JP6731045B2 - Labeled resin molded product and manufacturing method thereof - Google Patents

Description

The present invention relates to a labeled resin molded product. More specifically, the present invention relates to a labeled resin molded product in which the label is attached to the resin molded product by the porous layer of the label.

Conventionally, a blank or a label is previously inserted into a mold, and then a resin molded product such as a container is molded in the mold by injection molding, hollow molding, differential pressure molding, foam molding or the like, and the label is integrated. It is now being done to mold resin molded products. Such a label is called an in-mold molding label. Labels for in-mold molding include gravure-printed resin film, offset-printed synthetic paper, flexo-printed synthetic paper, or high-pressure low-density polyethylene, ethylene-vinyl acetate copolymer on the back surface of aluminum foil. Aluminum labels and the like, which are laminated and gravure-printed on the surface of the foil, are known and put to practical use.

In recent years, from the viewpoint of collection and utilization (material recycling) of plastic containers, there has been a demand for easy separation and removal of labels from labeled plastic containers using in-mold molding labels. In order to meet such a demand, a label provided with a layer that enables interfacial peeling or interlayer peeling has been proposed.

Most of such conventional labels for in-mold molding are provided with a high-density polyethylene or the like as a heat-sealing layer for joining with a resin-molded product. When the material of the molded article of this type of label is the same polyethylene resin as the heat seal layer, a strong adhesive force with the molded article can be obtained. However, when the material of the molded product is polypropylene, polystyrene, polyethylene terephthalate or the like different from the heat seal layer, the adhesive strength with the molded product is extremely low, and the label easily peels off from the molded product during transportation. There was a drawback. Therefore, in order to strengthen the bond between the label and the molded product, it is necessary to prepare a label that uses the resin of the same material as the molded product as the heat seal layer for each molded product, which complicates the inventory management of the label. Was causing problems. In addition, if the molding temperature of the molded product is low, sufficient adhesive strength cannot be obtained between the molded product and the label, so it is necessary to set the molding temperature of the molded product to a high value, and there is a drawback that productivity decreases. It had been.

Therefore, a new type of in-mold molding that has a porous resin layer with an open surface on the bonding side surface instead of the conventional in-mold molding label that is bonded by heat-sealing a heat-sealing layer made of low melting point resin Labels have been proposed (for example, see Patent Document 1). With this in-mold molding label, the molded resin exerts an anchoring effect by entering into the opening on the surface of the porous resin layer under the pressure during molding, so the bond between the label and molded product is strong regardless of the material of the molded product. Can be By using such a porous resin layer for the label, it becomes possible to attach the label under a wide range of molding condition molding conditions, and the label can be easily formed from the in-mold labeled resin molding product. It became possible to separate.

Patent Document 1: JP 2012-215799 A

By the way, printing information is given in advance to the sticking surface of the label used for the new type of labeled resin molded product as described above, and the exposed surface of the resin molded product side exposed by peeling the label from the resin molded product. If the print information can be confirmed on the surface exposed by peeling or the exposed surface of the label peeled from the resin molded product (the surface exposed by peeling), the information can be used for various purposes. Can and is useful. For example, from the printing information, it is possible to identify the resin molded product from which the label has been peeled off and prevent reuse or forgery of the resin molded product, and further precautions and cautions from the resin molded product after peeling off the label or Product information and the like can be transmitted, and further functions such as secondary use of the peeled label as a coupon ticket can be provided. However, there is no report that actually realizes such a function when the label sticking surface is a porous layer.
For example, after printing is performed on the sticking surface of the label as described in Patent Document 1 and the label is peeled from the labeled resin molded product, the printing remains on the exposed surface of the resin molded product after peeling. It is useful to be able to do so or to allow the printing to remain on the exposed surface after peeling on the label side. However, there is no description or suggestion regarding means for achieving this in the document. In addition, the present inventors print an ink pattern on the sticking surface of the label manufactured under the conditions described in Patent Document 1, and in-mold a labeled resin molded product using the obtained printed label. Then, when the label was peeled off from the resin molded product, it was found that the pattern of the ink could not be confirmed at all on the exposed surface after peeling the label.
Therefore, the present inventors, in the labeled resin molded product in which the label is attached to the resin molded product in the porous layer, when the label is peeled from the resin molded product, the exposed surface after peeling of the resin molded product or the label The subject was to obtain a resin molded product with a label in which a visible ink pattern appears.

In order to solve the above problems, the present inventors have made earnest studies using a label having a laminated structure of a base layer (A) and a porous layer (B). As a result, a label in which the pattern of the ink printed on the surface of the porous layer (B) has penetrated into the porous layer (B) is used, and the porous layer (B) is destroyed when the label is peeled from the resin molded product. It was found that the problem could be solved by designing it as described above. Specifically, the present invention solves the problems by the following means.

[1] A labeled resin molded article having a resin molded article and a label attached to the resin molded article, wherein the label is provided on a base layer (A) and on the base layer (A). The label comprises the porous layer (B), a void present inside the porous layer (B), and an ink composition present so as to occupy a part of the void. ) Side surface is adhered to the resin molded product, and a cut is made from the end face of the porous layer (B) so that the porous layer (B) bisects in the thickness direction, and the cut extends. When the label is peeled from the resin molded product by pulling the base layer (A) as described above, the first porous separation layer (B) in which the porous layer (B) remains attached to the resin molded product. ¹ ) and a second porous separation layer (B ² ) that separates along with the base layer (A), and the surface of the first porous separation layer (B ¹ ) opposite to the resin molded product. said first ink pattern by the ink composition (P ¹⁾ appears, labeled resin shaped article, characterized in that said first ink pattern (P ¹⁾ can be confirmed visually on.
[2] In the first ink pattern (P ¹ ), the ink composition is supplied to the surface of the porous layer (B) opposite to the base layer (A), and the ink composition is added to the porous layer (P ¹ ). The labeled resin molded article according to [1], which is penetrated into the voids of B).
[3] The labeled resin-molded article according to [1] or [2], wherein the ink composition is a colorless ink composition containing substantially no coloring material.
[4] On the surface of the first porous separation layer (B ¹ ) on the side opposite to the resin molded article, a plurality of voids in the pattern formation region in which the first ink pattern (P ¹ ) is formed are Labeled according to [3], which is filled with a colorless ink composition and has different opacity between the pattern formation region and the pattern non-formation region where the first ink pattern (P ¹ ) is not formed. Resin molded product.
[5] On the surface of the first porous separation layer (B ¹ ) on the side opposite to the resin molded product, the pattern non-formed region where the first ink pattern (P ¹ ) is not formed and the resin molded product are formed. Pattern formation in which the first ink pattern (P ¹ ) is formed on the color difference (ΔE _B ) from the surface and on the surface of the first porous separation layer (B ¹ ) opposite to the resin molded product. The labeled resin molded article according to [3] or [4], wherein the difference (ΔE _B −ΔE _P ) between the area and the color difference (ΔE _P ) between the surface of the resin molded article is 1 to 50.
[6] On the surface of the first porous separation layer (B ¹ ) on the side opposite to the resin molded product, the pattern formation region in which the first ink pattern (P ¹ ) is formed and the first ink pattern ( The labeled resin molded article according to any one of [3] to [5], which has a color difference ΔE of 3 or more with respect to a pattern non-formation region in which P ¹ ) is not formed.
[7] A corresponding region (P′) on the surface of the second porous separation layer (B ² ) opposite to the base layer (A) and having a mirror image relationship with the first ink pattern (P ¹ ). The labeled resin molded article according to any one of [3] to [6], in which the ink pattern cannot be visually confirmed.
[8] The labeled resin molded article according to [7], wherein the ink composition is present inside the voids of the corresponding region (P′).
[9] The labeled resin molded article according to [1] or [2], wherein the ink composition is a colored ink composition containing a coloring material.
[10] A notch is formed from the end surface of the porous layer (B) so as to divide the porous layer (B) into two in the thickness direction, and the base layer (A) is pulled so that the notch expands, and the resin molding is performed. When the label is peeled from the product, the ink composition penetrates into the voids inside the base layer (A) rather than the peeling surface of the porous layer (B), so that the first porous separation layer (B ¹ ), the first ink pattern (P ¹ ) of the ink composition appears on the surface opposite to the resin molded article, and the second porous separation layer (B ² ) is peeled off along with the base layer (A). The second ink pattern (P ² ) of the ink composition appears on the surface opposite to the base layer (A), and the label according to [9] allows the second ink pattern (P ² ) to be visually confirmed. Resin molded product.
[11] A pattern formation region in which the second ink pattern (P ² ) is formed on the surface of the second porous separation layer (B ² ) opposite to the base layer (A); The labeled resin molded article according to [10], which has a color difference ΔE of 3 or more with respect to a pattern non-formation region in which the ink pattern (P ² ) is not formed.
[12] The labeled resin molded article according to [10] or [11], wherein the first ink pattern (P ¹ ) and the second ink pattern (P ² ) are in a mirror image relationship with each other.
[13] After the adhesive surface of the adhesive tape is attached to the surface of the second ink pattern (P ² ) on the surface of the second porous separation layer (B ² ), the adhesive tape is separated into the second porous separation layer. When peeled off from the layer (B ² ) at a peeling angle of 180° and a speed of 300 mm/min, the second ink pattern (P ² ) can be visually confirmed on the surface of the second porous separation layer (B ² ). At the same time, the labeled resin molded article according to any one of [10] to [12], wherein the reverse pattern of the second ink pattern (P ² ) can be visually confirmed on the adhesive surface of the adhesive tape.
[14] The labeled resin-molded product according to any one of [1] to [13], which has a porosity of 30 to 70% observed from a cross section in the thickness direction of the porous layer (B).
[15] The porosity observed from the cross section in the thickness direction of the porous layer (B) is larger than the porosity observed from the cross section in the thickness direction of the base layer (A) [1] to [14]. The resin molded product with a label according to any one of claims.
[16] The 180° peel strength according to JIS Z 1707: 1997 plastic film packaging plastic film general rule when peeling the label having the base layer (A) from the resin molded product is 0.3 to 1.6 N/15 mm. The labeled resin molded article according to any one of [1] to [15].

[17] A resin molded article and a resin molded article which remain after peeling the base layer (A) and the second porous separation layer (B ² ) from the labeled resin molded article according to any one of [1] to [16]. 1. A resin molded product with a porous layer having a porous separation layer (B ¹ ).
[18] With the porous layer according to [17], which has a first ink pattern (P ¹ ) of an ink composition on the surface of the first porous separation layer (B ¹ ) opposite to the resin molded product. Resin molded product.

[19] A method for producing the labeled resin molded article according to any one of [1] to [16], which comprises a base layer (A) and a porous layer (B) provided on the base layer. A laminated resin film forming step of forming a laminated resin film having a) and an ink pattern by printing an ink composition on a surface of the laminated resin film opposite to the base layer (A) of the porous layer (B). A printing step for forming a label to form a label, and the label on which the ink pattern is formed, the base layer (A) side is the inner wall side of the mold, the porous layer (B) side is the cavity side And a molding step of obtaining a labeled resin molded article by an in-mold molding method so that the resin molded article with a label is manufactured.
[20] The method for producing a resin molded article with a label layer according to [19], wherein the ink composition is colorless and transparent.
[21] The method for producing a labeled resin molded article according to [19], wherein the color difference ΔE _P0 between the first ink pattern (P ¹ ) and the surface of the resin molded article is less than 3.
[22] The labeled resin molded article according to [19], wherein the ink composition is colored and the color difference ΔE ₀ between the first ink pattern (P ¹ ) and the porous layer (B) is 3 or more. Manufacturing method.
[23] The method for producing a labeled resin molded article according to any one of [19] to [22], wherein the ink composition has a viscosity of 10 to 1500 mPa·s measured by a B-type viscometer according to JIS Z8803:2011. ..
[24] The method for producing a labeled resin molded article according to any one of [19] to [23], wherein a flexographic printing method is used as a printing method of the ink composition in the printing step.
[25] Any one of [19] to [24], which has a step of printing a heat-sealing resin composition on the surface of the porous layer having the ink pattern formed between the printing step and the molding step. A method for producing a labeled resin molded article according to item.
[26] Any one of [19] to [24], which has a step of applying a heat-sealing resin composition to the surface of the porous layer having the ink pattern formed between the printing step and the molding step. A method for producing a labeled resin molded article according to item 1.

In the labeled resin molded product of the present invention, when the label having the base layer (A) is peeled off from the resin molded product, at the same time, the porous layer (B) of the label attached to the resin molded product undergoes cohesive failure. The first porous separation layer (B ¹ ) on the side of the molded product that remains attached to the resin molded product and the second porous separation layer (B ² ) on the side of the base layer that separates along with the base layer (A). After separation, the surfaces of the separation layers (B ¹ ) and (B ² ) are exposed to the outside. At this time, in the labeled resin molded article of the present invention, at least the ink composition is present in the voids present inside the porous layer (B) so as to occupy a part of the void spaces, An ink pattern that can be visually confirmed appears on the exposed surface of the first porous separation layer (B ¹ ). From this ink pattern, the pattern of the ink composition applied to the surface of the porous layer (B) can be confirmed.

It is a front view showing one mode of a resin molding with a label of the present invention. It is a top view which shows an example of the ink pattern (P) formed in the surface of the porous layer (B) of the label used by this invention. It is sectional drawing which shows the uniform aspect of the label used by this invention. In an example of the labeled resin molded article of the present invention, the state after peeling off the label having the base layer (A) from the resin molded article is shown, (a) shows the first porous separation remaining after peeling off the label. is a front view showing a resin molded article having a layer (B ^1), (b) is a plan view of a label peeling from the second porous separating layer (B ²⁾ side. In another example of the labeled resin molded article of the present invention, the state after peeling off the label having the base layer (A) from the resin molded article is shown, and (a) shows the first porosity remaining after peeling off the label. is a front view showing a resin molded article having quality separating layer (B ^1), (b) is a plan view of a label peeling from the second porous separating layer (B ²⁾ side.

Hereinafter, the labeled resin molded product of the present invention and the method for producing the same will be described in detail. The description of the constituent elements described below may be made based on a typical embodiment of the present invention, but the present invention is not limited to such an embodiment. In addition, in this invention, "-" means the range which includes the numerical value described before and behind that as a minimum value and a maximum value, respectively.

<<Resin molded product with label>>
The labeled resin molded product of the present invention will be described by taking the labeled resin molded product 3 shown in FIG. 1 as an example. The configuration of the labeled resin molded product of the present invention is not limited to the configuration shown in FIG. 1, and the form of each part can be appropriately changed.
The labeled resin molded product 3 of the present invention includes a resin molded product 1 and a label 2 attached to the resin molded product 1 (see FIGS. 1 and 2).
Below, each part which comprises the labeled resin molded product of this invention is demonstrated.

<Basic structure of label>
As shown in FIG. 3, the label 2 used in the present invention is present inside the base layer (A), the porous layer (B) provided on the base layer (A), and the porous layer (B). A surface on the side of the porous layer (B) (a surface on the side opposite to the base layer (A) of the porous layer (B)), which includes a plurality of voids 11 and the ink composition 12 existing so as to occupy a part of the voids 11. ) To be attached to the resin molded product 1. Further, the label 2 is attached to the resin molded product 1, and a cut is made from the end face of the porous layer (B) so that the porous layer (B) bisects in the thickness direction. When the label 2 is peeled off from the resin molded product 1 by pulling the base layer (A) so as to expand, the porous layer (B) remains attached to the resin molded product 1 as shown in FIGS. the first porous separating layer remaining as (B ^1), the resin of the base layer second porous separating layer to peeling with the (a) with the separation in (B ^2), the first porous separating layer (B ¹⁾ The first ink pattern (P ¹ ) that can be visually confirmed by the ink composition 12 appears on the surface opposite to the molded product 1.
The "existing so as to occupy a part of the voids" in the "ink composition existing so as to occupy a part of the voids" in the present invention means that at least a part of the plurality of voids in the porous layer (B). Means that the ink composition is present so as to occupy a part of the void space. The voids in which the ink composition is present may be all or some of the voids in the porous layer (B). Further, of the plurality of voids in which the ink composition is present, the ink composition may be present so as to occupy a part of the voids, may be all or some of the plurality of voids. .. That is, a part of the plurality of voids may be filled with the ink composition.
The ink composition existing so as to occupy a part of the voids of the porous layer (B) is, for example, the ink composition supplied to the surface of the porous layer (B) opposite to the base layer (A). It penetrates from the opening of the void on the surface to the inside and is absorbed into the inside of the porous layer (B).
In the present invention, the “first ink pattern (P ¹ )” can be visually confirmed. Here, "visible" means that a person who has normal and normal visual acuity (for example, visual acuity that is not color blindness, corrected visual acuity is 0.7 or more, and is not extreme astigmatism) visually sees the object. When viewed, it means that the object can be confirmed (visually confirmed).
In the following description, the surface of the porous layer (B) opposite to the base layer (A) may be simply referred to as “surface”. In addition, an exposed surface that appears on the surface by peeling the label 2 from the resin molded product 1 as described above, and the surface of the first porous separation layer (B ¹ ) opposite to the resin molded product 1, and , The surface of the second porous separation layer (B ² ) opposite to the base layer (A) is referred to as a “fracture surface”. Of the fracture surface of the first porous separation layer (B ¹ ), the area (printing area) where the “first ink pattern (P ¹ )” is formed is referred to as a “pattern formation area” or a “first ink pattern formation area”. The area (margin area) 21 in which the “first ink pattern (P ¹ )” is not formed is referred to as “pattern non-formation area” or “first ink pattern non-formation area”.
An ink pattern (“second ink pattern (P ² )”) that can be visually confirmed may or may not appear on the fracture surface of the second porous separation layer (B ² ). As shown in FIG. 5, the second porous separating layer if (B ²⁾ "second ink pattern (P ^2)" to the fracture surface appears, among the fracture surface, "second ink pattern (P ²⁾ The area (printing area) in which "" is formed is referred to as a "pattern forming area" or "second ink pattern forming area", and the area (margin area) 22 in which the "second ink pattern (P ² )" is not formed 22 Is referred to as a “pattern non-formation region” or a “second ink pattern non-formation region”. Further, as shown in FIG. 4, when the “second ink pattern (P ² )” does not appear on the fracture surface of the second porous separation layer (B ² ), the first ink pattern (P 2 ^The area having a mirror image relationship with ¹ ) is called "ink pattern corresponding area (P')", and the other area (margin area) 22 is called "pattern non-forming area" or "second ink pattern non-forming area".
In the present invention, as a general index showing that the ink pattern can be visually confirmed, the color difference measured between the formation area (printing area) and the non-formation area (margin area) of the ink pattern on the observation surface. ΔE is preferably 3 or more.
Each layer of the label used in the present invention will be described below.

[Base layer (A)]
The strength of the base layer (A) is higher than that of the porous layer (B) described later, and the base layer (A) has such strength that the label itself does not break when the label is peeled off with the (A) layer. It is a thing. More specifically, the cohesive force (peeling strength or tensile strength at break) of the base layer (A) itself is preferably 200 gf/15 mm or more. The material of the base layer (A) is not particularly limited, but preferably contains a thermoplastic resin. The base layer (A) may be transparent, semitransparent, or opaque.

(Thermoplastic resin)
The type of thermoplastic resin used for the base layer (A) is not particularly limited. For example, high density polyethylene, medium density polyethylene, low density polyethylene, propylene resin, polymethyl-1-pentene, polyolefin resin such as ethylene-cyclic olefin copolymer, ethylene/vinyl acetate copolymer, ethylene/acrylic acid copolymer Polymers, functional group-containing polyolefin resins such as maleic acid-modified polyethylene and maleic acid-modified polypropylene, polyamide resins such as nylon-6 and nylon-6,6, polyethylene terephthalate and its copolymers, polybutylene terephthalate, polybutylene Thermoplastic polyester resins such as succinate, polylactic acid and aliphatic polyester, polycarbonate, atactic polystyrene, syndiotactic polystyrene and the like can be used. Among these thermoplastic resins, it is preferable to use a polyolefin-based resin or a functional group-containing polyolefin-based resin that is excellent in processability. More specific examples of the polyolefin resin include ethylene, propylene, butylene, butadiene, isoprene, chloroprene, methyl-1-pentene, homopolymers of olefins such as cyclic olefins, and two or more kinds of these olefins. The following copolymers are listed.

More specific examples of the functional group-containing polyolefin resin include copolymers of the above-mentioned olefins and a functional group-containing monomer that is copolymerizable. Such functional group-containing monomers include styrene, styrenes such as α-methylstyrene, vinyl acetate, vinyl alcohol, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl caproate, vinyl laurate, vinyl stearate, vinyl benzoate. Carboxylic acid vinyl esters such as vinyl butyl benzoate and vinyl cyclohexanecarboxylate, acrylic acid, methacrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, octyl ( (Meth)acrylate, 2-ethylhexyl (meth)acrylate, stearyl (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, (meth)acrylamide, (Meth)acrylic acid esters such as N-metallol (meth)acrylamide ((meth)acrylic acid ester means acrylic acid ester and methacrylic acid ester), methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, cyclopentyl vinyl ether Vinyl ethers such as cyclohexyl vinyl ether, benzyl vinyl ether, and phenyl vinyl ether are particularly representative. It is possible to use one obtained by appropriately selecting one or two or more kinds from these functional group-containing monomers and polymerizing them. Furthermore, these polyolefin resins and functional group-containing polyolefin resins can be used after being graft-modified, if necessary.

A known method can be used for the graft modification. Specific examples include graft modification with unsaturated carboxylic acids or their derivatives. Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid and the like. As the derivative of the unsaturated carboxylic acid, acid anhydride, ester, amide, imide, metal salt and the like can be used. Specifically, maleic anhydride, itaconic anhydride, citraconic anhydride, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, glycidyl acrylate, glycidyl methacrylate, malein. Acid monoethyl ester, maleic acid diethyl ester, fumaric acid monomethyl ester, fumaric acid dimethyl ester, itaconic acid monomethyl ester, itaconic acid diethyl ester, acrylamide, methacrylamide, maleic acid monoamide, maleic acid diamide, maleic acid-N-monoethyl ester Amide, maleic acid-N,N-diethylamide, maleic acid-N-monobutylamide, maleic acid-N,N-dibutylamide, fumaric acid monoamide, fumaric acid diamide, fumaric acid-N-monoethylamide, fumaric acid- N,N-diethylamide, fumaric acid-N-monobutylamide, fumaric acid-N,N-dibutylamide, maleimide, N-butylmaleimide, N-phenylmaleimide, sodium acrylate, sodium methacrylate, potassium acrylate, methacryl Potassium acid etc. can be mentioned. The graft-modified product is preferably a graft-modified product of the graft monomer with respect to the polyolefin resin and the functional group-containing polyolefin resin in an amount of generally 0.005 to 10% by weight, preferably 0.01 to 5% by weight.

As the thermoplastic resin of the base layer (A), one kind may be selected from the above-mentioned thermoplastic resins and used alone, or two or more kinds may be selected and used in combination. Further, among these polyolefin-based resins and functional group-containing polyolefin-based resins, propylene-based resins are preferable in terms of chemical resistance and cost. The propylene resin is a propylene homopolymer and is isotactic or syndiotactic and polypropylene showing various degrees of stereoregularity, and propylene is a main component, and ethylene, 1-butene, 1-hexene, It is desirable to use, as a main component, a copolymer obtained by copolymerizing α-olefin such as 1-heptene or 4-methyl-1-pentene. This copolymer may be a binary system, a ternary system or more, and may be a random copolymer or a block copolymer. The propylene-based resin is preferably used by blending a resin having a melting point lower than that of the propylene homopolymer in an amount of 2 to 25% by weight. As such a resin having a low melting point, high-density or low-density polyethylene can be exemplified.

In addition to the thermoplastic resin, an inorganic fine powder, an organic filler, a heat stabilizer (antioxidant), a light stabilizer, a dispersant, a lubricant and the like can be added to the base layer (A), if necessary. When the inorganic fine powder is added, the average particle size is usually 0.01 to 15 μm, preferably 0.1 to 5 μm. Specifically, calcium carbonate, calcined clay, silica, diatomaceous earth, clay, talc, titanium oxide, barium sulfate, alumina, zeolite, mica, sericite, bentonite, sepiolite, vermiculite, dolomite, wollastonite, glass fiber, etc. Can be used.

When the organic filler is added, it is preferable to select a resin of a type different from the thermoplastic resin as the main component. For example, when the thermoplastic resin film is a polyolefin resin film, examples of the organic filler include polyethylene terephthalate, polybutylene terephthalate, polycarbonate, nylon-6, nylon-6,6, cyclic polyolefin, polystyrene and polymethacrylate. It is possible to use a polymer which has a melting point (eg 170 to 300° C.) or a glass transition temperature (eg 170 to 280° C.) higher than the melting point of the polyolefin resin and is incompatible. The organic filler is preferably used as an organic fine powder. The average dispersed particle diameter of the organic filler is preferably 0.01 μm or more, more preferably 0.1 μm or more, still more preferably 0.5 μm or more, from the viewpoint of easiness of mixing with the thermoplastic resin and pore formability. Further, the average dispersed particle diameter of the organic filler is preferably 30 μm or less, more preferably 15 μm or less, and further preferably 5 μm or less.
The total addition amount of the inorganic fine powder and the organic filler is usually 70% by weight or less, preferably 60% by weight or less, more preferably 50% by weight or less, based on 100% by weight of the entire base layer (A). The lower limit of the amount of addition of the inorganic fine powder and the organic filler is usually 0.1% by weight or more, preferably 3% by weight or more, and more preferably 10% by weight or more.

When the heat stabilizer is added, the total amount of the base layer (A) is 100% by weight, and is usually added in the range of 0.001 to 1% by weight. Specifically, a sterically hindered phenol-based, phosphorus-based, amine-based stabilizer or the like can be used. When a light stabilizer is used, it is usually used within the range of 0.001 to 1% by weight. Specifically, sterically hindered amine-based, benzotriazole-based, and benzophenone-based light stabilizers can be used. The dispersant and the lubricant are used, for example, for the purpose of dispersing the inorganic fine powder. The amount added is usually within the range of 0.01 to 4% by weight. Specifically, a silane coupling agent, a higher fatty acid such as oleic acid or stearic acid, metal soap, polyacrylic acid, polymethacrylic acid, or a salt thereof can be used.

The thickness of the base layer (A) is usually 30 to 500 μm, preferably 70 to 300 μm. If it is 30 μm or more, it has sufficient rigidity when applied to a resin molded product as an in-mold molding label, so wrinkles do not easily occur and it is easy to cleanly adhere to the molded product and breaks when peeled. Tends to be difficult to do. If it is 500 μm or less, the rigidity of the label for in-mold molding does not become too high, so that the label tends to be easily held in the mold.

(Multilayer)
The base layer (A) may have a single layer structure or a multilayer structure of two or more layers. By making the base layer (A) multi-layered, various functions such as writability, printability, scratch resistance, and secondary processing suitability can be added.
When the base layer (A) has a multi-layer structure, the total content of the inorganic fine powder and the organic filler in the layer (A1), which is a layer in contact with the porous layer (B) described later, is 5 than that of the porous layer (B). It is desirable that the amount is less than or equal to wt %, preferably less than or equal to 10 wt %. Difference in porosity between the porous layer (B) and the (A1) layer due to the total content of the inorganic fine powder and the organic filler in the (A1) layer being 5% by weight or more lower than that of the porous layer (B). Therefore, when the label is peeled from the resin molded product, it can be easily propagated to the porous layer (B) only by breaking. Specifically, the layer (A1) contains 35 to 100% by weight of a thermoplastic resin, preferably 40 to 100% by weight, and contains at least one of an inorganic fine powder and an organic filler in an amount of 0 to 65% by weight, preferably 0 to 60% by weight. % Is preferable.
In the case of a two-layer structure, for example, in the case of a two-layer structure, the number of stretching axes of this multilayer structure is as follows: non-stretching/uniaxial, non-stretching/biaxial, monoaxial/uniaxial, monoaxial/biaxial, Two axes/1 axis, 2 axes/2 axes can be illustrated.

[Porous layer (B)]
The porous layer (B) in the present invention is a layer having a large number of fine voids which are open facing the surface of the porous layer (B), and the ink composition is present inside the voids. The ink composition present in the voids is, for example, an opening of voids in which the ink composition supplied to the surface of the porous layer (B) opposite to the base layer (A) faces the surface of the porous layer (B). Permeated from the inside to the inside and absorbed in the porous layer (B). Here, for example, when an ink pattern (P) of the ink composition 12 is formed on the surface of the porous layer (B) of the label 2 before being attached, as shown in FIG. 2, the pattern is retained. Then, the ink composition 12 is absorbed in the porous layer (B). In this case, the reverse pattern of the ink pattern (P) can be visually confirmed as the first ink pattern (P ¹ ) on the resin molded product 3 after the label is peeled off by the mechanism described later. When the ink composition 12 has penetrated to a relatively deep position in the porous layer (B), the second ink pattern (P) corresponding to the ink pattern (P) is peeled off on the label. ² ) You can check.
According to such a porous layer (B), when the label is attached to a resin molded article as a label for in-mold molding, the molten resin is formed on the surface of the porous layer (B) by resin pressure during molding of the resin molded article. The label can be attached to the resin molded product by entering the opening and anchoring it. Therefore, the label can be attached to the resin molded product regardless of the material of the resin molded product. Further, the porous layer (B) is a layer that is more brittle and weaker than the base layer (A), and when the label is peeled off from the resin molded product by pulling the base layer (A), at the same time, the porous layer (B) Easily coagulates and breaks and remains on the resin molded product side (the first porous separation layer (B ¹ )), and the base layer side part (second porous separation layer (B ¹ )) is peeled off along with the base layer (A). Separation into a porous separation layer (B ² ). Therefore, the base layer (A) can be easily peeled off from the labeled resin molded product.
Further, since the porous layer (B) in the present invention has a large number of voids (communication holes) communicating with each other inside, when the same label is attached to a resin molded product, it is between the label and the resin molded product. Even if the air remains, the air is pushed out by the resin through the communication hole and discharged to the outside, so that it does not remain between them and the label does not swell.
In the porous layer (B) of the present invention, the first porous separation layer (B ¹ ) which remains attached to the resin molded article is particularly due to the presence of the ink composition inside the voids. The first ink pattern (P ¹ ) due to the ink composition appears on the fracture surface of No. 1, and the first ink pattern (P ¹ ) can be visually confirmed. Therefore, when the ink composition is supplied to the surface of the porous layer (B) with the ink pattern (P) showing specific information as shown in FIG. 2, as shown in FIGS. The first ink pattern (P ¹ ) appears as a reverse pattern of the ink pattern (P) on the fracture surface of the first porous separation layer (B ¹ ), and information can be known from the pattern. This makes it possible to add a further function such as identifying the resin molded product from which the label has been peeled off from the known information and preventing reuse or forgery of the resin molded product.
Further, when the ink composition is present also in the voids located at relatively deep positions in the porous layer (B), as shown in FIG. 5, the second porous layer exfoliated along with the base layer (A). A second ink pattern (P ² ) which is a mirror image of the first ink pattern (P ¹ ) appears on the fracture surface of the quality separation layer (B ² ) and the second ink pattern (P ² ) is visually confirmed. be able to. In this case, based on the information obtained from the second ink pattern (P ² ), the resin molded product from which the label is peeled off is specified to prevent reuse or forgery of the resin molded product, and the peeled off label. It is possible to add further functions such as secondary use of as a coupon ticket or the like.

The material of the porous layer (B) is not particularly limited, but a resin film containing a blend of a crystalline polypropylene resin and a thermoplastic resin incompatible with the crystalline polypropylene resin, and a fine powder is at least uniaxial. It is preferable to use a stretched film stretched in the direction.
The peeling of the label in the labeled resin molded product of the present invention is performed by the destruction (cohesive failure) of the porous layer (B). Here, when at least two kinds of resins which are incompatible with each other are used as the resin material, and the blended product of the resins is stretched in a phase-separated state to form the porous layer (B), the porous layer (B) is formed. When B) breaks, peeling occurs not only at the interface of the voids but also at the interface between these resins, and it becomes possible to peel the porous layer (B) in a uniform plane.
Further, when the porous layer (B) contains an inorganic fine powder, preferably an inorganic fine powder whose surface has been hydrophilized, good printability can be obtained.

(Mixing ratio)
Stretching at least uniaxially a resin film containing, as the porous layer (B), a crystalline polypropylene resin, a blend of the crystalline polypropylene resin and an incompatible thermoplastic resin, and fine powder When a film is used, the content of the blend of the crystalline polypropylene resin and the thermoplastic resin incompatible with the crystalline polypropylene resin in the porous layer (B) is 100 parts by weight of the entire porous layer (B). %, 30 to 60% by weight is preferable, and 35 to 50% by weight is more preferable. Further, the content of the fine powder in the porous layer (B) is preferably 40 to 70% by weight, more preferably 50 to 65% by weight. When the content of the fine powder in the porous layer (B) is 40% by weight or more, sufficient peelability can be easily obtained. Further, when it is 70% by weight or less, molding stability is easily obtained.
In the blend, the blending ratio of the thermoplastic resin which is incompatible with the crystalline polypropylene resin is preferably 105 to 300 parts by weight, and 120 to 280 parts by weight with respect to 100 parts by weight of the crystalline polypropylene resin. More preferably, it is more preferably 140 to 270 parts by weight.

(Crystalline polypropylene resin)
As the crystalline polypropylene resin, it is preferable to use the above propylene resin having a crystallinity of 65% or more. The crystallinity of the crystalline polypropylene is more preferably 66% or more, and particularly preferably 67-80%. When the degree of crystallinity is 65% or more, the compatibility between the amorphous part of the crystalline polypropylene resin and the thermoplastic resin does not easily proceed, and the desired interfacial peeling effect is easily obtained, and the stress required for peeling (peeling strength ) Can be appropriately reduced. Further, when the crystallinity is 80% or less, it is easy to obtain commercially.

In the present specification, the crystallinity of the crystalline polypropylene resin is determined by subjecting the resin sample to an annealing treatment in an oven set at 105° C. for 90 minutes, and then under a condition of a temperature of 23° C., a density gradient tube method or water test. It was calculated using the following formula (1) from the density of the crystalline polypropylene resin obtained by the substitution method (both can be mutually corrected by a conversion formula).
(In the formula (1), ρS is the density of the crystalline polypropylene resin, ρC is the theoretically obtained density of the crystal part of the polypropylene resin (0.938 g/cm ³ ), and ρA is the logical value. The obtained density of the amorphous portion of the polypropylene resin is 0.852 g/cm ^3. )
Therefore in order to achieve the above crystallinity, is preferably, 0.907 g / cm ³ or more that the density of the crystalline polypropylene resin used in the porous layer (B) is 0.906 g / cm ³ or more More preferably, it is particularly preferably 0.908 g/cm ³ or more.

(Thermoplastic resin incompatible with crystalline polypropylene resin)
The thermoplastic resin which is incompatible with the crystalline polypropylene resin includes polyethylene resin, styrene resin, cyclic polyolefin resin, ethylene-cyclic olefin copolymer resin, propylene-α olefin copolymer resin, nylon-6, nylon-6, and nylon-6. Polyamide resins such as 6, nylon-6,10, nylon-6,12, thermoplastics such as polyethylene terephthalate and its copolymers, polyethylene naphthalate, polybutylene terephthalate, polybutylene succinate, polylactic acid, and aliphatic polyester. Examples include polyester resins and polycarbonates. These may be used as a mixture of two or more. Among these, polyethylene resin is preferably used from the viewpoint of chemical resistance, production cost, and the like. Due to the presence of the incompatible thermoplastic resin, interfacial peeling occurs between the crystalline polypropylene resin and the polypropylene resin incompatible thermoplastic resin during the production of the stretched film to improve the peelability. When the amount of the incompatible thermoplastic resin is set to 105 to 300 parts by weight with respect to 100 parts by weight of the polypropylene resin, sufficient releasability is easily obtained.
In the present specification, “incompatible” has a morphology of a sea-island structure when a blend of a crystalline polypropylene resin and an incompatible thermoplastic resin is observed with an electron microscope, and the dimension of the structure. Is 0.3 to 10 μm.

(Fine powder)
As the fine powder, it is possible to use hydrophilic fine inorganic powder, or non-hydrophilic fine inorganic powder or organic fine powder. As the fine powder, only the hydrophilic fine inorganic powder may be used, or only the non-hydrophilic inorganic fine powder or the organic fine powder may be used, or the hydrophilic fine inorganic powder may be used. The powder may be used in combination with the inorganic fine powder and/or the organic fine powder which has not been subjected to the hydrophilic treatment.
Examples of the inorganic fine powder include heavy calcium carbonate, light calcium carbonate, calcined clay, talc, titanium oxide, barium sulfate, zinc oxide, magnesium oxide, diatomaceous earth, silicon oxide and the like, and the periphery of the core of the inorganic fine powder. Examples thereof include composite inorganic fine powder having aluminum oxide or hydroxide, hollow glass beads and the like. Of these, heavy calcium carbonate, calcined clay, and diatomaceous earth are preferable because they are inexpensive and can form many pores during stretching.
As the organic fine powder, it is preferable to select a resin of a type different from the thermoplastic resin used for the porous layer (B). For example, it is a polymer such as polyethylene terephthalate, polybutylene terephthalate, polycarbonate, nylon-6, nylon-6,6, cyclic polyolefin, polystyrene, and polymethacrylate, and is higher than the thermoplastic resin used for the porous layer (B). It is preferable to use those which have a melting point or glass transition temperature and are incompatible. For example, it is possible to use an incompatible one having a melting point (eg 170 to 300° C.) or a glass transition temperature (eg 170 to 280° C.) higher than that of the polypropylene resin.

As the fine powder in the present invention, it is preferable to use at least one of the above-exemplified inorganic fine powders whose surface is hydrophilized with a surface treatment agent.
When the porous layer (B) is formed by using the inorganic fine powder whose surface has been hydrophilized, the printability of the surface of the porous layer (B) is improved and a beautiful labeled molded product is obtained at the same time. Since the porous layer (B) formed by these is more likely to cause interfacial peeling between the inorganic fine powder and the crystalline polypropylene, it is possible to provide an in-mold molding label that can be more easily separated from the molded product. Become.

Examples of the surface treatment agent include water-soluble anionic surfactants, water-soluble cationic surfactants, and water-soluble nonionic surfactants.
Specific examples of such a surfactant include, for example, a water-soluble anionic surfactant having a sulfonate having a hydrocarbon group having 4 to 40 carbon atoms and a hydrocarbon group having 4 to 40 carbon atoms. Examples thereof include a phosphate ester salt, a salt of a phosphoric acid mono- or diester of a higher alcohol having a carbon number of 4 to 40, and an alkyl betaine or an alkyl sulfobetaine having a hydrocarbon group having a carbon number of 4 to 40. For example, water-soluble cationic surfactants include diallylamine salts, alkyldiallylamine salts having 1 to 4 carbon atoms and dialkyldiallylamine salts, that is, methyldiallylamine salts, ethyldiallylamine salts, dimethyldiallylamine salts, methacryloyloxyethyltrimethylammonium, acryloyl. Epoxy Clyde, bromide, methosulfate, ethosulfate, N,N-dimethylaminoethyl methacrylate or N,N-dimethylaminoethyl acrylate of oxyethyl trimeryl ammonium, methacryloyl oxyethyl dimethyl ethyl ammonium or acryloyl oxyethyl dimethyl ethyl ammonium. Examples thereof include quaternary ammonium salts obtained by alkylation with an epoxy compound such as chlorohydrin, glycidol and glycidyl trimethyl ammonium chloride. Among these, preferred are diallylamine salts, methyldiallylamine salts and dimethyldiallylamine salts. For example, as the water-soluble nonionic surfactant, acrylamide, methacrylamide, N-vinylformamide, N-vinylacetamide, N-vinylpyrodrine, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxy(meth ) Acrylate, 3-hydroxypropyl (meth)acrylate, (meth)acrylic acid methyl ester, (meth)acrylic acid ethyl ester, and (meth)acrylic acid butyl ester. Of these, acrylamide and methacrylamide are preferable.

As a surface treatment method for the inorganic fine powder, for example, 100 parts by weight of calcium carbonate coarse particles having a particle size of 10 to 50 μm are wet-ground in an aqueous medium in the presence of a necessary amount of a surface treatment agent to obtain a desired particle size. Can be mentioned. Specifically, water is added to calcium carbonate so that the weight ratio of calcium carbonate/aqueous medium (specifically water) is 70/30 to 30/70, preferably 60/40 to 40/60. Then, 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, of a surface treatment agent is added to 100 parts by weight of calcium carbonate, and wet pulverization is carried out by an ordinary method. Further, an aqueous medium prepared by previously dissolving the surface treating agent in an amount within the above range may be prepared, the aqueous medium may be mixed with calcium carbonate, and wet pulverized by a conventional method. The wet pulverization may be a batch type or a continuous type, and a mill using a pulverizing device such as a sand mill, an attritor, or a ball mill can be used.
Specific examples of the inorganic fine powder which has been surface-treated with these surface-treating agents include, for example, the product name "AFF" manufactured by Phimatech Co., Ltd.

In the porous layer (B) of the present invention, in addition to the above-mentioned inorganic fine powder whose surface is hydrophilized, inorganic fine powder or organic fine powder whose surface is not hydrophilized may be combined and blended. preferable. The blending ratio is 50 to 99.9% by weight of the inorganic fine powder whose surface is hydrophilized, and the inorganic fine powder and the organic fine powder whose surface is not hydrophilized, when the fine powder used is 100% by weight. It is preferable that at least one of the above is 0.1 to 50% by weight, the inorganic fine powder whose surface is hydrophilized is 55 to 80% by weight, and the inorganic fine powder and the organic fine powder whose surface is not hydrophilized. It is more preferable that at least one of the above is 20 to 45% by weight. In the porous layer (B), the content of the inorganic fine powder and the organic fine powder whose surfaces have not been hydrophilized is preferably 0.1 to 30% by weight.
Here, the "inorganic fine powder whose surface has not been hydrophilized" refers to an inorganic fine powder that has not been intentionally hydrophilized with the above-mentioned surface treatment agent, and is a normal pulverizing, classifying, or sedimenting process. It refers to the inorganic fine powder obtained by the above process. For example, the amount of eluate from the porous layer (B) can be adjusted by mixing the hydrophilized calcium carbonate fine powder and a normal heavy calcium carbonate fine powder. For example, the hydrophilized calcium carbonate can be adjusted. The water absorption can be adjusted by combining the fine powder and the organic fine powder. Even when different types of fine powders are blended, if the total amount of the fine powders contained in the porous layer (B) exceeds 70% by weight, the stretchability of the water-absorptive peelable film deteriorates. It is not preferable because the molding stability is impaired.

(Dispersant)
The porous layer (B) of the present invention preferably contains a dispersant in order to uniformly finely disperse the inorganic fine powder.
Examples of the dispersant for the inorganic fine powder include acid-modified polyolefin and silanol-modified polyolefin. In the present invention, it is particularly preferable to use maleic acid-modified polyolefin and silanol-modified polypropylene.
Examples of the acid-modified polyolefin include hydroxyl-free polyolefin obtained by random copolymerization or graft copolymerization of maleic anhydride, or carboxylic acid group-containing polyolefin obtained by random copolymerization or graft copolymerization of unsaturated carboxylic acid such as methacrylic acid and acrylic acid. , Epoxy group-containing polyolefin obtained by random copolymerization or graft copolymerization of glycidyl methacrylate, and the like. Specific examples include maleic anhydride modified polypropylene, maleic anhydride modified polyethylene, acrylic acid modified polypropylene, ethylene/methacrylic acid random copolymer, ethylene/glycidyl methacrylate random copolymer, ethylene/glycidyl methacrylate graft copolymer, glycidyl. Methacrylate-modified polypropylene and the like can be mentioned, with maleic anhydride-modified polypropylene and maleic anhydride-modified polyethylene being particularly preferred.
Specific examples of maleic anhydride-modified polypropylene and maleic anhydride-modified polyethylene include MODIC AP manufactured by Mitsubishi Chemical Co., Ltd., trade name "P513V", trade name "M513", trade name "P928", Sanyo Kasei Co., Ltd. ), trade name “Umex1001”, trade name “Umex1010”, trade name “Umex2000”, HPR manufactured by Mitsui DuPont Chemical Co., Ltd., trade name “VR101”.
The acid modification rate of the acid-modified polyolefin is preferably 0.01 to 20%, more preferably 0.05 to 15%. When the acid modification rate is 0.01% or more, it is easy to sufficiently obtain the effect of dispersing the inorganic fine powder in the resin blend. When the acid modification rate is 20% or less, the softening point of the acid modified polyolefin does not become too low, and thus the compounding with the thermoplastic resin is relatively easy.

When the dispersant is added to the porous layer (B), the content of the dispersant is usually 0.5 to 30 parts by weight, preferably 1 to 20 parts by weight, based on 100 parts by weight of the inorganic fine powder. When the content of the dispersant is 0.5 part by weight or more, the inorganic fine powder is sufficiently dispersed, so that a desired surface aperture ratio can be easily obtained and the liquid absorption volume can be easily improved. Further, when it is 30 parts by weight or less, the stretchability is good and the breakage of the stretch during the molding can be suppressed.

(Thickness of porous layer (B))
The thickness of the porous layer (B) is usually 0.1 to 20 μm, preferably 3 to 18 μm, more preferably 6 to 15 μm, and particularly preferably 7 to 12 μm. If the thickness of the layer (B) is too thin, the melt of the resin that constitutes the molded product penetrates into the vicinity of the base layer (A) through the inside of the porous layer (B), and the adhesive strength is improved, but it is labeled. Even if the label is peeled off from the resin molded product, it is difficult to stably perform cohesive failure in the porous layer (B), and peeling tends to be difficult. When the thickness of the layer (B) is too thick, there is no problem in peel strength when peeling, but the peeling position is not stable and the peeling surface is not uniform, so the stress required for peeling is not stable. In addition, irregularities remain on the surfaces of both the resin molded product and the peeled film, and there is a tendency that the porous layer (B) side cannot be clearly seen even when printed. The porous layer (B) is a stretched resin film layer stretched in at least a uniaxial direction. It is possible to form surface openings and internal voids by stretch molding to obtain a layer (B) that is easily peeled uniformly due to the orientation of the resin, and at the same time obtain a porous layer (B) having a uniform thickness. Become.

(Aperture ratio of the surface of the porous layer (B))
The surface opening ratio of the porous layer (B) is preferably 7 to 60%, more preferably 12 to 50%, and particularly preferably 15 to 40%. If the surface opening ratio is 7% or more, sufficient adhesiveness tends to be easily obtained. When the surface opening ratio is 60% or less, the porous layer (B) is less likely to be broken during stretch molding which will be described later, and a stable laminated resin film can be molded.
The “surface open area ratio” in the present invention indicates the area ratio of pores in the observation region when the surface on the porous layer (B) side is observed with an electron microscope. Specifically, an arbitrary part is cut out from the labeled resin molded product or the sample of the label and attached to an observation sample stand, and gold or gold-palladium is vapor-deposited on the observation surface of the electron microscope (for example, Hitachi ( It can be determined by observing the pores on the surface at an arbitrary magnification (for example, magnified 500 times to 3000 times) which is easy to observe using a scanning microscope S-2400 manufactured by Co. Furthermore, the observed area is photographed, the pores are traced on a tracing film and the filled figure is image-processed with an image analysis device (manufactured by Nireco Corporation: model Luzex IID) to determine the area ratio of the pores. The aperture ratio of the surface of the porous layer (B) was used.
The surface open area ratio of the porous layer (B) can be controlled by stretching the resin composition layer that will be the porous layer (B), performing heat treatment, and adjusting the heat treatment temperature.

(Cross-section porosity in thickness direction of porous layer (B))
The cross-sectional porosity in the thickness direction of the porous layer (B) is preferably 30 to 70%, more preferably 31 to 60%, further preferably 33 to 55%, further preferably 35 to 50%. % Is particularly preferable. If the cross-sectional porosity in the thickness direction is 30% or more, the absorption capacity of the ink composition in the porous layer (B) becomes large, so that the first resin molded article side separated by cohesive failure of the porous layer (B) 1st ink pattern (P ¹ ) that appears on the fracture surface of the first porous separation layer (B ¹ ), and further, the second ink that appears on the fracture surface of the second porous separation layer (B ² ) on the base layer (A) side The pattern (P ² ) can be confirmed more easily. If the cross-sectional porosity in the thickness direction is 30% or more, sufficient adhesiveness tends to be easily obtained. On the other hand, when the cross-sectional porosity in the thickness direction is 70% or less, the porous layer (B) is unlikely to break during stretch molding described later, and a stable laminated resin film can be molded.
The cross-section porosity of the porous layer (B) in the thickness direction is preferably higher than the cross-section porosity of the base layer (A) in the thickness direction. As a result, when the label is peeled off from the resin molded article by pulling the base layer (A), the porous layer (B) is preferentially cohesively destroyed than the base layer (A), and the shape of the base layer (A) is retained. At the same time, it becomes easy to separate the porous layer (B) into the first porous separation layer (B ¹ ) and the second porous separation layer (B ² ). Further, the stabilization of the cohesive failure in the thickness direction of the porous layer (B) stabilizes the fracture surface of the first porous separation layer (B ¹ ) and further the fracture of the second porous separation layer (B ² ). On the cross section, the contrast between the ink pattern forming region and the ink pattern non-forming region appears clearly, and it becomes easy to confirm the first ink pattern (P ¹ ) and the second ink pattern (P ² ).
The "porosity in the cross-section in the thickness direction" in the present invention is obtained by taking an electron micrograph of the cross section of the porous layer (B) and determining the area ratio (%) of the pores in the cross-sectional area taken in the photo. Is obtained by Specifically, cut an arbitrary part from the labeled resin molded product or the sample of the label, embed it in an epoxy resin and solidify it, and then use a microtome to make it parallel to the thickness direction of the film (ie (Vertical to the direction), a cut surface is formed, the cut surface is vapor-deposited and metallized, and then a photograph taken by enlarging the cut surface to an arbitrary magnification (for example, 500 to 3000 times) easy to observe with the electron microscope is taken. The image was subjected to a value conversion process, and image processing was performed by the above-mentioned image analysis device, and the area ratio (%) of the pores occupying the measurement range was determined to be the cross-sectional porosity (%) in the thickness direction.
The cross-sectional porosity in the thickness direction of the porous layer (B) can be controlled by adjusting the stretching temperature when the resin composition to be the porous layer (B) is laterally stretched.

(Arithmetic mean roughness of the surface of the porous layer (B))
The arithmetic average roughness Ra of the surface of the porous layer (B) is preferably 0.3 to 1.8 μm, more preferably 0.5 to 1.6 μm, and 0.7 to 1.4 μm. Is particularly preferable. When the arithmetic average roughness is 0.3 μm or more, the resin pressure at the time of molding the molded product resin can provide a fitting effect in which the resin enters the irregularities on the surface of the porous layer (B), which can contribute to the improvement of the adhesive strength. When the arithmetic average roughness is 1.8 μm or less, image quality is not deteriorated due to dot omission or the like caused by unevenness when printing is performed.
The "arithmetic mean roughness" in the present invention was measured using a surface roughness meter (manufactured by Kosaka Laboratory Ltd., trade name: Surfcoder SE30) in accordance with JIS-B0601.

(Oil absorption of the porous layer (B))
In the present specification, the oil absorbency of the porous layer (B) is the time required for oil absorption under certain conditions, which is measured by partially modifying the oil absorption test method defined in JAPAN TAPPI 67-2000. .. Specifically, 20 μm of mineral oil was dripped from the burette on the surface of the porous layer (B), 5 test pieces were used, and it was lowered to the point where 5 scales were added from the case of the test piece only. Instead of measuring the time required, the time required for the roller to return to the value of the pointer of the galvanometer when passing over the test piece is measured, except that the oil absorption degree specified in JAPAN TAPPI 67-2000 is used. It is measured according to the test method. It can be presumed that the shorter the time, the higher the oil absorption and the easier the ink composition penetrates. The oil absorbency is preferably 200 seconds or less, more preferably 100 seconds or less, and further preferably 60 seconds or less.

[Ink composition]
The ink composition is present inside the voids of the porous layer (B). For the existing state and function, the section of the porous layer (B) can be referred to.
In the present invention, the ink composition may be a colored liquid material containing a coloring material (colorant), or a colorless liquid material containing substantially no coloring material. Here, “the ink composition does not substantially contain a color material” means that the color material is not intentionally mixed in the ink composition, and specifically, the content of the color material in the ink composition. Is 0.1% by mass or less. Description and scope of the "coloring material" when the ink composition does not substantially contain the coloring material, and specific examples are as follows: Explanation and scope of the coloring material when the ink composition contains the coloring material, and specific examples Can be referenced. The colorless ink composition containing substantially no coloring material is preferably colorless and transparent.
Examples of the ink composition include oil-based offset ink, UV-curable offset ink, gravure ink, water-based flexo ink, UV flexo ink, oil-based screen ink, UV screen ink, water-based inkjet ink, oil-based inkjet ink, and UV inkjet ink. A gravure ink, a flexo ink, and an inkjet ink are preferable because they have low viscosity and easily penetrate into the voids of the porous layer.
When the ink composition contains a coloring material and is colored, as the coloring material, black or white, dyes or pigments exhibiting normal four process colors or special colors, or fine metal powder exhibiting a metallic effect or the like can be used. .. Further, the coloring material may include one that absorbs ultraviolet rays or infrared rays, or one that absorbs ultraviolet rays or infrared rays and emits visible light. Even if the coloring material of the ink composition is white, by coloring the base layer (A) and the porous layer (B) side of the resin molded product or the label with a color other than white, the ink pattern forming area and the ink are formed. The ink pattern can be visually recognized by obtaining a sufficient color difference ΔE between the pattern non-formation regions.

As the coloring material, dyes such as basic dyes, acid dyes, direct dyes, fluorescent dyes, disperse dyes, and reactive dyes can be used.For example, inorganic pigments containing a metal oxide or sulfide as a main component, and ordinary lakes It can be widely used as an organic pigment made insoluble by adding a precipitant to a so-called dissolved dye.

Specific inorganic pigments include titanium white (titanium dioxide), zinc white (zinc oxide), calcium carbonate, kaolin, graphite (carbon black), ultramarine blue (ultramarine blue), navy blue (Prussian blue), ocher (yellow ocher). ), yellow lead (chrome yellow), zinc yellow (zinc yellow), nickel titanium yellow, bismuth vanadium yellow, cadmium yellow, rouge (iron oxide), red lead, cinnabar (mercury sulfide), cadmium red, precipitated barium sulfate , Baryta powder and the like. Examples of organic pigments include lake pigments, polycyclic pigments, phthalocyanine pigments, soluble azo pigments, insoluble azo pigments, polyazo pigments, and dyeing pigments.

In addition to process four-color pigments, white pigments, special color pigments, and extender pigments, pearl pigments (talc particles, kaolin particles, mica particles, plate-like silica surface-treated with inorganic salts such as silicon oxide, titanium oxide, and iron oxide). , Plate-like alumina, plate-like calcium carbonate, etc.), metal powder (bronze powder, bronze paste, leafing type aluminum paste, non-leafing type aluminum paste, etc.) and the like. You may use these in combination.
Further, the ink composition may contain various additives other than the colorant, and for example, it is preferable to contain a silicone resin as an additive.

As the colorless ink composition containing substantially no coloring material, a liquid material having the same composition as the above ink composition can be used, except that it does not substantially contain a coloring material. Varnishes, clear inks, invisible inks, compounds and the like can also be used as colorless ink compositions containing substantially no coloring material. In addition, as a specific example of a colorless ink composition containing substantially no coloring material, a UV flexo ink (trade name: UV flexomedium 500, manufactured by T&K TOKA) or a UV offset ink (trade name: UV161 medium S, T&K). TOKA Co., Ltd.) and the like.
The mechanism by which a visible ink pattern appears with a colorless ink composition containing substantially no coloring material will be described below.
That is, the porous layer (B) usually has high opacity and whiteness because the transmitted light is diffusely reflected by a large number of voids inside the layer. In a certain region of the porous layer (B), when a colorless ink composition containing substantially no coloring material is filled inside the voids in the region, the region filled with the ink composition (ink pattern formation The opacity of the area) is reduced, and an opacity difference occurs between the ink pattern forming area and the surrounding ink pattern non-forming area. As a result, the ink pattern can be visually recognized as a “watermark”. In addition, at this time, if the base layer (A) of the resin molded product or the label is colored with a color other than white, those colors can be seen through in the ink pattern forming area, so that the ink pattern forming area and the ink pattern non-forming area are A sufficient color difference ΔE can be obtained between them, and the ink pattern can be more clearly visually recognized. Here, for example, in the case where the color of the resin molded product is transparent in the ink pattern forming region, the smaller the color difference ΔE between the ink pattern forming region and the resin molded product is, the smaller the color difference ΔE is. Preferably, it is less than 2, more preferably less than 1, and even more preferably less than 1.

[Heat seal layer]
The label used in the present invention may be provided with a heat seal layer on the surface on the porous layer side, if necessary. The heat seal layer is for reinforcing the adhesive force between the label and the resin molded product, and is solid at room temperature, but activated by the heat of the molten resin for molding the resin molded product in the mold, After being fused with the molten resin and cooled, it becomes solid again and can exhibit a strong adhesive force.

It is preferable that the thermoplastic resin constituting the heat seal layer has a melting point of 60 to 130° C. determined as a peak temperature by DSC measurement. When the temperature is lower than 60°C, stickiness at room temperature deteriorates the slipperiness of the label, and blocking or the like is likely to occur. Therefore, when inserting the label into the mold, many problems such as inserting two labels are likely to occur. If it is higher than 130° C., the adhesiveness between the label and the molded body tends to deteriorate, which is not preferable.

Specific examples of the thermoplastic resin are polyolefin resins, low-density to medium-density high-pressure polyethylene, linear linear polyethylene, ethylene, α-olefin copolymer, propylene/α-olefin photopolymer, Ethylene/vinyl acetate copolymer, ethylene/acrylic acid copolymer, ethylene/acrylic acid alkyl ester copolymer, ethylene/methacrylic acid alkyl ester copolymer (alkyl group has 1 to 8 carbon atoms), ethylene/methacrylic acid Examples thereof include polyethylene-based resins having a melting point of 60 to 130° C., such as metal salts of acid copolymers (Zn, Al, Li, K, Na, etc.). These resins may be used alone or in combination of two or more.

Other known additives for resins can be optionally added to the heat seal layer as long as the performance required for the heat seal layer is not impaired. Examples of such additives include dyes, nucleating agents, plasticizers, release agents, antioxidants, antiblocking agents, flame retardants, ultraviolet absorbers, and dispersants.

The thickness of the heat-sealing layer is preferably 0.1 μm or more, and more preferably 0.5 μm or more, from the viewpoint of obtaining sufficient adhesive strength to the resin molded product. On the other hand, it is preferably 20 μm or less, and more preferably 10 μm or less, from the viewpoint of making it difficult for the label to curl during offset printing on a sheet or when inserting the label into the mold.

<Resin molding>
The resin molded product used in the present invention may be a molded product containing a resin, and is preferably a molded product containing a thermoplastic resin because molding is easy. Examples of the thermoplastic resin include polypropylene resin, polyethylene resin, polystyrene resin, polyethylene terephthalate resin and the like. These may be used alone or in combination of two or more.
Examples of the form of the resin molded product include a container obtained by hollow molding or injection molding.

<Peeling off>
In the labeled resin molded article of the present invention, when the label is peeled off from the resin molded article by pulling the base layer (A), at the same time, the porous layer (B) undergoes cohesive failure and the base layer (A) becomes the porous layer. Peel off with a part of. At this time, the porous layer (B) is separated from the first porous separation layer (B ¹ ) which remains adhered to the resin molded product and the second porous separation layer (B ² ) which is separated along with the base layer (A). ) And two layers. Here, in the porous layer (B) of the present invention, the presence of the ink composition in the voids inside the porous layer (B) results in the first porous separation layer (B ¹ ) as shown in FIGS. The first ink pattern (P ¹ ) appears on the fracture surface of the. The first ink pattern (P ¹⁾ is an ink pattern formation region formed (printed portion), a first ink pattern (P ¹⁾ is not formed ink pattern non-formation region of its fracture surfaces ( The first ink pattern (P ¹ ) can be visually confirmed by a sufficient color difference with the margin portion 21.
Further, when the ink composition is sufficiently permeated into the porous layer (B), as shown in FIG. 5, the second porous separation layer (B ² ) is peeled off along with the base layer (A). A second ink pattern (P ² ) due to the ink composition appears on the fracture surface. The color difference between the second ink pattern (P ²⁾ ink are formed patterned region and the second ink pattern (P ²⁾ is not formed ink pattern non-formation region 22 of the fracture surface is sufficiently When it is, the second ink pattern (P ² ) can be visually confirmed.
On the other hand, and if penetration into the porous layer (B) of the ink composition is not sufficient, the second ink pattern (P ²⁾ ink are formed patterned region and the second ink pattern (P ²⁾ is formed When the color difference with the non-ink pattern non-formed area is not sufficient, the second ink pattern (P ² ) cannot be visually confirmed as shown in FIG. In this case, the area corresponding to the second ink pattern (P ² ), that is, the area having a mirror image relationship with the first ink pattern (P ¹ ) is referred to as an ink pattern corresponding area (P′).

<Peel strength>
The peel strength (stress required for peeling) when peeling the base layer (A) of the label attached to the resin molded product is preferably in the range of 0.3 to 1.6 N/15 mm, and 1 to 1.6 N/ The range of 15 mm is more preferable, and the range of 1.2 to 1.6 N/15 mm is particularly preferable. The peel strength indicates the strength required for peeling the base layer (A) after it is attached to a resin molded product. The peeling preferably proceeds in a uniform plane due to cohesive failure in the porous layer (B).
When the peeling strength is 0.3 N/15 mm or more, when it is attached to a resin molded product, it tends to be difficult to peel off due to an external impact. If the peel strength is 1.6 N/15 mm or less, the strength of the adhesive will not be exceeded, and the surface strength of the resin molded product when attached to the resin molded product will not be exceeded, so that the porous layer (B ) Tend to cause cohesive failure.
"Peeling strength" in the present specification refers to JIS K 6854-2:1999 Adhesive-Peeling adhesive strength test method-Part 2: The estimated average value of the peeling force by 180 degree peeling is used, It is the stress required when peeling the label (base material layer (A)) from the resin molded product. Specifically, in the labeled resin molded product, the label-attached portion of the molded product is cut into a width of 15 mm and a length of 100 mm, and a tensile tester (manufactured by Shimadzu Corporation, product name "AUTOGRAPH") is used, At a pulling speed of 300 mm/min, the base layer (A) and the molded product were peeled off at an angle of 180°, and the stress when stable was measured by a load cell. The average value of the measured values was calculated.
The peeling strength is obtained by setting the crystallinity of the crystalline polypropylene used for the porous layer (B) to 65% or more, blending a predetermined amount of incompatible thermoplastic resin or inorganic fine powder, and This can be achieved by stretching the porous layer (B) in at least a uniaxial direction. Further, this peel strength is preferably that the surface of the inorganic fine powder is hydrophilized, the stretching is carried out at a temperature lower than the melting point of the crystallization site of the crystalline polypropylene, It can be adjusted by selecting a resin having a relatively low viscosity as the plastic resin and setting the porosity of the porous layer (B) within a specific range.

Further, peeling in the porous layer (B) proceeds due to the destruction of the porous layer (B) portion where the melt of the resin constituting the molded article does not penetrate, and therefore the peel strength is the label's porous layer (B). It is also possible to affix an adhesive tape to (1) and pseudo-obtain the strength required for peeling the adhesive tape to measure the strength of the porous layer (B) in the label.
The peel strength of the label alone was measured by sticking an adhesive tape (cellophane tape manufactured by Nichiban Co., Ltd., product name “Cellotape (registered trademark)”, brand name “CT-18”) on the surface of the porous layer (B) Using a tensile tester (manufactured by Shimadzu Corporation, trade name "AUTOGRAPH"), the base layer (A) and the adhesive tape are peeled off at an angle of 180° at a pulling speed of 300 mm/min. Was generated in the porous layer (B), the stress when peeling was stable was measured by a load cell, and it was determined from the respective average values in the horizontal direction and the vertical direction of the label. The peel strength obtained by this method is preferably 0.4 to 2.0 N/18 mm, more preferably 0.5 to 1.9 N/18 mm, and 0.6 to 1.8 N/18 mm. It is particularly preferable to have. This peel strength can be adjusted by using the above-described method described as a method for adjusting the stress required when peeling the label (base material layer (A)).

<Fracture state of porous separation layer>
The labeled resin-molded product of the present invention was cut at the end face of the porous layer of the label with a cutter knife to make a stripping margin, and the peeling margin and the resin-molded product were pulled in a direction away from each other at a pulling speed of 100 mm/min. At this time, it is preferable that the porous layer (B) can be ruptured cleanly in the layer without unevenness and can be divided into the first porous separation layer (B ¹ ) and the second porous separation layer (B ² ). For details of the cut and peeling conditions referred to herein, the section “Visibility of ink pattern on fracture surface” described later can be referred to.
As a measure of the fact that the porous layer (B) broke cleanly without irregularities, each of the surfaces exposed by peeling the label from the resin molded product (the fracture surface on the resin molded product side and the fracture surface on the peeled label side) The remaining area ratio of the porous separation layers (B ¹ ) and (B ² ) can be used, and the larger the ratio of the two, the more clearly the porous layer (B) is broken without unevenness. Specifically, it is preferable that the first porous separation layer (B ¹ ) occupy 80% or more of the fracture surface on the resin molded product side exposed by peeling the label, and the ratio is 90% or more. Is more preferable, 95% or more is still more preferable, 99% or more is still more preferable, and 100% is particularly preferable. The second porous separation layer (B ² ) preferably occupies 80% or more of the label-side fracture surface exposed by peeling, more preferably 90% or more, and 95% or more. Is more preferable, 99% or more is still more preferable, and 100% is particularly preferable.

<Color difference ΔE at fracture surface of porous separation layer>
In the labeled resin molded article of the present invention, a cut is made from the end surface of the porous layer (B) so as to divide the porous layer (B) into two in the thickness direction, and the base layer (A) is formed so that the cut extends. When the label is peeled off from the resin molded product by pulling, the porous layer (B) becomes a label having the first porous separation layer (B ¹ ) and the base layer (A) which remain attached to the resin molded product. The first ink formed by the ink composition is separated into the second porous separation layer (B ² ) which is peeled off along with it, and also on the surface (fracture surface) of the first porous separation layer (B ¹ ) opposite to the resin molded product. The pattern (P ¹ ) appears.
Here, on the fracture surface of the first porous separation layer (B ^1), and the ink pattern formation region in which the first ink pattern (P ¹⁾ is formed, the first ink pattern (P ¹⁾ is being formed The color difference ΔE with respect to the non-ink-pattern non-formed area is not particularly limited, but is preferably 3 or more, more preferably 5 or more, and further preferably 10 or more. When the color difference ΔE is 3 or more, the color difference between the ink pattern forming region and the ink pattern non-forming region is high, so that the first ink pattern (P ¹ ) can be easily recognized. As a result, when the ink composition is supplied (printed) on the surface of the porous layer (B) with an ink pattern representing specific information, the first porous material after peeling the label from the resin molded product The information can be obtained from the first ink pattern (P ¹ ) on the fracture surface of the separation layer (B ¹ ). Since information can be obtained on the fracture surface in this way, additional information different from the information given to the label surface is obtained from the resin molded product with the label peeled off, and the authenticity judgment as to whether the product is a genuine product is made. It is possible to add a further function to the labeled resin molded product, such as secondary use as a coupon or the like such as an application code.
When a colorless ink composition containing substantially no coloring material is used as the ink composition for forming the ink pattern, the first ink pattern (of the fracture surface of the first porous separation layer (B ¹ ) ( P ¹ ), the color difference ΔE _B between the pattern non-formed area where the pattern is not formed and the surface of the resin molded product (the surface of the portion of the labeled resin molded product where the label is not attached) and the first porous separation. The difference (ΔE _B −ΔE _P ) between the color difference ΔE _P between the pattern forming region where the first ink pattern (P ¹ ) is formed on the fracture surface of the layer (B ¹ ) and the surface of the resin molded product is 1 to It is preferably in the range of 50, more preferably in the range of 3 to 30. Even when using a colorless ink composition, if the difference (ΔE _B −ΔE _P ) is 1 or more, the first ink pattern (P ¹ ) can be easily formed on the fracture surface of the first porous separation layer (B ¹ ). Can be seen.

On the other hand, the first ink pattern (P ¹ ) of the first porous separation layer (B ¹ ) is present on the fracture surface of the second porous separation layer (B ² ) which is peeled off along with the label having the base layer (A). It is possible to form a second ink pattern (P ² ) which has a mirror image relationship with. This is due to the fact that the ink composition layer inside the porous layer (B) was divided into two in the thickness direction as the porous layer (B) was separated.
For viewing a second ink pattern (P ^2), the second porous separating layer (B ²⁾ of the base layer (A) and of the opposite surface (fracture surface), a second ink pattern (P ²⁾ It is preferable that the color difference ΔE between the ink pattern forming region where the ink is formed and the pattern non-forming region where the second ink pattern (P ² ) is not formed is 3 or more, more preferably 5 or more, It is more preferably 9 or more. When the color difference ΔE is 3 or more, the second ink pattern (P ² ) can be easily visually recognized because the color difference between the ink pattern forming region and the ink pattern non-forming region is high.
When a colorless ink composition containing substantially no coloring material is used as the ink composition for forming the ink pattern, the second ink pattern on the fracture surface of the second porous separation layer (B ² ). (P ² ) may be invisible. The state in which the first ink pattern can be visually recognized while the second ink pattern cannot be visually recognized has a higher anti-counterfeiting effect. Even if the second ink pattern (P ² ) is not easily visible, when the colorless ink composition has sufficiently penetrated into the porous layer (B), the second porous separation layer (B ² The ink composition is present in the corresponding region of the second ink pattern (P ² ) on the fracture surface of FIG. Therefore, if the same ink composition that absorbs ultraviolet rays or infrared rays and emits visible rays is adopted, the authenticity can be determined more reliably, and the forgery prevention effect can be further enhanced.
In the labeled resin molded product of the present invention, the first ink pattern (P ¹ ) and the second ink pattern (P ² ) have a mirror image relationship with each other. Here, whether the normal image is the first ink pattern (P ¹ ) side or the second ink pattern (P ² ) side (the mirror image is the second ink pattern (P ² ) side, The ink pattern (P ¹ ) side can be arbitrarily set according to the intention of the user. When it is desired to form a normal image on the second ink pattern (P ² ) on the peeled label side, printing on the porous layer (B) may be performed with the normal image, and conversely the first ink pattern on the resin molded product side. When it is desired to provide a normal image on (P ¹ ), printing on the porous layer (B) may be carried out with a reverse image (mirror image) obtained by reversing in advance.

The “color difference ΔE” on the surface (broken surface) of the first porous separation layer (B ¹ ) or the surface (broken surface) of the second porous separation layer (B ² ) is the ink pattern formation region (or ink pattern corresponding). For each of the (region) and the ink pattern non-formed region, the lightness L ^* value and the color coordinate a ^* value and b ^* value are measured using a color difference meter, and calculated from the measured values using the following formula.

In the above formula, L ^* _x represents an L ^* value of the ink pattern forming region, L ^* _y represents an L ^* value of the ink pattern non-forming region, a ^* _x is, a ^* value of the ink pattern formation region the stands, a ^* _y represents an a ^* value of the ink pattern non-formation region, b ^* _x represents the b ^* value of the ink pattern formation region, b ^* _y is the b ^* value of the ink pattern non-forming region Represents.
Further, the color difference ΔE _B between the pattern non-formation area and the surface of the resin molded product and the color difference ΔE _P between the pattern formation area and the surface of the resin molded product are also L for each area (surface) using a colorimeter. ^{The *} value and the color coordinate a ^* value and the b ^* value are measured, and can be obtained from the measured values by following the above-described calculation method of ΔE. In this case, in the above formula, L ^* _x represents an L ^* value of one region (surface) to obtain the color difference, L ^* _y represents an L ^* value of the other regions to determine the color difference (surface), a ^* _x represents an a ^* value of one region (surface) to obtain the color difference, while a ^* _y represents the a ^* values of the other regions to determine the color difference (surface), b ^* _x is seeking chrominance The respective color differences are calculated assuming that the b ^* value of the area is represented by b ^* _y and the b ^* _y is the b ^* value of the other area (front surface) for which the color difference is obtained.

<Adhesive tape peeling test>
By "pressure-sensitive adhesive tape peeling test" herein, the adhesive surface of the adhesive tape on the surface of the second porous separating layer as said second ink pattern appearing on the surface of (B ²⁾ (P ²⁾ Is attached and the adhesive tape is peeled off at a rate of 300 mm/min at 180°, and then the visibility of the ink pattern on the surface of the second porous separation layer (B ² ) and the adhesive surface of the adhesive tape is evaluated. .. After this adhesive tape peeling test, the reversal pattern of the second ink pattern (P ² ) can be visually recognized on the adhesive surface of the adhesive tape, and the second ink pattern (P ² ) on the surface of the second porous separation layer (B ² ). Is preferably visible. Particularly, the visibility of the second ink pattern (P ² ) in the second porous separation layer (B ² ) after the adhesive tape peeling test is an index of the penetration depth of the ink composition in the porous layer (B). And the clearer the second ink pattern (P ² ) visually recognized in the second porous separation layer (B ² ), the deeper the penetration depth of the ink composition in the porous layer (B) is. To do.

<Uses of resin molded products with labels and resin molded products with porous layers>
The labeled resin molded product of the present invention, and the resin molded product (the porous product having the first porous separation layer (B ¹ ) remaining after peeling the base layer (A) and the second porous separation layer (B ² ) Resin molded products with quality layers) are oil containers (bottles) used for lubricating oil, vacuum pump oil, machine oil, engine oil, motor oil, etc.; household detergent, laundry detergent, dishwashing detergent, bath detergent, toilet bowl Detergents, pipe cleaners, car wash detergents, softeners, bleaches, optical brighteners, facial cleansers, liquid soaps, shampoos, rinses, mouthwashes, deodorants, liquid bath salts, iron pastes, disinfectants, Chemical containers (bottles) used for germicides, alcohol for sterilization, waxes for polishing, pesticides, herbicides, insecticides, etc.; soft drinks, sake, soy sauce, sauces, sauces, cooking oils, food containers used for dressing, etc. (Bottle); Squeeze container used for spread of jam, margarine, peanut butter, ketchup, mayonnaise, etc.; Container for food (cup) such as ice cream, yogurt; Container for wet tissue (wide mouth bottle).

<< Manufacturing method of labeled resin moldings >>
The method for producing a labeled resin molded article of the present invention comprises a laminated resin film forming step of forming a laminated resin film having a base layer (A) and a porous layer (B) provided on the base layer (A). A printing step of printing an ink composition to form an ink pattern on the surface of the laminated resin film opposite to the base layer (A) of the porous layer (B) to obtain a label, and the ink pattern is formed. The label is inserted into the mold so that the base layer (A) side is the inner wall side of the mold and the porous layer (B) side is the cavity side of the mold so that it can come into contact with the molten resin and is labeled by the in-mold molding method And a molding step for obtaining a resin molded product.
In the production method of the present invention, when the ink composition used is colored, the color difference ΔE ₀ between the ink composition and the surface of the label on the porous layer (B) side is preferably 3 or more. On the other hand, when the ink composition used is colorless, the colorless ink composition is preferably transparent, and the color difference ΔE _P0 between the first ink pattern forming region and the surface of the resin molded product is less than 3. It is preferable. The color differences ΔE ₀ and ΔE _P0 can be obtained by following the method of calculating ΔE described in <Color difference ΔE on broken surface of porous separation layer> above. In this case, in the equation for calculating ΔE, L ^* _x represents the L ^* value of the first ink pattern forming region, and L ^* _y represents the surface of the label on the porous layer (B) side or the surface of the resin molded product. L ^* represents a value, a ^* _x represents an a ^* value of the first ink pattern formation region, a ^* _y is the porous layer of the label a ^* value of (B) side surface or a resin molded article surface expressed as b ^* _x represents the b ^* value of the first ink pattern formation region, b ^* _y represents the b ^* value of the porous layer (B) side surface or a resin molded article of the surface of the label, the color difference ΔE ₀ and ΔE _P0 are calculated.
Hereinafter, each step of the method for producing a labeled resin molded product of the present invention will be described in detail.

[1] Step of forming laminated resin film In this step, a laminated resin film having a base layer (A) and a porous layer (B) is formed.
The laminated resin film includes a laminating step of laminating a layer formed of the resin composition containing the material of the base layer (A) and a layer formed of the resin composition containing the material of the porous layer (B), and stretching each layer. It can be formed in combination with the stretching step. For specific examples and preferable ranges of the materials of the base layer (A) and the porous layer (B), the description in the section <Basic structure of label> can be referred to.
The stretching step may be carried out separately for the layers formed by the respective resin compositions, or may be carried out after laminating the respective resin compositions, but after laminating the respective resin compositions, at least uniaxially It is preferable to stretch. Since the porous layer (B) of the present invention has a low strength and a small wall thickness, it is extremely difficult to stretch and form a single layer of the porous layer (B). By stretching after laminating the base layer (A) and the porous layer (B), the porous layer (B) can be easily stretched. Therefore, the base layer (A) is also useful as a carrier for stretching the porous layer (B).
As a specific procedure, a layer of the resin composition containing the material of the base layer (A) is stretched in the longitudinal direction to obtain a longitudinally uniaxially stretched film, and then the material of the porous layer (B) is contained thereon. There may be mentioned a method in which layers of a resin composition are laminated and the laminate is stretched in the transverse direction to form a laminated resin film.

(Lamination of resin composition)
As the method for laminating the resin composition, various known methods can be used, but specific examples include a plurality of extruders and feed blocks, a multi-manifold, a multilayer die method using a multilayer die, and a plurality of extruders. There is an extrusion lamination method using a die. It is also possible to use a combination of the multilayer die method and the extrusion lamination method.

(Stretch)
Various known methods can be used for stretching. The stretching temperature is the glass transition temperature of the thermoplastic resin mainly used for the base layer (A) (for example, the thermoplastic resin occupying a majority amount (50% by mass or more) of the thermoplastic resin in the base layer (A)) or higher. It can be carried out within a known temperature range suitable for the stretching of the thermoplastic resin within the temperature range below the melting point of the crystal part. Specifically, when the thermoplastic resin of the base layer (A) is a propylene homopolymer (melting point 155 to 167°C), it is usually 100 to 166°C, and when it is high density polyethylene (melting point 121 to 136°C), it is usually. Stretching is performed at a temperature of 70 to 135° C., which is 1 to 70° C. lower than each melting point.
Here, it is particularly preferable that the layer of the resin composition to be the base layer (A) is longitudinally stretched at a temperature higher by 2 to 5° C. than the above temperature range. Thereby, the base layer (A) having high strength can be obtained.
Further, it is preferable that the layer of the resin composition to be the porous layer (B) is transversely stretched at a temperature 3 to 10° C. lower than the above temperature range. The preferred temperature range for transversely stretching the layer of the resin composition to be the porous layer (B) depends on the material used for the porous layer (B), but the thermoplastic resin of the porous layer (B) is propylene alone. When it contains a polymer, it is preferably 145 to 160°C. Thus, by performing the transverse stretching in a temperature range relatively lower than the above temperature range, the number of voids observed from the cross section in the thickness direction of the porous layer (B) becomes relatively large. As a result, it is possible to obtain a label in which the porous layer has a large absorption capacity for liquid or the like and a high filling rate of the ink composition. In the labeled resin molded article having such a label, when the porous layer (B) is separated by peeling off the base layer (A), the first porous separation layer (B ¹ ) and the base layer (A) on the resin molded article side are separated. ) Side, in each fracture surface of the second porous separation layer (B ² ), the color difference ΔE between the ink pattern forming region and the ink pattern non-forming region can be increased, and the first ink pattern (P ¹ ) or It becomes possible to easily recognize the two-ink pattern (P ² ).
Specific methods of stretching include stretching between rolls using the peripheral speed difference between rolls, clip stretching using a tenter oven, and the like. You may implement combining these stretching methods. The stretching between rolls has an advantage that the stretching ratio can be easily adjusted by changing the peripheral speed difference between the rolls. Tenter stretching has the advantage that the yield of products can be improved because a wide stretched film can be obtained, and since the sheet surface does not touch the equipment during heat stretching, problems such as sticking of the sheet and equipment occur. There are also difficult advantages.
The draw ratio is not particularly limited and is determined in consideration of the characteristics of the thermoplastic resin used for the label. When the number of stretching axes is uniaxial, the stretching ratio is usually 2 to 11 times, preferably 3 to 10 times. For example, when a polyolefin-based resin is used as the thermoplastic resin, the draw ratio during roll stretching is preferably 4 to 7 times, and the draw ratio during clip stretching using a tenter oven is preferably 4 to 11 times. When the number of stretching axes is biaxial, the area ratio is usually 2 to 80 times, preferably 3 to 60 times, and more preferably 4 to 50 times. When the area magnification is 2 times or more, it becomes easy to give a desired porosity to the film. On the other hand, if the area ratio is 80 times or less, there is an advantage that troubles such as sheet breakage and coarse perforation during stretching are less likely to occur in the laminated resin film forming step.

As a particularly preferable laminated resin film forming step, a resin composition containing a material for the base layer (A) is extruded from a die into a sheet shape and longitudinally stretched by utilizing a peripheral speed difference between rolls to obtain a longitudinal uniaxially stretched film. Then, a method in which a resin composition containing the material of the porous layer (B) is laminated on the longitudinally uniaxially stretched film and then transversely stretched using a tenter can be mentioned. At this time, as described above, in order to increase the strength of the base layer (A), the longitudinal stretching is carried out at a temperature 2 to 5° C. higher than the longitudinal stretching temperature of the usual thermoplastic resin film, and the ink of the porous layer (B) is used. In order to increase the absorption capacity, it is preferable to carry out the transverse stretching at a temperature 3 to 10° C. lower than the transverse stretching temperature of the usual thermoplastic resin film.

(Heat treatment)
It is preferable to heat-treat the laminated resin film after stretching. The heat treatment temperature is preferably selected to be 10 to 30° C. higher than the stretching temperature. The preferable range of the heat treatment temperature varies depending on the thermoplastic resin used for the porous layer (B), but it is preferable to select 165 to 180° C. when the thermoplastic resin of the base layer (A) is a propylene homopolymer. .. By heat-treating the laminated resin film, the thermal shrinkage in the stretching direction is reduced, and winding tightness during product storage and waviness due to shrinkage during in-mold molding are reduced. In addition, by performing the heat treatment at a temperature higher than the temperature of the heat treatment performed on a general stretched film, a part of the surface of the porous layer (B) is melted and the voids are reduced. Thereby, when the ink composition is printed on the surface of the porous layer (B) in the next printing step, the ink composition permeates so as to be extruded into the voids due to the capillary phenomenon, and the porous layer ( The ink composition can be penetrated to a deeper position of B).
Further, by performing the heat treatment, it is possible to obtain an effect that the irregularities on the surface of the porous layer (B) can be leveled to further smooth the surface of the porous layer (B). Here, in the in-mold molding performed in the subsequent step [4], if there are many convex portions on the surface of the porous layer (B), the surface and the resin molded product are in point contact with each other and the contact area is small. Therefore, in the obtained labeled resin molded product, the adhesive strength at the interface between the label (porous layer (B)) and the resin molded product tends to decrease. On the other hand, when the surface of the porous layer (B) is smoothed by the heat treatment, it is possible to obtain a labeled resin molded product in which the label is bonded to the resin molded product with high strength by in-mold molding. In such a labeled resin-molded product, when the base layer (A) of the label is peeled off from the resin-molded product, the porous layer (B) is less likely to peel at the interface between the porous layer (B) and the resin-molded product. Peeling due to cohesive failure of ( ¹ ) proceeds preferentially, and the porous layer (B) is easily separated into the first porous separation layer (B ¹ ) and the second porous separation layer (B ² ). Thereby, the color difference (contrast) between the ink pattern forming region and the ink pattern non-forming region is formed on the fracture surface of the first porous separation layer (B ¹ ) and further on the fracture surface of the second porous separation layer (B ² ). ) Clearly appears, and it becomes easy to visually recognize the first ink pattern (P ¹ ) and further the second ink pattern (P ² ).
The heat treatment method is generally performed with a hot roll and a hot oven, but these may be combined. It is preferable to perform these treatments in a state where the stretched film is held under tension because a higher treatment effect can be obtained.

After the heat treatment, it is preferable to subject the surface of the laminated resin film to oxidation treatment such as corona discharge treatment or plasma treatment. The oxidation treatment has an advantage that the wettability of the surface is further improved and the ink acceptability at the time of printing is improved.

[2] Printing step In this step, an ink pattern is formed by printing the ink composition on the surface of the laminated resin film formed in step [1] on the side of the porous layer (B). The ink composition of the ink pattern formed on the surface of the porous layer (B) penetrates into the voids through the openings on the surface of the porous layer (B) and is absorbed in the porous layer (B).
For the preferable ranges and specific examples of the components used in the ink composition, the description in the above section of [Ink composition] can be referred to.
The viscosity of the ink composition used in the present invention is preferably 10 mPa·s or more, more preferably 15 mPa·s or more, and further preferably 20 mPa·s or more. The viscosity of the ink composition is preferably 1500 mPa·s or less, more preferably 1200 mPa·s or less, and further preferably 1000 mPa·s or less. When the viscosity of the ink composition is 10 mPa·s or more, it is possible to prevent the ink composition from flowing too much, and the ink pattern that has penetrated into the porous layer (B) tends to be less likely to be blurred. Further, the handleability of the ink composition tends to be improved. On the other hand, when the viscosity of the ink composition is 1500 mPa·s or less, the ink composition printed on the surface of the porous layer (B) easily penetrates into the voids inside the porous layer (B), and the ink composition Can be absorbed to a deep position in the porous layer (B). As a result, in each fractured surface of the first porous separation layer (B ¹ ) and the second porous separation layer (B ² ) that appeared by peeling off the base layer (A) from the obtained labeled resin molded article, It is easy to obtain a high color difference ΔE between the ink pattern forming area and the ink pattern non-forming area.
The “viscosity of the ink composition” in the present specification refers to the viscosity of the ink composition measured by a single cylinder type rotational viscometer (B type viscometer) of JIS Z8803:2011. The viscosity of the ink composition can be adjusted and controlled by the type of composition in the ink composition, the concentration of solids, the type of solvent, the concentration of solvent, the use of additives such as reducers, and the like.

Here, since the viscosity of the ink composition used in the example of Patent Document 1 is too high, even if a large amount of the ink composition is supplied to the surface of the porous layer of the label, the ink composition has void openings. It stays in the vicinity (near the surface) and does not easily penetrate into the inside of the porous layer. The label thus obtained is attached to a resin molded product, the base layer of the label is peeled off, and the porous layer is separated into a porous separation layer on the base layer side and a porous separation layer on the molded product side. The ink composition has not reached the separation position (broken surface), and the ink pattern is covered with the porous separation layer. Therefore, even when looking at the fracture surface of the porous separation layer on the side of the molded product, the color difference between the ink pattern forming region and the ink pattern non-forming region is not sufficient, and it is not easy to visually recognize the ink pattern.
In order to make it easy to reveal the ink pattern by the ink composition on each fracture surface of the first porous separation layer (B ¹ ) on the molded product side and the second porous separation layer (B ² ) on the label side, As described above, (1) the transverse stretching temperature of the porous layer (B) is set relatively low to increase the porosity of the porous layer (B) to increase the ink absorption capacity, and (2) the porosity. The temperature during the heat treatment of the porous layer (B) is set to be relatively high to reduce the porosity in the vicinity of the surface of the porous layer (B), and (3) an ink composition used for forming an ink pattern. It is preferable to carry out, for example, to make the viscosity relatively low (within a specific range).

Examples of the method for printing the ink composition on the surface of the porous layer (B) include offset printing, gravure printing, letterpress printing, flexographic printing, screen printing, inkjet printing, electrophotographic printing, and various other printing methods. Among them, the flexographic printing method is preferable because it is suitable for printing an ink composition having a low viscosity.
The ink pattern printed on the surface of the porous layer (B) is not particularly limited. As a specific example, a pattern or a character, a barcode such as a QR code (registered trademark), a pattern representing a design or information such as a manufacturer, a sales company name, a character, or a product name can be given.

In addition, in this step, the ink composition may be printed on the surface of the porous layer (B) and also on the surface of the base layer (A) opposite to the porous layer (B). .. The label used in the present invention can be added with various functions such as writability, printability, scratch resistance, and secondary processing suitability by making the base layer (A) multi-layered.

[3] Heat Seal Layer Forming Step This step is an optional step, and a heat seal layer is formed on the surface of the porous layer (B) having the ink pattern formed in the step [2].
The heat seal layer can be formed by laminating a resin composition containing the material of the heat seal layer on the surface of the porous layer (B) having the ink pattern formed thereon by coating or printing. For the preferable range and specific examples of the material of the heat seal layer, the description in the above section of “Heat seal layer” can be referred to.
For specific examples of the printing method, various printing methods exemplified as the method of printing the ink composition in the step [2] can be referred to. Examples of the coating method include roll coating, gravure coating, curtain coating, spray coating and die coating.

[4] Molding step In this step, the label having the ink pattern is placed in the mold so that the base layer (A) side is the inner wall surface side of the mold and the porous layer (B) side is in contact with the molten resin. Insert and obtain a labeled resin molded product by the in-mold molding method.
The label used in the present invention is also suitable for direct blow molding in which a molten resin parison is pressure-bonded to the inner wall of the mold by compressed air and for stretch blow molding using a preform, but the molten resin is injected into the mold by an injection device. An in-mold molding label for injection molding in which it is poured and cooled and solidified can also be suitably subjected to the molding process.
Furthermore, as a label for differential pressure molding, after installing so that the printing surface of the label contacts the inner surface of the lower female die of the differential pressure molding die, it is fixed to the inner wall of the die by suction, and then the It is also possible to guide the melted material of the resin sheet to above the lower female die and fuse the label integrally to the outer wall of the molded product by differential pressure. As the differential pressure molding, either vacuum molding or pressure molding can be adopted, but in general, both are used in combination and differential pressure molding utilizing plug assist is preferable.
The labeled resin molded product of the present invention, after the label is fixed in the mold, the label and the resin molded product are integrally molded, so that there is no deformation of the label and the molded product and the label have an appropriate adhesive strength. It has a blister and has a good appearance decorated with a label.

Hereinafter, the present invention will be described more specifically with reference to Examples and Test Examples. Materials, amounts to be used, ratios, processing contents, processing procedures and the like used in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be limitedly interpreted by the following specific examples.

[Test example]
The tests performed in this example are shown below. The operation in which the temperature is not described is performed at 20°C.
(Viscosity of ink composition)
The viscosity of each ink composition was measured by storing each ink composition in a thermostatic chamber (temperature 20°C, relative humidity 65%) for 12 hours, and then using a single cylindrical viscometer (manufactured by Toki Sangyo Co., Ltd., device name). : TV-25) and a measuring method of a single cylinder type rotational viscometer described in JIS Z8803:2011 “Viscosity of liquid—Measuring method” at a rotation speed of 6 rpm.

(Porosity of porous layer (B))
After cooling the composition [B] obtained by melt-kneading the compound for the porous layer (B) used in the production example of each stretched film with an extruder, the true density ρ ₀ was measured according to JIS K7112:1999. ..
On the other hand, a cutter knife was put on the end surface of each stretched film obtained in the production example of the stretched film to obtain a gripping margin, and the porous layer (B) was slowly peeled by hand. The density ρ of the porous layer (B) was measured according to JIS K7222:2005. The porosity of the porous layer (B) was calculated by the following formula (1) from the true density ρ ₀ and the density ρ obtained as described above.

(Oil absorption)
The oil absorption of each of the stretched films obtained in the production example of the stretched film was measured using an oil absorption meter (manufactured by Kumagai Riki Kogyo Co., Ltd.). The oil absorption was measured by dropping 20 μm of mineral oil from the burette on the surface of the porous layer (B), using 5 test pieces, and dropping to the point where 5 scales were added from the case of the test piece only. The oil absorption specified in JAPAN TAPPI 67-2000 except that the time required for the roller to return to the value of the indicator of the galvanometer when passing over the test piece was measured instead of measuring the time required for the oil absorption. According to the test method.

(Peel strength of resin molded product with label)
A sample with a width of 15 mm and a length of 100 mm was cut out from the label-attached portion of the labeled resin molded product manufactured in each of the examples and each of the comparative examples, and each sample was placed in a thermostatic chamber (temperature 20° C., relative humidity 65%) for 12 hours. Stored for hours. Then, a slit was made on the end surface of the porous layer of the label with a cutter knife to make a stripping margin. The cuts were made from the end surface (the surface extending in the thickness direction) of the porous layer in a direction perpendicular to the end surface so that the porous layer was divided into two in the thickness direction, and the cut depth was 1 cm.
By using a tensile tester (manufactured by Shimadzu Corporation, device name: AUTOGRAPH), at a pulling speed of 300 mm/min, the stripping margin and the resin molded product are pulled at an angle of 180° from each other. The base layer (A) and the resin molded product were peeled off, and the stress when the peeling was stable was measured by a load cell. The stress was measured in the lateral direction and the longitudinal direction of each laminated resin film (the stretching direction of the porous layer (B) and the direction orthogonal thereto), and the average value thereof was calculated as the peel strength.

(Visibility of the ink pattern on the fracture surface)
The edges of the porous layer of the labels of the resin molded articles with labels manufactured in each of the examples and each of the comparative examples were cut with a cutter knife to make a stripping margin. The cut was made from the end face of the porous layer in a direction perpendicular to the end face so that the porous layer was divided into two in the thickness direction, and the cut depth was 1 cm.
The label was peeled from the resin molded product by hand by sandwiching the peeling margin with fingers and pulling the peeling margin and the resin molded product at a speed of about 100 mm/min in a direction away from each other at an angle of 180°.
After peeling the label, the print visibility of the first ink pattern (P ¹ ) appearing on the fracture surface of the first porous separation layer (B ¹ ) remaining in the resin molded product, and the second porous separation of the peeled label layer (B ²⁾ on the first ink pattern (P ¹⁾ of the corresponding region (P ') or exfoliated second porous separating layer of the label (B ²⁾ a second ink pattern that appeared on the fracture surface (P ² The print visibility of) was determined as follows.
The labeled resin-molded articles of the respective examples were cleanly broken in the porous layer (B) at the time of peeling the label, and were divided into the resin-molded article side and the label side, and both were laminated in a thin skin state. The base layer (A) was not exposed on the fracture surface on the label side, and the resin molded product was not exposed on the fracture surface on the resin molded product side.
⊚: The printed part can be seen darkly. ○: The printed part can be seen slightly lightly. Δ: The printed part can be seen lightly. ×: The printed part is difficult or impossible to see. Further, the first ink pattern (P ¹ ) and The relationship with the two-ink pattern (P ² ) was recorded.

(Adhesive tape peel test)
Regarding the labels peeled from the labeled resin molded products of Examples 7 to 19 and Comparative Examples 4 and 5 during the evaluation of the visibility of the ink pattern, the fracture surface of the second porous separation layer (B ² ) was observed. Adhesive tape (cellophane tape manufactured by Nichiban Co., Ltd., trade name: Cellotape (registered trademark), brand name: CT-18) was manually stuck on the second ink pattern (P ² ) that appeared, and the pulling speed The adhesive tape and the label were peeled by hand by pulling the adhesive tape and the label at an angle of 180° in a direction away from each other at a rate of about 100 mm/min. The visibility of the ink pattern on the adhesive surface of the adhesive tape after peeling and the peeling surface of the second porous separation layer (B ² ) was evaluated as follows.
○: Ink pattern is visible △: Ink pattern is unclear but visible ×: Ink pattern is not visible

(Measurement of color difference ΔE between the ink pattern forming area on the porous layer fracture surface and the ink pattern non-forming area on the same surface and systematic color judgment)
The ink pattern (P ¹ ) forming area and the non-forming area on the first porous separation layer (B ¹ ) remaining in the resin molded article during the peel strength test of the labeled resin molded article, and the number of the peeled label 2 porous separation layer (B ²⁾ on the corresponding area (P ') or ink pattern (P ²⁾ forming region, and for each of the non-forming region, a color difference meter (video jet Rite Co., equipment Name: X-rite 530) was used to measure the lightness L ^* value and the color coordinates a ^* , b ^* value, and the color difference ΔE was determined by the following formula.

In the above formula, L ^* _x represents an L ^* value of the ink pattern formation region or the corresponding region, L ^* _y represents an L ^* value of the ink pattern non-forming region, a ^* _x is an ink pattern formation region or represents a ^* value of the corresponding region, a ^* _y represents an a ^* value of the ink pattern non-formation region, b ^* _x represents the b ^* value of the ink pattern formation region or the corresponding region, b ^* _y is It represents the b ^* value of the ink pattern non-formed area.
Here, when the color difference ΔE is 3 or less, it is determined to be “same system color”, and when the color difference ΔE exceeds 3, it is determined to be “different system color”.

(Measurement of color difference ΔE between the area where the ink pattern (P ¹ ) is formed on the fracture surface of the porous layer and the resin molded product, and systematic color determination)
At the time of measuring the color difference ΔE, a color difference meter (manufactured by Videojet X-Rite Co., Ltd., device name: X-rite 530) was used to measure the label non-adhered portion of the resin molded article (body portion of the hollow molded article). The lightness L ^* value and the color coordinates a ^* and b ^* values were measured. Next, with respect to the labeled resin molded products of Examples 1 to 6 and Comparative Examples 1 and 2, the color difference ΔE between the ink pattern (P ¹ ) forming region of the porous layer fracture surface and the resin molded product was determined by the following formula.

In the above formula, L ^* _x represents an L ^* value of the ink pattern (P ¹⁾ forming region, L ^* _y represents an L ^* value of the resin molded article, a ^* _x is an ink pattern (P ¹⁾ represents a ^* value of formation region, a ^* _y represents the a ^* values of the resin molded article, b ^* _x represents the b ^* value of the ink pattern (P ¹⁾ formation region, b ^* _y, the resin ^Indicates the b ^* value of the molded product.
Here, when the color difference ΔE is 3 or less, it is determined to be “same system color”, and when the color difference ΔE exceeds 3, it is determined to be “different system color”.

(Measurement of color difference ΔE between the ink pattern (P ¹ ) non-formed area of the porous layer fracture surface and the resin molded product and systematic color determination)
At the time of measuring the color difference ΔE, regarding the labeled resin molded products of Examples 1 to 6 and Comparative Examples 1 to 3, the ink pattern (P ¹ ) non-formed region of the porous layer fracture surface and the resin molded product were calculated by the following formula. The color difference ΔE with
In the above formula, L ^* _x represents an L ^* value of the ink pattern (P ¹⁾ non-forming region, L ^* _y represents an L ^* value of the resin molded article, a ^* _x is an ink pattern (P ¹ ) represents the a ^* values of the non-forming region, a ^* _y represents the a ^* values of the resin molded article, b ^* _x is an ink pattern (P ¹⁾ represents the b ^* value of the non-formation region, b ^* _y Represents the b ^* value of the resin molded product.
Here, when the color difference ΔE is 3 or less, it is determined to be “same system color”, and when the color difference ΔE exceeds 3, it is determined to be “different system color”.

[Electron microscope observation]
The laminated resin film produced in each production example was embedded with an epoxy resin and solidified, and then a cut surface parallel to the thickness direction of the film (that is, perpendicular to the plane direction) was produced using a microtome. After metallizing this cut surface by metallizing, a scanning electron microscope (manufactured by Hitachi, Ltd., device name: S-2400) was used to magnify 3000 times and photographed, and the image was analyzed. A cross-sectional image was obtained by performing binarization processing and image processing with a device (manufactured by Nireco Corporation, device name: Luzex IID). The porosity of each layer was obtained using this cross-sectional image.

(Cross Section Porosity of Base Layer (A) and Porous Layer (B))
For each of the base layer (A) and the porous layer (B) on the cross-sectional image, a value obtained by dividing the area of the void region partitioned by the thermoplastic resin composition by the area of the entire observation region was calculated as the cross-sectional porosity. .. The inorganic filler in the voids observed in the cross-sectional image was treated as voids.

[Production of stretched film]
Table 1 collectively describes the materials used in each production example, and Table 2 collectively describes the composition of the formulation used in each production example. "MFR" in Table 1 means a melt flow rate.

(Production Example 1 of laminated resin film)
Base layer (A) comprising 34% by mass of PP-1 and 20% by mass of PP-2 as a crystalline polypropylene resin, 45% by mass of F-3 as an inorganic fine powder, and 1% by mass of D-3 as a dispersant. The compound d for use in the composition was melt-kneaded with an extruder set at 250° C., extruded into a sheet through a die, and cooled to 70° C. with a cooling device to obtain a single-layer unstretched sheet. This unstretched sheet was reheated to 145° C. and then stretched 5 times in the machine direction by utilizing the peripheral speed difference between a large number of rolls to obtain a longitudinal uniaxially stretched film.
Separately, 16% by mass of PP-1 as a crystalline polypropylene resin, 19.5% by mass of PE-1 as a thermoplastic resin incompatible with the crystalline polypropylene resin, and 62% of F-1 as an inorganic fine powder. % By mass, and a compound a for a porous layer (B) consisting of 0.5% by mass of D-1 and 2% by mass of D-2 as a dispersant are melt-kneaded by an extruder set at 250° C., It was extruded in a sheet form through a die and laminated on one side of the longitudinally uniaxially stretched film to obtain a laminate having a two-layer structure of d/a.
Then, the laminate was reheated to 153° C. using an oven, then stretched 9 times in the transverse direction using a tenter stretching machine, and then heat-treated at 170° C. to be biaxially/uniaxially stretched. Further, a two-layer stretched film (laminated resin film) of Production Example 1 was obtained. The total thickness of the two-layer stretched film of Production Example 1 was 105 μm, of which the thickness of the porous layer (B) was 6 μm and the porosity of the porous layer (B) was 60%.

(Production Example 2 of laminated resin film)
Two-layer stretching was performed in the same manner as in Production Example 1 except that the reheating temperature when stretching the laminate in the transverse direction was 158° C., and the temperature of the heat treatment performed after stretching in the transverse direction was 160° C. A film (laminated resin film) was obtained. The total thickness of the two-layer stretched film of Production Example 2 was 95 μm, of which the thickness of the porous layer (B) was 5 μm and the porosity of the porous layer (B) was 52%.

(Production Example 3 of laminated resin film)
A single-layer longitudinally uniaxially stretched film made of the compound d was obtained by the same process as the forming process of the longitudinally uniaxially stretched film in Production Example 1.
Separately from this, a compound e for the base layer (A) comprising 50% by mass of PP-1 and 30% by mass of PP-2 as a crystalline polypropylene resin and 20% by mass of F-3 as an inorganic fine powder is prepared. The mixture was melt-kneaded with an extruder set at 250° C., extruded into a sheet through a die, and laminated on one surface of the longitudinally uniaxially stretched film.
Separately, 13% by mass of PP-3 as a crystalline polypropylene resin, 25% by mass of PE-2 as a thermoplastic resin incompatible with the crystalline polypropylene resin, 60% by mass of F-4 as an inorganic fine powder, and The compound b for the porous layer (B) consisting of 2% by mass of D-3 as a dispersant is melt-kneaded by an extruder set at 250° C., extruded into a sheet through a die, and the above-mentioned longitudinal uniaxial stretching is performed. The compound e of the film was laminated on the surface opposite to the laminated surface to obtain a laminate having a three-layer structure of e/d/b.
Then, the laminate was reheated to 153° C. using an oven, then stretched 9 times in the transverse direction using a tenter stretching machine, and then heat-treated at 170° C. to perform uniaxial stretching/biaxial stretching/ A uniaxially stretched three-layer stretched film (laminated resin film) of Production Example 3 was obtained. The total thickness of the three-layer stretched film of Production Example 3 was 100 μm, of which the thickness of the porous layer (B) was 10 μm and the porosity of the porous layer (B) was 60%.

(Production Example 4 of laminated resin film)
Three-layer drawing was performed in the same manner as in Production Example 3 except that the reheating temperature when stretching the laminate in the transverse direction was 158° C. and the temperature of the heat treatment performed after stretching in the transverse direction was 160° C. A film (laminated resin film) was obtained. The total thickness of the three-layer stretched film of Production Example 4 was 91 μm, of which the thickness of the porous layer (B) was 9 μm and the porosity of the porous layer (B) was 50%. Production Example 4 of the stretched film employs the same transverse stretching temperature as that in Example 3 of JP 2012-215799 A.

(Production Example 5 of laminated resin film)
A single-layer longitudinally uniaxially stretched film made of the compound d was obtained by the same process as the forming process of the longitudinally uniaxially stretched film in Production Example 1.
Separately, 42% by mass of PP-3 as a crystalline polypropylene resin, 3.5% by mass of PO-1 as a thermoplastic resin incompatible with the crystalline polypropylene resin, 52% of F-2 as an inorganic fine powder. 0.5% by mass and 0.5% by mass of F-5, and 0.5% by mass of D-1 and 1% by mass of D-2 as a dispersant for the formulation c for the porous layer (B). The mixture was melt-kneaded with an extruder set at 250° C., extruded into a sheet through a die and laminated on one side of the longitudinally uniaxially stretched film to obtain a laminate having a two-layer structure of d/c.
Then, the above laminate was reheated to 158° C. using an oven, then stretched 9 times in the transverse direction using a tenter stretching machine, and then heat treated at 160° C. to be biaxially/uniaxially stretched. Moreover, a two-layer stretched film (laminated resin film) of Production Example 5 was obtained. The total thickness of the two-layer stretched film of Production Example 5 was 95 μm, of which the thickness of the porous layer (B) was 4 μm and the porosity of the porous layer (B) was 30%.

Table 3 shows the formulations and conditions used in each of the above Production Examples, the porosity and oil absorbency of the porous layer (B) of the produced laminated resin film.

[Manufacture of labeled resin moldings]
(Example 1)
On the surface of the laminated resin film obtained in Production Example 1 on the side of the base layer (A), an offset printing machine (manufactured by Mitsubishi Heavy Industries, Ltd., device name: Diamond II type) and a UV offset ink I-4 (T&K TOKA Corporation). Product name: Best Cure 161 black ink, ink viscosity: 25000 mPa·s) was used to print a design of a character and a design including 50% halftone dots.
Next, a flexo printing machine (manufactured by Mark Andy, device name: 2200) and a colorless UV flexo ink I-1 (manufactured by T&K TOKA Co., Ltd., trade name: UV) are formed on the surface of the film on the side of the porous layer (B). Using Flexomedium 500, ink viscosity: 600 mPa·s), a pattern having 600 lines/inch and a halftone dot ratio of 70% was printed.
Next, using a gravure printing machine (manufactured by Okazaki Machinery Co., Ltd.) and a heat sealing agent H-1 (manufactured by Toyo Morton Co., Ltd., trade name: ADCOAT 1790) on the entire surface of the porous layer (B) side, 100% halftone dots with 200 lines/inch were printed and punched into a size of 109 mm in width and 171 mm in length to obtain an in-mold molding label.
Next, a hollow molding machine (manufactured by Placo Co., Ltd., device name: V-50 type), an automatic label supply device (manufactured by Pentel Co., Ltd.), and a split mold for hollow molding to obtain a bottle container having an internal capacity of 1,000 ml. Was used to obtain a labeled resin molded product by an in-mold molding method. Specifically, the label for in-mold molding obtained above was fixed to one of the split molds for blow molding by using vacuum so that the base layer (A) side was in contact with the mold, and then the high-density polyethylene (Japan 3. A blue resin colored blue with polyethylene Co., Ltd., trade name: Novatec HD HB330, melting point: 133°C) is melt extruded at 200°C to form a parison, and the split mold is clamped after being introduced between split molds, and then 4. 2 kg/cm ² of compressed air was supplied into the parison, and the parison was expanded and brought into close contact with the mold to form a container shape and adhered to the in-mold molding label, and then the split mold was cooled with cooling water at 10°C. Then, after about 10 seconds, the mold was opened to take out the hollow container to which the label was attached, and this was used as a labeled resin molded product.

(Examples 2 and 3)
A labeled resin molded product was produced in the same manner as in Example 1 except that the number of lines and the dot ratio of the pattern to be flexographically printed on the porous layer (B) side were changed as shown in Table 4.

(Comparative example 2)
The number of lines and the dot ratio of the flexographically printed pattern on the side of the porous layer (B) were changed as shown in Table 4, and instead of the high density polyethylene colored in blue, a natural color high density polyethylene (Japanese polyethylene) was used. A labeled resin molded product was manufactured in the same manner as in Example 1 except that a hollow container was molded using a trade name: Novatec HD HB330, melting point: 133°C manufactured by K.K.

(Examples 4 to 6, Comparative Example 1)
A labeled resin molded product was produced in the same manner as in Example 1 except that the laminated resin film obtained in the production example shown in Table 4 was used in place of the laminated resin film obtained in the production example 1.

(Comparative example 3)
An offset printing machine (manufactured by Mitsubishi Heavy Industries, Ltd., device name: Diamond II type) was formed on the surface of the laminated resin film on the side of the base layer (A) manufactured under the same conditions as in Example 3 described in JP 2012-215799 A. ) And UV offset ink I-4 (manufactured by T&K TOKA Co., Ltd., trade name: Best Cure 161 ink, ink viscosity: 25000 mPa·s) were used to print a design including a character pattern and 50% halftone dots.
Next, on the surface of the same film on the side of the porous layer (B), the same offset printing machine as described above and a different UV offset ink I-2 (manufactured by T&K TOKA Corp., UV161 medium S, ink viscosity: 24000 mPa·s) were used. ) Was used to print the same pattern as in Example 1.
Then, the heat-sealing agent H-1 was printed on the entire surface of the porous layer (B) side in the same manner as in Example 1, and the in-mold molding label obtained by punching into a size of 109 mm in width and 171 mm in length was used, As in Example 1, in-mold molding was performed using high-density polyethylene colored in blue to produce a labeled resin molded product.

(Example 7)
On the surface of the laminated resin film obtained in Production Example 1 on the side of the base layer (A), an offset printing machine (manufactured by Mitsubishi Heavy Industries, Ltd., device name: Diamond II type) and a UV offset ink I-4 (T&K TOKA Corporation). Product name: Best Cure 161 black ink, ink viscosity: 25000 mPa·s) was used to print a design of a character and a design including 50% halftone dots.
Next, on the surface of the film on the side of the porous layer (B), a flexographic printing machine (manufactured by Mark Andy, device name: 2200) and UV flexo ink I-3 (manufactured by T&K TOKA, trade name: UV). A flexo 500 ink, ink viscosity: 600 mPa·s) was used to print a pattern having 300 lines/inch and a dot rate of 90%.
Next, using a gravure printing machine (manufactured by Okazaki Machinery Co., Ltd.) and a heat sealing agent H-1 (manufactured by Toyo Morton Co., Ltd., trade name: ADCOAT 1790) on the entire surface of the porous layer (B) side, 100% halftone dots with 200 lines/inch were printed and punched into a size of 109 mm in width and 171 mm in length to obtain an in-mold molding label.
Next, a hollow molding machine (manufactured by Placo, Inc., model: V-50 type), an automatic label feeder (manufactured by Pentel Co., Ltd.) and a split mold for hollow molding capable of obtaining a bottle container with an internal capacity of 1,000 ml. A resin molded product with a label was obtained by in-mold molding. Specifically, the label for in-mold molding obtained above is punched into a size of 109 mm in width and 171 mm in length so that one side of the split mold for blow molding uses vacuum so that the base layer (A) side is in contact with the mold. After fixing the label on, the high density polyethylene (Nippon Polyethylene Co., Ltd., trade name: Novatec HD HB330, melting point: 133°C, natural color) is melt extruded at 200°C to form a parison, and the parison is introduced between the split molds. Is clamped, then 4.2 kg/cm ² of compressed air is supplied into the parison, and the parison is expanded and brought into close contact with the mold to form a container shape and adhered to the label for in-mold molding. After cooling with cooling water at 10° C., the mold was opened after about 10 seconds and the hollow container with the label attached was taken out, which was used as a labeled resin molded product.

(Examples 8 to 10)
A labeled resin molded article was produced in the same manner as in Example 7, except that the halftone dot ratio of the pattern to be flexographically printed on the porous layer (B) side was changed as shown in Table 4.

(Example 11)
Instead of gravure-printing the heat-sealing agent H-1 on the surface on the side of the porous layer (B), the heat-sealing agent is applied by hand using a Meyer bar #16, and at the same time, a natural-colored high-density polyethylene is used. Instead, a labeled resin molded product was manufactured in the same manner as in Example 7, except that the resin molded product was molded using high-density polyethylene colored in blue.

(Examples 12 and 13)
The halftone dot ratio of the pattern to be flexographically printed on the side of the porous layer (B) was changed as shown in Table 4, and blue-colored high-density polyethylene was used in place of the natural-color high-density polyethylene to form a resin molded product. A labeled resin molded product was manufactured in the same manner as in Example 7 except that the above was molded.

(Examples 14 to 16 and Comparative Example 4)
A labeled resin molded article was produced in the same manner as in Example 7, except that the laminated resin film obtained in the production example shown in Table 4 was used instead of the laminated resin film obtained in Production Example 1.

(Comparative example 5)
An offset printing machine (manufactured by Mitsubishi Heavy Industries, Ltd., device name: Diamond II type) was formed on the surface of the laminated resin film on the side of the base layer (A) manufactured under the same conditions as in Example 3 described in JP 2012-215799 A. ) And UV offset ink I-4 (manufactured by T&K TOKA Co., Ltd., trade name: Best Cure 161 ink, ink viscosity: 25000 mPa·s) were used to print a design including a character pattern and 50% halftone dots.
Next, on the surface of the same film on the side of the porous layer (B), the same offset printing machine as that used on the side of the base layer (A) and UV offset ink I-4 (manufactured by T&K TOKA, trade name: best) A pattern having halftone dots of 50% was printed using Cure 161 black ink and ink viscosity: 25,000 mPa·s).
Then, the heat-sealing agent H-1 was printed on the entire surface of the porous layer (B) side in the same manner as in Example 1, and the in-mold molding label obtained by punching into a size of 109 mm in width and 171 mm in length was used, In-mold molding was performed using natural-color high-density polyethylene to manufacture a labeled resin molded product.

(Example 17)
On the surface of the laminated resin film obtained in Production Example 2 on the side of the base layer (A), an offset printing machine (manufactured by Mitsubishi Heavy Industries, Ltd., device name: Diamond II type) and a UV offset ink I-4 (T&K TOKA Corporation). Product name: Best Cure 161 ink, ink viscosity: 25000 mPa·s) was used to print a design of a character and a design including 50% halftone dots.
Next, on the surface of the film on the side of the porous layer (B), an inkjet printer (manufactured by Seiko Epson Corp., device name: PX-V630) and UV inkjet ink I-5 (manufactured by CTC Japan Co., Ltd., product) Name: KY-G2-BLACK, ink viscosity: 20 mPa·s) was used, and printing mode: Super Fine was used to print a halftone dot ratio of 100%.
Next, using a gravure printing machine (manufactured by Okazaki Machinery Co., Ltd.) and a heat sealing agent H-1 (manufactured by Toyo Morton Co., Ltd., trade name: ADCOAT 1790) on the entire surface of the porous layer (B) side, 100% halftone dots with 200 lines/inch were printed and punched into a size of 109 mm in width and 171 mm in length to obtain an in-mold molding label.
Next, a hollow molding machine (manufactured by Placo, Inc., model: V-50 type), an automatic label feeder (manufactured by Pentel Co., Ltd.) and a split mold for hollow molding capable of obtaining a bottle container with an internal capacity of 1,000 ml. A resin molded product with a label was obtained by in-mold molding. Specifically, the label for in-mold molding obtained above is punched into a size of 109 mm in width and 171 mm in length so that one side of the split mold for blow molding uses vacuum so that the base layer (A) side is in contact with the mold. After fixing the label on, the high density polyethylene (Nippon Polyethylene Co., Ltd., trade name: Novatec HD HB330, melting point: 133°C, natural color) is melt extruded at 200°C to form a parison, and the parison is introduced between the split molds. Is clamped, then 4.2 kg/cm ² of compressed air is supplied into the parison, and the parison is expanded and brought into close contact with the mold to form a container shape and adhered to the label for in-mold molding. After cooling with cooling water at 10° C., the mold was opened after about 10 seconds and the hollow container with the label attached was taken out, which was used as a labeled resin molded product.

(Example 18)
Except that the ink for flexographic printing on the side of the porous layer (B) was UV flexo ink I-6 (manufactured by T&K TOKA Co., Ltd., trade name: UV flexo CF ink, ink viscosity: 1200 mPas). A labeled resin molded product was produced in the same manner as in Example 7.

(Example 19)
Using the laminated resin film obtained in Production Example 1, an inkjet printing machine for inkjet printing on the porous layer (B) side, Seiko Epson Corp., device name: PX-V630 was used, and an aqueous inkjet ink I was used as the inkjet ink. -7 (manufactured by Seiko Epson Corporation, trade name: ICBK31 cyan, magenta, yellow, ink viscosity: 10 mPa·s), printing mode: super fine 50% gray (R: 50%, G: 50%) , B: 50%) and halftone dot ratio: 100% were used to produce a labeled resin molded article in the same manner as in Example 17.

The measurement of the peel strength of the label from the resin molded product performed on the labeled resin molded products produced in each of the above Examples and Comparative Examples, the first ink pattern (P ¹ ) and the second ink pattern (P ² ) Table 5 shows the evaluation results of the visibility and the evaluation results of the adhesive tape peeling tests of Examples 7 to 19 and Comparative Examples 4 and 5 described above.
Color difference between the ink pattern (P ¹ ) forming region and the ink pattern (P ¹ ) non-forming region in the first porous separation layer (B ¹ ) in the labeled resin molded products produced in the above Examples and Comparative Examples. ΔE, and the color difference between the corresponding region (P′) or ink pattern (P ² ) forming region and the outside of the corresponding region (P′) or the ink pattern (P ² ) non-forming region in the second porous separation layer (B ² ). ΔE, the color difference ΔE _P between the ink pattern (P ¹ ) forming region and the resin molded product in the labeled resin molded products produced in Examples 1 to 6 and Comparative Examples 1 to 3 above, and the ink pattern (P ¹ ). Table 6 shows the evaluation results of the color difference ΔE _B between the non-formed area and the resin molded product.

As shown in Table 5, in the labeled resin molded products produced in Examples 1 to 19, when the base layer (A) of the label was peeled from the resin molded product, the porous layer (B) was formed on the resin molded product side and the base layer. The first ink pattern (P ¹ ) appeared on the first porous separation layer (B ¹ ) on the side of the resin molded product after being separated on both sides (A).
In particular, in each labeled resin molded product of Examples 1 to 6 using a label in which the porous layer (B) side was printed with a colorless medium ink, when the base layer (A) of the label was peeled from the resin molded product, The first ink pattern (P ¹ ) appeared on the first porous separation layer (B ¹ ) on the resin molded product side.
At this time, as shown in Table 6, the color difference ΔE between the ink pattern (P ¹ ) forming region (printing portion) and the ink pattern non-forming region (margin portion) exceeds 3 and is determined to be a different system color. It was possible, and the visibility of the ink pattern was practical.
On the other hand, in each of the labeled resin molded products of Examples 1 to 3 and Example 5, the corresponding region (P′) of the second porous separation layer (B ² ) separated along with the label having the base layer (A) was formed. No ink pattern was observed.
Further, in each of the labeled resin molded products of Examples 7 to 19 using the label in which the porous layer (B) side was printed with the colored flexo ink or the colored inkjet ink, the first porous separation on the resin molded product side was performed. The ink pattern (P ¹ ) and the second ink pattern (P ² ) are respectively present on both the layer (B ¹ ) and the second porous separation layer (B ² ) peeled off along with the label having the base layer (A). Appeared.
At this time, as shown in Table 6, the ink pattern on the first porous separation layer ^{(B 1) (P 1)} , second porous separation layer (B ²⁾ a second ink pattern on the (P ²⁾ is In both cases, the color difference ΔE between the ink pattern forming area (printed area) and the ink pattern non-forming area (margin area) exceeds 3, and it can be determined as a different system color, and the visibility of the ink pattern is practical. It was a thing.
Furthermore, in each of the labeled resin molded products of Examples 7 to 19, the second ink pattern (P ² ) that appeared on the second porous separation layer (B ² ) along with the label was evaluated by the adhesive tape peel test. Since ink patterns were recognized on both the fracture surface of the second porous separation layer (B ² ) and the adhesive surface of the adhesive tape, the ink composition penetrated deep into the porous layer (B). I was able to confirm that
On the other hand, in the labeled resin molded products manufactured in Comparative Examples 1 and 4, the ink pattern was formed on both the fracture surfaces of the first porous separation layer (B ¹ ) and the second porous separation layer (B ² ). Could not be seen. This is because the porous layer (B) of the laminated resin film of Production Example 5 has a low porosity and poor oil absorbency, so that the porous layer (B) was used even though an ink having a low viscosity was used. It is considered that this is because the ink composition does not penetrate to the inside of the ink.
Moreover, the laminated resin film used for the labeled resin molded articles of Comparative Examples 3 and 5 and produced under the same conditions as Example 3 of JP2012-215799A has an oil absorption of the porous layer (B). It was inferior in the property, and it was suggested that the permeability of the ink composition was low. Further, on the porous layer (B) side of this laminated resin film, the ink composition I-2 having a high viscosity and the UV offset ink (T&K TOKA Co., Ltd.) used in the examples of JP 2012-215799 A are used. Manufactured, trade name: Best Cure 161, ink viscosity: 25000 mPa·s, ink composition I-4) is used in the labeled resin molded article, the first porous separation layer (B ¹ ) and The ink pattern could not be visually recognized on any fracture surface of the two porous separation layers (B ² ). It is presumed that this is because the highly viscous ink remains near the surface of the porous layer (B) and hardly penetrates into the inside of the layer.
Further, comparison of Examples 2 and 3 and Comparative Example 2 in which the halftone dot ratio of the ink pattern to be printed on the porous layer (B) is changed from that of Example 1, and the halftone dot is similarly to Example 7. From the comparison of Examples 8 and 9 and Examples 10 and 13 in which the ratio was changed, the lower the halftone dot ratio of the ink pattern, the more difficult the ink composition penetrated into the porous layer (B), and the first It was found that the ink patterns in the porous separation layer (B ¹ ) and the second porous separation layer (B ² ) were hard to see.
Further, as shown in Table 5, the laminated resin film of Production Example 1 and the laminated resin film of Production Example 3, and Production Examples in which the temperature during transverse stretching was increased by 5°C and the temperature during heat treatment was decreased by 10°C. When the laminated resin film of No. 2 and the laminated resin film of Production Example 4 are compared, the porosity of the porous layer (B) in the laminated resin films of Production Examples 2 and 4 shows that in the laminated resin films of Production Examples 1 and 3. It is smaller than the porosity of the porous layer (B).
Relatedly, as shown in Table 6, labeled resin molded articles of Examples 1 and 5 using the laminated resin films of Production Examples 1 and 3, and Examples using the laminated resin films of Production Examples 2 and 4 comparing the 4 and 6 and a labeled resin shaped article, the ink pattern on the first porous separating layer in example ^{4,6 (B 1) (P 1} ) had become slightly unclear. This means that the porous layer (B) in Examples 4 and 6 has a shallow penetration depth of the ink composition as compared with the porous layer (B) in Examples 1 and 5. Similarly, the labeled resin molded products of Examples 7 and 15 using the laminated resin films of Production Examples 1 and 3, and the labeled resin molded products of Examples 14 and 16 using the laminated resin films of Production Examples 2 and 4. Comparing with, the ink pattern (P ² ) on the second porous separation layer (B ² ) after the adhesive tape peeling test was unclear. This means that the porous layer (B) in Examples 14 and 16 has a lower penetration depth of the ink composition than the porous layers (B) in Examples 7 and 15.
Therefore, in order to deepen the penetration depth of the ink composition into the porous layer (B), it is preferable to increase the porosity of the porous layer (B), and when forming the porous layer (B). It was found that it is preferable to set the transverse stretching temperature of No. 2 to be low and the heat treatment temperature to be high. It has also been found that it is preferable to use an ink having a low viscosity.

1 Resin molded product 2 Label 3 Labeled resin molded product A Base layer B Porous layer P Ink pattern 11 Void 12 Ink composition B ¹ First porous separation layer (resin molded product side)
B ² Second porous separation layer (base layer side)
P'corresponding area of ink pattern P ¹ first ink pattern P ² second ink pattern 21 pattern non-formation area where the first ink pattern is not formed 22 pattern non-formation area where the second ink pattern is not formed

Claims (29)

A resin molded article and a labeled resin molded article having a label attached to the resin molded article,
The label is present inside the base layer (A), the porous layer (B) provided on the base layer (A) and having a wall thickness of 0.1 to 20 μm, and the inside of the porous layer (B). A void and an ink composition present so as to occupy a part of the void,
The label is attached to the resin molded article on the surface of the porous layer (B) side,
The resin of the resin molded product has entered the openings on the surface of the porous layer (B),
A notch having a depth of 1 cm was made from the end face of the porous layer (B) in a direction perpendicular to the end face, and the peeling margin and the resin molded product thus formed were pulled at an angle of 180° in a direction away from each other. When the label is peeled off from the molded product, the porous layer (B) is accompanied by the first porous separation layer (B ¹ ) remaining attached to the resin molded product and the base layer (A). The first ink pattern (P) formed by the ink composition is formed on the surface of the first porous separation layer (B ¹ ) opposite to the resin molded product while separating into the second porous separation layer (B ² ) to be peeled off. ¹ ) appears,
A resin molded product with a label, wherein the first ink pattern (P ¹ ) can be visually confirmed. A resin molded article and a labeled resin molded article having a label attached to the resin molded article,
The label is present inside the base layer (A), the porous layer (B) provided on the base layer (A) and having a wall thickness of 0.1 to 20 μm, and the inside of the porous layer (B). A void and an ink composition present so as to occupy a part of the void,
The label is attached to the resin molded article on the surface of the porous layer (B) side,
The porous layer (B) is a stretched resin film stretched in at least a uniaxial direction,
A notch having a depth of 1 cm was made from the end face of the porous layer (B) in a direction perpendicular to the end face, and the peeling margin and the resin molded product thus formed were pulled at an angle of 180° in a direction away from each other. When the label is peeled off from the molded product, the porous layer (B) is accompanied by the first porous separation layer (B ¹ ) remaining attached to the resin molded product and the base layer (A). The first ink pattern (P) formed by the ink composition is formed on the surface of the first porous separation layer (B ¹ ) opposite to the resin molded product while separating into the second porous separation layer (B ² ) to be peeled off. ¹ ) appears,
A resin molded product with a label, wherein the first ink pattern (P ¹ ) can be visually confirmed. A resin film in which the porous layer (B) contains a crystalline polypropylene resin, a blend of a thermoplastic resin incompatible with the crystalline polypropylene resin, and a fine powder is stretched in at least one axial direction. The labeled resin molded article according to claim 2, which is a stretched film. The labeled resin molded article according to any one of claims 1 to 3, wherein the ink composition is a colorless ink composition containing substantially no coloring material. A resin molded article and a labeled resin molded article having a label attached to the resin molded article,
The label is present inside the base layer (A), the porous layer (B) provided on the base layer (A) and having a wall thickness of 0.1 to 20 μm, and the inside of the porous layer (B). A void and an ink composition present so as to occupy a part of the void,
The ink composition is a colorless ink composition containing substantially no coloring material,
The label is attached to the resin molded article on the surface of the porous layer (B) side,
A notch having a depth of 1 cm was made from the end face of the porous layer (B) in a direction perpendicular to the end face, and the peeling margin and the resin molded product thus formed were pulled at an angle of 180° in a direction away from each other. When the label is peeled off from the molded product, the porous layer (B) is accompanied by the first porous separation layer (B ¹ ) remaining attached to the resin molded product and the base layer (A). The first ink pattern (P) formed by the ink composition is formed on the surface of the first porous separation layer (B ¹ ) opposite to the resin molded product while separating into the second porous separation layer (B ² ) to be peeled off. ¹ ) appears,
A resin molded product with a label, wherein the first ink pattern (P ¹ ) can be visually confirmed. On the surface of the first porous separation layer (B ¹ ) opposite to the resin molded product, a plurality of voids in the pattern formation region in which the first ink pattern (P ¹ ) is formed are the colorless ink. The labeled resin according to claim 4 or 5 , which is filled with the composition and has different opacity between the pattern formation region and the pattern non-formation region where the first ink pattern (P ¹ ) is not formed. Molding. On the surface of the first porous separation layer (B ¹ ) on the side opposite to the resin molded product, the pattern non-formed region where the first ink pattern (P ¹ ) is not formed and the surface of the resin molded product are formed. The color difference (ΔE _B ) and the pattern formation region where the first ink pattern (P ¹ ) is formed on the surface of the first porous separation layer (B ¹ ) opposite to the resin molded product and the pattern formation region. The labeled resin molded product according to any one of claims 4 to 6, wherein a difference (ΔE _B −ΔE _P ) with a color difference (ΔE _P ) from the surface of the resin molded product is 1 to 50. Wherein the first porous separating layer (B ¹⁾ in the resin molded article surface opposite of said first ink pattern (P ¹⁾ pattern formation region is formed between the first ink pattern (P ¹⁾ The labeled resin molded article according to any one of claims 4 to 7, wherein a color difference ΔE with respect to a pattern non-formation region in which is not formed is 3 or more. An ink pattern is formed on a surface of the second porous separation layer (B ² ) opposite to the base layer (A) and in a corresponding area (P′) having a mirror image relationship with the first ink pattern (P ¹ ). The resin-molded article with a label according to any one of claims 4 to 8 , wherein is not visually confirmed. The labeled resin molded article according to claim 9 , wherein the ink composition is present inside the voids of the corresponding region (P′). The labeled resin molded article according to claim 1, wherein the ink composition is a colored ink composition containing a coloring material. A notch having a depth of 1 cm was made from the end face of the porous layer (B) in a direction perpendicular to the end face, and the peeling margin and the resin molded product thus formed were pulled at an angle of 180° in a direction away from each other. When peeling the label from the molded product,
By allowing the ink composition to penetrate into the voids inside the base layer (A) from the release surface of the porous layer (B),
The first ink pattern (P ¹ ) of the ink composition appears on the surface of the first porous separation layer (B ¹ ) opposite to the resin molded product, and the first ink pattern (P ¹ ) is peeled off along with the base layer (A). The second ink pattern (P ² ) of the ink composition appears on the surface of the second porous separation layer (B ² ) opposite to the base layer (A), and the second ink pattern (P ² ) is visually observed. The resin molded product with a label according to claim 11, which can be confirmed. On the surface of the second porous separation layer (B ² ) opposite to the base layer, a pattern formation region in which the second ink pattern (P ² ) is formed, and the second ink pattern (P ² ). 13. The labeled resin molded product according to claim 12 , wherein a color difference ΔE with respect to a pattern non-formation region in which is not formed is 3 or more. The labeled resin molded article according to claim 12 or 13 , wherein the first ink pattern (P ¹ ) and the second ink pattern (P ² ) are in a mirror image relationship with each other. After the adhesive surface of the adhesive tape is attached to the surface of the second ink pattern (P ² ) on the surface of the second porous separation layer (B ² ), the adhesive tape is attached to the second porous separation layer (B 2 ). ² ) when peeled off at a peeling angle of 180° and a speed of 300 mm/min, the second ink pattern (P ² ) can be visually confirmed on the surface of the second porous separation layer (B ² ) and labeled resin molded article according to any one of claims 12 to 14 which the reverse pattern can be confirmed visually in the second ink pattern in the adhesive surface of the adhesive tape (P ^2). The first ink pattern (P ¹ ) is supplied with the ink composition on the surface of the porous layer (B) opposite to the base layer (A), and the ink composition of the porous layer (B) is supplied. The labeled resin molded article according to any one of claims 1 to 15, wherein the resin molded article is permeated into the voids. Said porous layer (B) Labeled resin molded article according to any one of claims 1-16 porosity observed from the thickness direction of the cross-section is 30 to 70 percent. It said porous layer (B) porosity observed in the thickness direction of the cross-section of, in any one of the base layer (A) in the thickness direction of the claim is greater than the porosity observed in cross section 1-17 Labeled resin molded product as described. The 180° peel strength according to JIS Z 1707:1997 General rules for plastic film for tableware packaging when peeling the label having the base layer (A) from the resin molded product is 0.3 to 1.6 N/15 mm. A resin molded product with a label according to any one of items 1 to 18 . A resin molded product and a first porous separation layer which remain after the base layer (A) and the second porous separation layer (B ² ) are peeled from the labeled resin molded product according to any one of claims 1 to 19. A resin molded product with a porous layer having (B ¹ ). The resin molded article and opposite surface of the first porous separation layer (B ^1), a porous layer with a resin molded article of claim 20 having a first ink pattern by the ink composition (P ¹⁾ .. A method of manufacturing a labeled resin molded article, comprising:
The labeled resin molded product has a resin molded product and a label attached to the resin molded product,
The label is present inside the base layer (A), the porous layer (B) provided on the base layer (A) and having a wall thickness of 0.1 to 20 μm, and the inside of the porous layer (B). A void and an ink composition present so as to occupy a part of the void,
The label is attached to the resin molded article on the surface of the porous layer (B) side,
A notch having a depth of 1 cm was made from the end face of the porous layer (B) in a direction perpendicular to the end face, and the peeling margin and the resin molded product thus formed were pulled at an angle of 180° in a direction away from each other. When the label is peeled off from the molded product, the porous layer (B) is accompanied by the first porous separation layer (B ¹ ) remaining attached to the resin molded product and the base layer (A). thereby separating the second porous separating layer to peel (B ^2), wherein the first porous separating layer (B ¹⁾ a first ink pattern by the above ink composition on the opposite side of the surface and the resin molded article of (P ¹ ) appears, and the first ink pattern (P ¹ ) can be visually confirmed,
The method for producing the labeled resin molded article is
A laminated resin film forming step of forming a laminated resin film having a base layer (A) and a porous layer (B) provided on the base layer;
A printing step of printing an ink composition on the surface of the laminated resin film opposite to the base layer (A) of the porous layer (B) to form an ink pattern to obtain a label;
The label on which the ink pattern is formed is inserted into the mold so that the base layer (A) side is the inner wall side of the mold and the porous layer (B) side is the cavity side so as to be in contact with the molten resin, A method for producing a labeled resin molded article, comprising a molding step of obtaining a labeled resin molded article by an in-mold molding method. The method for producing a resin molded article with a label layer according to claim 22 , wherein the ink composition is colorless and transparent. The method for producing a labeled resin molded article according to claim 22 , wherein a color difference ΔE _P0 between the first ink pattern (P ¹ ) and the surface of the resin molded article is less than 3. The method for producing a labeled resin molded article according to claim 22 , wherein the ink composition is colored, and the color difference ΔE ₀ between the first ink pattern (P ¹ ) and the porous layer (B) is 3 or more. .. The method for producing a labeled resin molded article according to any one of claims 22 to 25 , wherein the ink composition has a viscosity of 10 to 1500 mPa·s measured by a B-type viscometer according to JIS Z8803:2011. The method for producing a labeled resin molded product according to any one of claims 22 to 26 , wherein a flexographic printing method is used as a method for printing the ink composition in the printing step. The label according to any one of claims 22 to 27 , comprising a step of printing a heat-sealing resin composition on the surface of the porous layer on which the ink pattern is formed, between the printing step and the molding step. For manufacturing resin molded products with adhesive. 29. The method according to claim 22 , further comprising a step of applying a heat seal resin composition on a surface of the porous layer having the ink pattern formed between the printing step and the molding step. A method for producing a labeled resin molded product.