2)>
On one side of the printable thermoplastic resin film (2) obtained in Production Example 9, black solid printing was performed by offset printing to provide a concealing layer (2b). The opacity of this was 100%.
<Production Example 11>
<Manufacture of printable thermoplastic resin film (2)>
On one side of the biaxially stretched film obtained in Production Example 3, a coating solution for a thermal transfer receiving layer containing the following composition was applied by wire bar coating so that the thickness when dried was 4 μm and dried to be printable. As a layer (2a), a printable thermoplastic resin film (2) was obtained. This film had a thermal shrinkage rate equivalent to that of the biaxially stretched film and an opacity of 95%.

<Composition of coating solution for thermal transfer receiving layer>
The following compositions were mixed to prepare a thermal transfer receiving layer coating solution.
・ Byron 200 (saturated polyester manufactured by Toyobo Co., Ltd .: TK = 67 ° C.) 5.3 parts by weight ・ Byron 290 (saturated polyester manufactured by Toyobo Co., Ltd .: TK = 77 ° C.) 5.3 parts by weight ・ Vinylite VYHH (vinyl chloride manufactured by Union Carbide) Copolymer) 4.5 parts by weight Titanium oxide (KA-10 manufactured by Titanium Industry Co., Ltd.) 1.5 parts by weight KF-393 (amino-modified silicone oil manufactured by Shin-Etsu Silicone) 1.1 parts by weight X-22 343 (Epoxy-modified silicone oil manufactured by Shin-Etsu Silicone) 1.1 parts by weight-Toluene 30 parts by weight-Methyl ethyl ketone 30 parts by weight-Cyclohexanone 22 parts by weight

<Production Example 12>
<Manufacture of IC chip and antenna>
The antenna circuit was printed on one side of a 125 μm thick polyester film by silk screen printing with an isocyanate solvent silver paste, dried with hot air, and left in a constant temperature room at 80 ° C. for 3 hours, and then taken out. Thereafter, an IC chip (thickness: 60 μm) was mounted on the antenna surface, the surface was embedded with an epoxy resin, and an IC module (thickness: 300 μm) composed of an IC chip and an antenna and having an RFID function was obtained.

[Example 1]
On one side of the printable thermoplastic resin film (2) obtained in Production Example 9, an acrylic pressure-sensitive adhesive (trade name: Olivevine BPS-1109, manufactured by Toyo Ink Chemical Co., Ltd.) was added at a solid content of 25 g / after coating such that m ^2, and formed the adhesive layer (3) is dried. The surface layer of the thermoplastic resin film (1) having the heat-sealable layer (1a) obtained in Production Example 1 on which the IC chip and the antenna obtained in Production Example 12 are mounted on the adhesive layer (3) ( 1c) and the adhesive (3) on the thermoplastic resin film (2) were stacked so as to be in contact with each other, and bonded through a pressure-bonding roll to obtain the in-mold molding label of the present invention.
The adhesive strength between the thermoplastic resin film (1) and the thermoplastic resin film (2) was 800 gf / 25 mm.

[Example 2]
On the side of the concealable layer (2b) of the printable thermoplastic resin film (2) obtained in Production Example 10, an ultraviolet curable adhesive (trade name: UV SPA, manufactured by Teikoku Mfg. Co., Ltd.) is used as a solid content. Then, the thermoplastic resin film (1) having the heat-sealable layer (1a) obtained in Production Example 2 is mounted after mounting the IC chip and the antenna obtained in Production Example 12 to 20 g / m ^2. The surface layer (1c) side and the adhesive on the thermoplastic resin film (2) were laminated so as to be in contact with each other, and were bonded via a pressure-bonding roll. Next, ultraviolet rays were irradiated from the thermoplastic resin film (1) side with an ultraviolet irradiator. At this time, ultraviolet rays were irradiated with an output of 280 W / cm using a metal halide lamp. The ultraviolet intensity at this time was 2100 mW / cm ² . Since the irradiation width of ultraviolet rays was 77 mm and the line speed was 40 m / min, the integrated amount of ultraviolet rays was 242 mJ / cm ² . Under such curing conditions, the ultraviolet curable adhesive was cured to form the adhesive layer (3), and the in-mold molding label of the present invention was obtained.
The adhesive strength between the thermoplastic resin film (1) and the thermoplastic resin film (2) was 4000 gf / 25 mm.

Example 3
An adhesive (trade name: TM265, manufactured by Toyo Morton Co., Ltd.) on the side of the printable thermoplastic resin film (2) obtained in Production Example 11 that is not the printable layer (2a) is 20 g / m in solid content. After coating to be ² , it was dried to form an adhesive layer (3). On the adhesive layer (3), the IC chip and the antenna obtained in Production Example 12 are mounted, and the heat-sealability of the thermoplastic resin film (1) having the heat-sealable layer (1a) obtained in Production Example 6. The in-mold molding label of the present invention is obtained by stacking and laminating the side that is not the layer (1a) and the adhesive (3) on the thermoplastic resin film (2) so as to be in contact with each other and bonding them via a crimping roll. It was.
The adhesive strength between the thermoplastic resin film (1) and the thermoplastic resin film (2) was 5000 gf / 25 mm.

Example 4
On the side of the thermoplastic resin film (1) having the heat-sealable layer (1a) obtained in Production Example 7 that is not the heat-sealable layer (1a), a polyurethane two-component curable resin adhesive (Toyo Morton Co., Ltd.) Product names: BLS-2080A, BLS-2080B) were applied at a rate of 25 g / m ² (ratio of solid components) to form an adhesive layer (3). The IC chip and the antenna obtained in Production Example 12 are mounted on the adhesive layer (3), and the printable thermoplastic resin film (2) obtained in Production Example 11 is used as a thermal transfer receiving layer (printable layer (2a )) Is laminated on the adhesive layer (3) so as to be on the outside, and bonded via a pressure-bonding roll to obtain an in-mold molding label of the present invention.
The adhesive strength between the thermoplastic resin film (1) and the thermoplastic resin film (2) after curing of the adhesive was 6000 gf / 25 mm.

Example 5
An in-mold molding label of the present invention was obtained in the same manner as in Example 2 except that the thermoplastic resin film (1) having a heat-sealable layer (1a) was obtained in Production Example 8. The adhesive strength between the thermoplastic resin film (1) and the thermoplastic resin film (2) was 4000 gf / 25 mm.
[Examples 6 to 8]
The label for in-mold molding obtained in Examples 1 to 3 was punched into a label size (width 70 mm, height 90 mm), and the printing surface side was applied to one of the blow mold split molds using an automatic label feeder. After fixing the mold in contact with the mold, a high-density polyethylene (melting point: 134 ° C.) parison was melt extruded at 200 ° C., and the split mold was clamped, and then 4.2 kg / cm ² of compressed air was supplied into the parison. A thermoplastic comprising a hollow container in which a parison is inflated to adhere to a mold to form a container and fused with an in-mold molding label, and then the mold is cooled and then the mold is opened and the label is attached. A resin container was obtained.
The adhesive strength between the in-mold label and the container was 830, 800, and 350 gf / 25 mm, respectively.

[Examples 9 to 10]
The label for in-mold molding obtained in Examples 4 to 5 is punched into a label size (width 70 mm, length 90 mm), and the printing surface side is applied to one of the split molds for injection molding using an automatic label feeder. After fixing the mold in contact with the mold and clamping it, high-density polyethylene (melting point: 134 ° C.) is melt-extruded, made into a container by injection molding and fused with an in-mold molding label, and then the mold is cooled A thermoplastic resin container (drink case) consisting of a container with the label opened and a label attached was obtained.
The adhesive strength between the in-mold label and the container was 350 and 370 gf / 25 mm, respectively.

<Evaluation>
An offset printing machine (Mitsubishi Heavy Industries, Model: Diamond II) was used on the printability layer surface of the in-mold molding labels obtained in Examples 1 to 5, and UV offset ink (manufactured by T & K TOKA, trade name: Characters and the like were printed by Best Cure 161S). This was able to be fed and discharged without problems on the printing press. Next, this was punched to obtain an in-mold forming label having a width of 70 mm and a length of 90 mm. The obtained label and the container obtained by the methods of Examples 6 to 10 had water resistance, and did not cause problems even in a frozen storage environment. In addition, no malfunction occurred in the function of the IC module.
The in-mold molding labels obtained in Examples 3 and 4 were punched out to obtain those having a width of 70 mm and a length of 90 mm. A printing device “Barcode Printer B-30-S5 (trade name)” manufactured by Tec Co., Ltd. and a hot-melt ink ribbon “wax type FTR (trade name)” manufactured by Fujikopian Co., Ltd. are used on this printable layer surface. Bar code etc. were printed. The obtained label and the container obtained by the methods of Examples 8 and 9 were water-resistant and did not cause problems even in a frozen storage environment. In addition, no malfunction occurred in the function of the IC module.

The present invention has an object of protecting an IC module from heat, pressure, and static electricity during label molding, printing, printing, in-mold molding, and for in-mold molding including an IC module that can solve production problems. It can be used in the field of labels and thermoplastic containers with labels.
The in-mold label has a function as an IC label, can be printed or printed on the surface, and there is no security concern that an internal IC chip or antenna can be seen through. Further, the internal IC chip and the antenna are not damaged in the process when the label is formed, when processing such as printing and printing, and when the label is attached to the thermoplastic resin container.
Moreover, the thermoplastic resin container obtained, and the label formed integrally therewith are excellent in strength, water resistance, and adhesive strength, and can be used in water both indoors and outdoors, frozen food containers, industrial products, It can be used for various chemical containers, manufacturing process management applications, logistics management applications, returnable boxes, etc.

Claims (22)

A label for in-mold forming to be used in in-mold molding, possess film layer having pores in the in-mold molding label heat-sealable layer (1a) and a layer in the (1b), thermal conductivity A thermoplastic resin film (1) having a thickness of 0.01 to 0.5 W / m · K and a printable thermoplastic resin film (2), and the thermoplastic resin film (1) and the thermoplastic resin film (2 An in-mold forming label comprising an antenna and an IC chip for transmitting and receiving data without contact with each other. In-mold label according to claim 1, porosity obtained from the following equation wherein the Ru 1-60% der of the thermoplastic resin film (1).
Porosity (%) = [(ρ ₀ −ρ) / ρ ₀ ] × 100
(Where ρ ₀ is the true density of the film and ρ is the density of the film.)   The in-mold molding label according to claim 2, wherein the film layer (1b) is stretched in at least a uniaxial direction.   The in-mold molding label according to any one of claims 1 to 3, wherein the thermoplastic resin film (1) and the thermoplastic resin film (2) have a thermal shrinkage of 0 to 5%.   5. The opacity of at least one of the thermoplastic resin film (1), the thermoplastic resin film (2), and the in-mold molding label is 70 to 100%. A label for in-mold molding described in 1.   It has an adhesive layer (3) between the thermoplastic resin film (1) and the thermoplastic resin film (2), and the adhesive layer (3) is a pressure-sensitive adhesive, a curable resin adhesive, and an ultraviolet curing. The in-mold molding label according to claim 1, comprising at least one of a mold adhesive and an electron beam curable adhesive.   The in-mold molding label according to any one of claims 1 to 6, wherein an adhesive strength between the thermoplastic resin film (1) and the thermoplastic resin film (2) is 300 gf / 25 mm or more.   At least one of the thermoplastic resin film (1) and the thermoplastic resin film (2) has a light transmittance of a wavelength of 380 nm of 60% or more, and the adhesive layer (3) is made of an ultraviolet curable adhesive. The label for in-mold molding according to claim 6 or 7.   The label for in-mold molding according to any one of claims 1 to 8, wherein the thermoplastic resin film (2) comprises a printable layer (2a) on at least one side.   The label for in-mold molding according to claim 9, wherein information including a barcode or a two-dimensional barcode is printed and printed on the printable layer (2a).   The label for in-mold molding according to any one of claims 1 to 10, wherein the thermoplastic resin film (2) includes a concealing layer (2b) on at least one side.   The label for in-mold molding according to claim 11, wherein the concealing layer (2b) comprises at least one of a metal thin film, a white pigment coat, white solid printing, and black solid printing.   The in-mold molding label according to any one of claims 1 to 12, wherein at least one of the thermoplastic resin film (1) and the thermoplastic resin film (2) contains a crystalline polyolefin resin.   The in-mold molding label according to claim 13, wherein the crystalline polyolefin-based resin is a propylene-based resin.   The in-house according to any one of claims 1 to 14, wherein at least one of the thermoplastic resin film (1) and the thermoplastic resin film (2) contains at least one of an inorganic fine powder and an organic filler. Label for molding.   The in-mold molding label according to any one of claims 1 to 15, wherein the heat-sealable layer (1a) is made of a heat-sealable resin containing an ethylene-based resin having a melting point of 50 to 130 ° C.   The heat-sealable layer (1a) was provided by applying and drying an aqueous coating liquid containing a heat-sealable resin dispersion having a phase transition temperature of 50 to 140 ° C. on the thermoplastic resin film (1). The label for in-mold molding according to any one of claims 1 to 16.   The in-mold molding label according to any one of claims 1 to 17, wherein the antenna and the IC chip for transmitting and receiving data in a non-contact manner have a function of any one of an RFID, a smart tag, and an active tag.   The label for in-mold molding according to any one of claims 1 to 18, which has an antistatic performance on at least one side.   A thermoplastic resin container in which the in-mold molding label according to claim 1 is integrally attached at the time of in-mold molding.   The thermoplastic resin container according to claim 20, wherein the adhesive strength between the thermoplastic resin container and the label for in-mold molding is 300 gf / 25 mm or more.   The thermoplastic resin container according to claim 20 or 21, wherein the thermoplastic resin container is molded in a mold by at least one molding means of injection molding, hollow molding, differential pressure molding, and foam molding.