JP2021154616A - Laminate, label and printed matter - Google Patents

Abstract

To provide a laminate which can suppress peeling of a printing layer when a printed matter is cut by punching or the like.SOLUTION: A laminate has a sheet having a thermoplastic resin layer on one surface, and a resin-containing layer provided on a surface of the thermoplastic resin layer of the sheet, in which the resin-containing layer contains a thermoplastic resin covering the sheet, and indentation hardness of the sheet is more than 0 N/mm2 and 60 N/mm2 or less.SELECTED DRAWING: Figure 1

Description

The present invention relates to laminates, labels and printed matter.

Conventionally, printed matter having a print layer on a print medium has been widely used for outdoor advertisements, books, calendars, display labels, and the like.

When the print layer is provided on the print medium, a layer formed of thermoplastic resin particles may be provided on the surface of the print medium from the viewpoint of printability of the print medium (see Patent Document 1).

Japanese Unexamined Patent Publication No. 2011-116125

However, when a resin-containing layer formed of thermoplastic resin particles is provided on the surface of the thermoplastic resin layer contained in the printing medium, printing is performed in relation to the resin-containing layer and the printing layer provided on the surface of the resin-containing layer. Although the properties are improved, the present inventors have found a problem that the printed matter provided with the printed layer is peeled off when the printed matter is cut by punching or the like. It is considered that this is because the adhesion between the resin-containing layer and the thermoplastic resin layer that is the base of the resin-containing layer was not sufficient for stress in the thickness direction such as cutting.

Therefore, an object of the present invention is to provide a laminate capable of suppressing peeling of a printed matter when a printed matter is cut by punching or the like.

As a result of diligent studies to solve the above problems, the present inventors have determined the pressing hardness of a sheet having a thermoplastic resin layer on one surface, which is a base of a resin-containing layer containing a thermoplastic resin covering the sheet. We have found that the above problems can be solved by making adjustments, and have completed the present invention.
That is, the present invention is as follows.

[1] A laminate having a sheet having a thermoplastic resin layer on one surface and a resin-containing layer provided on the surface of the thermoplastic resin layer of the sheet.
The resin-containing layer contains a thermoplastic resin that covers the sheet.
The indentation hardness of the sheet is not more than 0N / mm ² Ultra-60N / mm ^2, laminate.
[2] The laminate according to the above [1], wherein the indentation hardness of the sheet is 0.1 N / mm ² or more and 60 N / mm ^{2 or less.}
[3] The laminate according to the above [1] or [2], wherein the indentation hardness of the sheet is 10 N / mm ² or more and 60 N / mm ^{2 or less.}
[4] The laminate according to any one of [1] to [3] above, wherein the thermoplastic resin in the resin-containing layer contains a polyurethane resin.
[5] The laminate according to any one of [1] to [4] above, wherein the thermoplastic resin layer contains random polypropylene.
[6] The laminate according to the above [5], wherein the random polypropylene has a tensile elastic modulus of 30 to 1200 N / mm ^2.
[7] The laminate according to the above [5] or [6], wherein the random polypropylene has a melting point of 100 to 145 ° C.
[8] The laminate according to any one of [5] to [7], wherein the content of the random polypropylene in the thermoplastic resin layer is 60% by mass or more.
[9] The laminate according to any one of [1] to [8] above, wherein the resin-containing layer contains functional particles.
[10] The laminate according to the above [9], wherein the functional particles contain particles having a cationic metal oxide.
[11] The laminate according to the above [9], wherein the functional particles contain olefin polymer particles.
[12] The laminate according to any one of [1] to [11], wherein the sheet has a base material layer and the thermoplastic resin layer provided on the surface of the base material layer.
[13] The laminate according to any one of the above [1] to [12] and
An adhesive layer provided on a surface of the laminate opposite to the resin-containing layer side,
Has a label.
[14] The laminate according to any one of the above [1] to [12] and
A printing layer provided on the surface of the resin-containing layer of the laminate, and
Have a printed matter.

According to the present invention, it is possible to provide a laminated body capable of suppressing peeling of a printed matter when a printed matter is cut by punching or the like.

It is sectional drawing which shows the structural example of the laminated body of this embodiment. It is sectional drawing which shows the other structural example of the laminated body of this embodiment. It is sectional drawing which shows the structural example of the printed matter of this embodiment. It is sectional drawing which shows the other structural example of the printed matter of this embodiment. It is sectional drawing which shows the other structural example of the printed matter of this embodiment. It is sectional drawing which shows the other structural example of the printed matter of this embodiment.

Hereinafter, the laminate and the printed matter of the present invention will be described in detail, but the description of the constituent requirements described below is an example (representative example) as an embodiment of the present invention, and is specified by these contents. It's not a thing. Further, the dimensional ratio in the drawings is not limited to the ratio shown in the drawing.

In this specification, for example, the notation of the numerical range of "1 to 100" includes both the lower limit value "1" and the upper limit value "100".
Moreover, the description of "(meth) acrylic" indicates both acrylic and methacryl.

(Laminated body)
The laminate of the present invention has a sheet and a resin-containing layer.
The sheet has a thermoplastic resin layer on one surface.
The resin-containing layer is provided on the surface of the thermoplastic resin layer of the sheet.
The resin-containing layer contains a thermoplastic resin that covers the sheet.
Sheet has a 0N / mm ² Ultra-60N / mm ² or less of indentation hardness.

The resin-containing layer can improve the wettability when forming the print layer, the adhesion between the print layer and the laminate, and the like. On the other hand, the resin-containing layer does not have sufficient adhesion to stress such as punching between the resin-containing layer and the underlying thermoplastic resin layer, and the printed layer may be peeled off.
Accordingly, the present inventors have made intensive studies, as a result, by the indentation hardness of the sheet having a thermoplastic resin layer serving as a base of the resin-containing layer on one surface and 0N / mm ² Ultra-60N / mm ² or less , It has been found that peeling of the printed layer when the printed matter is cut by punching or the like can be suppressed, and the present invention has been completed.

The laminate is used, for example, as printing paper, wrapping paper, wallpaper, and the like.

<Sheet>
The sheet has a thermoplastic resin layer on one surface.
The sheet, for example, imparts rigidity (stiffness) to the laminated body.

Indentation hardness of the sheet (HIT) is less 0N / mm ² Ultra-60N / mm ^2. The indentation hardness of the sheet is measured by a nanoindene test on the thermoplastic resin layer side (that is, the surface on which the resin-containing layer is provided) of the sheet, as shown in Examples described later. The nanoindenation test for measuring indentation hardness (HIT) is established by the international standard ISO14577. By providing a flexible thermoplastic resin layer having an indentation hardness of 60 N / mm ² or less on the surface of the sheet, the thermoplastic resin layer and the resin-containing layer provided on the surface of the thermoplastic resin layer It is considered that the stress generated at the interface between the two can be dispersed (relaxed) and a strong adhesive force can be imparted between the resin-containing layer and the thermoplastic resin layer. As a result, even when stress is applied to the laminated body from the outside due to punching or the like after printing, peeling of the printed layer can be suppressed. The above effect is thermoplastic resin is formed into a layer in the resin-containing layer, 0.05 g / m ² or more as a mass per unit area (further, 0.1 g / m ² or more) When the resin-containing layer is provided in Even so, you can get enough.

The smaller the pressing hardness of the sheet, the smaller the better, from the viewpoint of imparting a strong adhesive force between the resin-containing layer and the thermoplastic resin layer and suppressing peeling of the printed matter when the printed matter is cut by punching or the like. It is not particularly limited as long as it is 60 N / mm ^{2 or less, but 50 N / mm 2} or less is preferable. The indentation hardness of the sheet may be, for example, 0.1 N / mm ² or more, or 10 N / mm ² or more. From the viewpoint of suppressing the stickiness of the sheet, the pressing hardness of the sheet ^{is preferably 10 N / mm 2} or more.
Here, the stickiness of the sheet means the feeling of adhesion of the thermoplastic resin layer to the object. If the sheets are sticky, blocking between the sheets is likely to occur when the sheets are rolled up in a roll shape or the sheets are stacked and stored.

The sheet may have a one-layer structure, a two-layer structure, or a three-layer structure or more.
The sheet has, for example, a base material layer and a thermoplastic resin layer provided on the surface of the base material layer.
When the sheet has a structure of three or more layers having a base material layer, the layer structure on one surface side of the base material layer and the layer structure on the other surface side may have a symmetrical layer structure in the sheet. , It may have an asymmetric layer structure. For example, the sheet may have a thermoplastic resin layer on both sides of the base material layer. In this case, the two thermoplastic resin layers on both sides may have the same material, thickness, or the like, or may be different.

The thickness of the sheet is not particularly limited, but is preferably 20 μm or more, more preferably 40 μm or more, still more preferably 60 μm or more, from the viewpoint of ease of handling and prevention of wrinkles. On the other hand, from the viewpoint of ease of handling and productivity, 250 μm or less is preferable, and 200 μm or less is more preferable.
The thickness of the sheet is measured using a constant pressure thickness measuring device according to, for example, JISK7130: 1999.

<< Thermoplastic resin layer >>
The sheet has a thermoplastic resin layer on one surface.
The sheet may have a thermoplastic resin layer on both sides of the base material layer. In this case, the two thermoplastic resin layers on both sides may have the same material, thickness, or the like, or may be different.
The thermoplastic resin layer contains a thermoplastic resin.
The thermoplastic resin layer is composed of, for example, a thermoplastic resin. At that time, the thermoplastic resin is, for example, a matrix resin.
Sheet, if the both surfaces of the base layer has a thermoplastic resin layer, the indentation hardness of the sheet, meet 0N / mm ² Ultra-60N / mm ² or less at least one surface, 0N / mm in both It is preferable to satisfy more than ^{2 and} 60 N / mm ^{2 or less.}

The thermoplastic resin contained in the thermoplastic resin layer preferably contains a low-elasticity thermoplastic resin in order to obtain a flexible thermoplastic resin layer having a sheet pressing hardness of 60 N / mm ^{2 or less.} .. Examples of the low-elasticity thermoplastic resin include low-elasticity polyolefin-based resins. Even in the case of a polyolefin resin, the tensile elastic modulus varies depending on the type of olefin, molecular weight, degree of branching, crystallinity, copolymerization ratio, and the like. Therefore, it is preferable to select and use a polyolefin-based resin having low elasticity (that is, one having a low tensile elastic modulus).
Examples of the polyolefin-based resin include polyethylene-based resins, polypropylene-based resins, polybutenes, 4-methyl-1-pentene (co) polymers, and the like.
Examples of the polyethylene-based resin include low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, low-crystalline or amorphous ethylene / α-olefin copolymer, and ethylene-cyclic olefin. Examples include polymers.
Examples of the polypropylene-based resin include crystalline polypropylene, low crystalline polypropylene, amorphous polypropylene, propylene / ethylene copolymer (random copolymer or block copolymer), propylene / α-olefin copolymer, and Examples thereof include propylene / ethylene / α-olefin copolymers.
The propylene / α-olefin copolymer and the α-olefin constituting the propylene / ethylene / α-olefin copolymer are not particularly limited as long as they can be copolymerized with ethylene and propylene, for example, 1-. Examples thereof include butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene and the like.
Among these, random polypropylene is preferable from the viewpoint that a predetermined elastic modulus can be easily obtained and that a part of the thermoplastic resin layer is prevented from peeling off during sheet molding to contaminate the surface of the laminate. Random polypropylene is a random copolymer of propylene and ethylene, which is a kind of propylene / ethylene copolymer, and in the present specification, it refers to one having a molar ratio of propylene to all monomers of 0.5 or more. The propylene / ethylene copolymer may be a copolymer of propylene, ethylene, and another comonomer.

The tensile elastic modulus of the low-elasticity thermoplastic resin is not particularly limited, but is preferably 1200 MPa or less, more preferably 1150 MPa or less, and even more preferably 1100 MPa or less. When the tensile elastic modulus is 1200 MPa or less, the pressing hardness of the sheet surface can be reduced, and the peeling of the printed layer when the printed matter is cut by punching or the like tends to be further suppressed. On the other hand, when the tensile elastic modulus is 30 MPa or more, the stickiness of the sheet tends to be suppressed.
The tensile modulus can be determined in accordance with JIS K 7162.

The melting point of the low-elasticity thermoplastic resin is not particularly limited, but is preferably 160 ° C. or lower, more preferably 145 ° C. or lower, and even more preferably 140 ° C. or lower. When the melting point is equal to or lower than the above upper limit temperature, the amount of pores generated in the resin-containing layer tends to be reduced during stretching during the sheet manufacturing process. As a result, the smoothness of the sheet surface is improved, excellent cosmeticity is obtained, and dot skipping is less likely to occur in gravure printing. The melting point is preferably 60 ° C. or higher, more preferably 75 ° C. or higher, and even more preferably 90 ° C. or higher. When the melting point is 60 ° C. or higher, blocking can be easily prevented.
The melting point (melting temperature) can be determined in accordance with JIS K 7121: 1987.

The content of the low-elasticity thermoplastic resin in the thermoplastic resin layer depends on the tensile elastic modulus of the low-elasticity thermoplastic resin, but is preferably 40% by mass or more, more preferably 50% by mass or more, and 60% by mass. % Or more is more preferable. When the content is 40% by mass or more, the pressing hardness of the sheet surface tends to be lowered, and the peeling of the printed layer when the printed matter is cut by punching or the like tends to be further suppressed. The content of the low-elasticity thermoplastic resin in the thermoplastic resin layer may be 100% by mass or less than 100% by mass. For example, from the viewpoint of the balance with the shrinkage rate of other layers, the content may be 95% by mass or less, or 90% by mass or less.

When the low-elasticity thermoplastic resin is incompatible with the resin material contained in the layer adjacent to the thermoplastic resin layer, in the thermoplastic resin layer, the low-elasticity thermoplastic resin is a resin compatible with the resin material. It is preferably used with. For example, when a polypropylene-based resin is used for the base material layer and a polyethylene-based resin is selected as the low-elasticity thermoplastic resin constituting the thermoplastic resin layer, the polyethylene-based resin is used together with the polypropylene-based resin in the thermoplastic resin layer. It is preferable to be done.

The thermoplastic resin used for the thermoplastic resin layer may contain a thermoplastic resin other than the low-elasticity thermoplastic resin. Examples of such thermoplastic resins include olefin resins, polyester resins, polyamide resins, styrene resins, and polyphenylene sulfides.

The thermoplastic resin layer may or may not contain particles such as inorganic particles and organic particles, but is preferably contained. When the thermoplastic resin layer contains these particles, the surface is appropriately roughened by the pores and the particles, and the adhesion to the printing layer due to the anchoring effect is easily improved. When the thermoplastic resin layer contains particles, the content of the particles in the thermoplastic resin layer is, for example, 10 to 50% by mass. When the content is 50% by mass or less, the pressing hardness of the sheet is likely to be reduced.

The thickness of the thermoplastic resin layer is not particularly limited, but is preferably 1 μm or more, more preferably 1.5 μm or more, still more preferably 2 μm or more, from the viewpoint of easy control of the pressing hardness of the sheet. On the other hand, from the viewpoint of ease of handling, 10 μm or less is preferable, and 5 μm or less is more preferable.

<< Base material layer >>
The base material layer contains, for example, a thermoplastic resin. The base material layer may contain a filler or the like in addition to the thermoplastic resin.

<<< Thermoplastic Resin >>>
In the substrate layer, the thermoplastic resin is, for example, a matrix resin, which imparts mechanical strength to the sheet.
Examples of the thermoplastic resin contained in the base material layer include polyolefin-based resins such as polyethylene-based resins, polypropylene-based resins, polybutenes, and 4-methyl-1-pentene (co) polymers; ethylene-vinyl acetate copolymer. Combined, ethylene- (meth) acrylic acid copolymer, metal salt (ionomer) of ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid alkyl ester copolymer (alkyl group has 1 carbon number) ~ 8), functional group-containing olefinic resins such as maleic acid-modified polyethylene and maleic acid-modified polypropylene; aromatic polyesters (polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc.), and aliphatic polyesters. Polyester resins such as (polybutylene succinate, polylactic acid, etc.); polyamide resins such as nylon-6, nylon-6,6, nylon-6,10, and nylon-6,12; syndiotactic polystyrene, Styrene resins such as atactic polystyrene, acrylonitrile-styrene (AS) copolymer, styrene-butadiene (SBR) copolymer, and acrylonitrile-butadiene-styrene (ABS) copolymer; polyvinyl chloride resin; polycarbonate resin; In addition, polyphenylene sulfide and the like can be mentioned.

Examples of the polyethylene-based resin include low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, low-crystalline or amorphous ethylene / α-olefin copolymer, and ethylene-cyclic olefin. Examples include polymers.
Examples of the polypropylene-based resin include crystalline polypropylene, low crystalline polypropylene, amorphous polypropylene, propylene / ethylene copolymer (random copolymer or block copolymer), propylene / α-olefin copolymer, and the like. And propylene / ethylene / α-olefin copolymer, etc.) and the like.
The propylene / α-olefin copolymer and the α-olefin constituting the propylene / ethylene / α-olefin copolymer are not particularly limited as long as they can be copolymerized with ethylene and propylene. Examples thereof include −butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene and the like.
Among these thermoplastic resins, polyolefin-based resins are preferable in that water resistance and chemical resistance can be obtained at low cost, and polypropylene can give an appropriate rigidity as a printing medium to a laminate. A based resin is preferable.

The content of the thermoplastic resin in the base material layer is not particularly limited, but is preferably 20% by mass or more, more preferably 30% by mass or more, from the viewpoint of stretching stability and the like. On the other hand, from the viewpoint of obtaining opacity and whiteness as a print medium, 95% by mass or less is preferable, 90% by mass or less is more preferable, and 80% by mass or less is further preferable.

<<< Filler >>>
The filler contributes, for example, to the formation of pores when forming the substrate layer. By forming the pores in the base material layer, the laminate can obtain the desired whiteness and opacity. On the other hand, when producing a transparent laminate, the base material layer does not have to contain a filler.
Examples of the filler contained in the base material layer include an inorganic filler and an organic filler.

The average particle size of the filler is represented by the volume average particle size measured by the laser diffraction method, and the volume average particle size is 0.01 μm or more from the viewpoint of whitening and opaqueness of the base material layer by stretching. It is preferably 0.1 μm or more, more preferably 1 μm or more. On the other hand, the volume average particle size is preferably 15 μm or less, and more preferably 5 μm or less, from the viewpoint of improving the appearance of the surface of the laminate.

Inorganic fillers are preferred in that a large number of products with different particle sizes are commercially available at low cost. Examples of inorganic fillers include heavy calcium carbonate, light calcium carbonate, calcined clay, silica, silica soil, white clay, talc, titanium oxide, barium sulfate, alumina, zeolite, mica, sericite, bentonite, sepiolite, vermiculite, etc. Examples thereof include dolomite, wallastonite, and glass fiber, but the present invention is not particularly limited thereto. Of these, heavy calcium carbonate, light calcium carbonate, and titanium oxide are preferable, and heavy calcium carbonate is more preferable, from the viewpoint of pore forming property and cost.
These inorganic fillers can be used alone or in combination of two or more.

The content of the filler in the base material layer is not particularly limited, but is preferably 2% by mass or more, more preferably 4% by mass or more, and 10% by mass or more from the viewpoint of forming sufficient pores in the base material layer. More preferably, 14% by mass or more is particularly preferable. On the other hand, from the viewpoint of suppressing a decrease in the strength of the base material layer, the content is preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 30% by mass or less, and particularly preferably 25% by mass or less. When producing a transparent laminate, the content may be less than 2% by mass.

The thickness of the base material layer is not particularly limited, but is preferably 20 μm or more, more preferably 40 μm or more, still more preferably 60 μm or more, from the viewpoint of imparting appropriate rigidity to the laminated body. On the other hand, from the viewpoint of manufacturing cost and the like, 250 μm or less is preferable, and 200 μm or less is more preferable.

<< Sheet manufacturing method >>
The method for manufacturing the sheet is not particularly limited. For example, a thermoplastic resin layer using cast molding, calender molding, rolling molding, inflation molding, etc., in which molten resin is extruded into a sheet by a single-layer or multi-layer T-die or I-die connected to a screw-type extruder. The base material layer can be molded. Further, the thermoplastic resin layer and the base material layer may be formed by using a method of cast molding or calendar molding a mixture of a thermoplastic resin and an organic solvent or oil and then removing the solvent or oil.

The sheet may be a stretched sheet or an unstretched sheet.
The method for stretching the sheet is not particularly limited, and is, for example, vertical (MD) stretching using the peripheral speed difference of the roll group, horizontal (TD) stretching using a tenter oven, rolling, or a combination of a tenter oven and a linear motor. Simultaneous biaxial stretching, simultaneous biaxial stretching by a combination of a tenter and a pantograph, a combination thereof, and the like can be mentioned.

When the sheet has a multi-layer structure, the number of stretches and the stretch direction of each layer may be the same or different. For example, when the sheet has a base material layer and a thermoplastic resin layer, the vertically stretched base material layer and the non-stretched thermoplastic resin layer may be overlapped and horizontally stretched to produce the sheet. In this case, the base material layer is a biaxially stretched layer stretched in the vertical and horizontal directions, and the thermoplastic resin layer is a uniaxially stretched layer stretched in the horizontal direction.

Stretching of each layer of the sheet is preferably carried out within a temperature range suitable for the thermoplastic resin contained in each layer. When the thermoplastic resin used for each layer is a non-crystalline resin, the stretching temperature of each layer is preferably in a range equal to or higher than the glass transition temperature of the thermoplastic resin. When the thermoplastic resin used for each layer is a crystalline resin, it is at least the glass transition point of the amorphous portion of the thermoplastic resin and within the range below the melting point of the crystalline portion of the thermoplastic resin. Is preferable. Specifically, the stretching temperature of each layer is preferably 2 to 60 ° C. lower than the melting point of the thermoplastic resin used for each layer.

When the thermoplastic resin used for each layer is a homopolymer of propylene (melting point 155 to 167 ° C.), the stretching temperature of each layer is preferably in the range of 152 to 164 ° C. When the thermoplastic resin used for each layer is high-density polyethylene (melting point 121 to 134 ° C.), the stretching temperature of each layer is preferably in the range of 110 to 120 ° C. When the thermoplastic resin used for each layer is polyethylene terephthalate (melting point 246 to 252 ° C.), the stretching temperature of each layer is preferably in the range of 104 to 115 ° C.

The stretching speed is not particularly limited, but is preferably in the range of 20 to 350 m / min. The draw ratio is not particularly limited, and is appropriately determined in consideration of the characteristics of the thermoplastic resin used for each layer. For example, when the thermoplastic resin used for each layer is a homopolymer of propylene or a copolymer thereof, the draw ratio when stretched in one direction is preferably about 1.2 to 12 times, and 2 to 10 times. Double is more preferable. In the case of biaxial stretching, the stretching ratio is preferably 1.5 to 60 times, more preferably 10 to 50 times in terms of area magnification. When a thermoplastic resin other than the above is used, the draw ratio when stretching in one direction is preferably 1.2 to 10 times, more preferably 2 to 5 times. In the case of biaxial stretching, the stretching ratio is preferably 1.5 to 20 times, more preferably 4 to 12 times in terms of area magnification.

<Resin-containing layer>
The resin-containing layer contains a thermoplastic resin that covers the sheet.
The resin-containing layer further contains, for example, functional particles, a water-soluble polymer, and the like.
In the laminated body, the resin-containing layer is provided on the surface of the thermoplastic resin layer of the sheet.

<< Thermoplastic resin >>
The thermoplastic resin is, for example, a matrix resin constituting a resin-containing layer.
The thermoplastic resin is present in, for example, a layered resin-containing layer and covers the sheet. By covering the sheet with the thermoplastic resin, water resistance can be easily obtained, but the printed matter is easily peeled off when the printed matter is cut by punching or the like. Therefore, the present invention solves the problem.
The thermoplastic resin is, for example, a fusion product of thermoplastic resin particles. The fused product of the thermoplastic resin particles is a fused product of the thermoplastic resin particles by heating. Fusion occurs, for example, by heating when forming the resin-containing layer. As a result, the thermoplastic resin is formed in layers, and water resistance can be easily obtained. In addition, the functional particles are taken into the thermoplastic resin formed in layers and fixed to the laminate, so that the functions of the functional particles can be easily exhibited. In the fused product, the interface between the thermoplastic resin particles may disappear, or the interface may remain as long as the effect of the present invention is not impaired.

When it is desired to fuse the thermoplastic resin particles, the minimum film forming temperature of the thermoplastic resin particles is not particularly limited, but is preferably 40 ° C. or lower. When the minimum film-forming temperature is 40 ° C. or lower, the thermoplastic resin particles are easily fused by heating when forming the resin-containing layer. The lower limit of the minimum film forming temperature is not particularly limited, but may be, for example, −10 ° C. or higher.

Examples of the thermoplastic resin constituting the resin-containing layer include vinyl-based resins and polyurethane resins.

The vinyl-based monomer constituting the vinyl-based resin may have, for example, olefins; vinyl esters; unsaturated carboxylic acids and alkali metal salts or acid anhydrides thereof; branched or cyclic structures having up to 12 carbon atoms. An ester of an alkyl group; one or more selected from the group consisting of (meth) acrylamide, a derivative having an alkyl group having 1 to 4 carbon atoms and an alkylene group having 1 or 2 carbon atoms at the same time; and a dimethyldiallyl ammonium salt. You can. The above salt is an acid residue, and the acid ion is preferably methyl sulfate ion or chloride ion.

Examples of olefins include ethylene, propylene, 1-butene, butadiene and the like.
Examples of vinyl esters include vinyl acetate and the like.
Examples of unsaturated carboxylic acids include (meth) acrylic acid and maleic acid.
Examples of the derivative having (meth) acrylamide, an alkyl group having 1 to 4 carbon atoms and an alkylene group having 1 or 2 carbon atoms at the same time include N-alkylaminoalkylene (meth) acrylate and N-alkylaminoalkylene (meth) acrylamide. , N, N-dialkylaminoalkylene (meth) acrylate, N, N-dialkylaminoalkylene (meth) acrylamide, (meth) acryloyloxyalkylene trialkylammonium salt, (meth) acryloylaminoalkylene trialkylammonium salt and the like. Be done.

In order to obtain a copolymer having a quaternary ammonium salt structure in the molecule as a vinyl resin, a monomer having a quaternary ammonium salt structure may be directly copolymerized as an essential component from the above. After obtaining a copolymer using a monomer having a tertiary amine structure as an essential component, the tertiary amine is quaternized with dimethyl sulfate, 3-chloro-2-hydroxypropyltrimethylammonium chloride, glycidyltrimethylammonium chloride and the like. It may be quaternized with an agent, or a monomer having a quaternary ammonium salt structure may be grafted after obtaining a copolymer using only a monomer containing no nitrogen.

The polyurethane resin may be a cationic polyurethane resin. The cationic polyurethane resin is a copolymer in which a cationic group is introduced into the polyurethane resin skeleton. The copolymer is, for example, a urethane resin obtained by reacting a tertiary amino group-containing polyol obtained by reacting a compound having two epoxy groups in one molecule with a secondary amine with polyisocyanate. It is obtained by quaternizing with a classifying agent. In addition, the copolymer includes N, N-dialkyl alkanolamines as a part of the polyol; N-alkyl-N, N- such as N-methyl-N, N-diethanolamine, N-butyl-N, N-diethanolamine and the like. A urethane resin obtained by reacting with polyisocyanate by adding one or more selected from the group consisting of dialkanolamines; and trialkanolamines is quaternized with the quaternizing agent. May be good.

For example, when forming the resin-containing layer, the thermoplastic resin is used in the form of an emulsion of thermoplastic resin particles. As a method of obtaining an emulsion, a method of emulsifying and dispersing a monomer constituting the target polymer in water to polymerize it, and a method of obtaining the target polymer by bulk polymerization or the like, and then using a twin-screw extruder as a raw material. Examples thereof include a method in which the resin is melt-kneaded and emulsified in sequence. The amount of cations introduced into a vinyl resin having a quaternary ammonium salt structure in the molecule or a copolymer in which a cationic hydrophilic group is introduced into a polyurethane resin skeleton is, for example, potassium polyvinyl sulfate of a thermoplastic resin. Evaluate by the colloid equivalent obtained by the colloidal titration method using a solution. In order for the particles having the metal oxide to be dispersed and stably exist in the coating agent for forming the resin-containing layer, the colloid equivalent of the thermoplastic resin particles is preferably 0.2 meq / g or more, preferably 0.6 meq. / G or more is more preferable, and 1.0 meq / g or more is further preferable. On the other hand, if the cation equivalent of a vinyl resin having a quaternary ammonium salt structure in the molecule or a copolymer in which a cationic hydrophilic group is introduced into a polyurethane resin skeleton is too high, the resin-containing layer is redissolved in water. The rate tends to rise. Therefore, the cation equivalent of the thermoplastic resin is preferably 5 meq / g or less, more preferably 4 meq / g or less, and even more preferably 3 meq / g.

The softening point of the thermoplastic resin constituting the resin-containing layer is not particularly limited, but may be 30 ° C. or higher, or 50 ° C. or higher, from the viewpoint of suppressing blocking. On the other hand, the softening point is preferably 300 ° C. or lower.
The softening point can be measured by a high-grade flow tester.

The content of the thermoplastic resin in the resin-containing layer is not particularly limited, but is preferably 15% by mass or more, and more preferably 30% by mass or more. When the content is 15% by mass or more, the printability is improved. On the other hand, the content of the thermoplastic resin in the resin-containing layer is preferably 65% by mass or less, more preferably 60% by mass or less. When the content is 65% by mass or less, antistatic properties are likely to be exhibited.
The content here means the content of all the thermoplastic resins in the resin-containing layer. For example, when a fused product of thermoplastic resin particles and particulate thermoplastic particles coexist in the resin-containing layer, the content here is the total content thereof.

<< Functional particles >>
The functional particles are inorganic particles or organic particles capable of imparting various functions to the surface of the laminate.
Examples of the function include an antistatic function, a printability improving function, a blocking prevention function, and the like.
The functional particles are fixed to the resin-containing layer by the thermoplastic resin constituting the resin-containing layer. The functional particles are distributed in, for example, the thermoplastic resin constituting the resin-containing layer. The functional particles may be embedded in the layered thermoplastic resin constituting the resin-containing layer, or may be exposed on the surface of the layered thermoplastic resin constituting the resin-containing layer.

Examples of the functional particles having an antistatic function include particles having a metal oxide.
Examples of the particles having a metal oxide include cationic compound particles and cationic compound coated particles.
Examples of the particles having a metal oxide include inorganic particles having a layer of a metal oxide on the surface and metal oxide particles.

The inorganic particles having a metal oxide layer on the surface may be colloidal silica particles having a metal oxide layer on the surface of colloidal silica. When forming the resin-containing layer, the colloidal silica particles are used, for example, in the state of a sol containing the colloidal silica particles (hereinafter, may be referred to as "coloidal silica sol"). The method for producing the colloidal silica sol is not particularly limited, but an alkali metal silicate aqueous solution (for example, water glass) is used as a raw material, and the alkali metal salt is removed by an ion exchange resin or an electrophoresis method to obtain an anhydrous silicate sol. Further, a method of adding an acid or an alkali to adjust and stabilize the pH, a method of hydrolyzing an alkoxide such as tetraethoxydo orthosilicate (TEOS) with an acid or an alkali (so-called sol-gel method), and an organic substance such as silicon tetrachloride. Examples thereof include a method of introducing a silicon compound into a flame such as hydrogen to synthesize it (so-called vapor phase method).

The colloidal silica sol may be a cationic colloidal silica sol or an anionic colloidal silica. The colloidal silica sol may be a cationic compound-coated colloidal silica sol in which the surface of the anionic colloidal silica is coated with a cationic compound. The cationic compound-coated colloidal silica sol may be a metal oxide-coated colloidal silica sol in which the surface of the anionic colloidal silica is coated with a metal oxide. The cationic compound-coated colloidal silica sol can be obtained, for example, by adding a cationic compound or a precursor thereof to the colloidal silica sol in the steps after the dispersion step of dispersing silica in a dispersion medium. The metal oxide-coated colloidal silica sol can be obtained, for example, by adding a metal oxide or a precursor thereof to the colloidal silica sol in the steps after the silica dispersion step. For example, by treating the surface of colloidal silica by adding an aluminum water-soluble salt to colloidal silica sol, an alumina-coated colloidal silica sol can be obtained. By using the cationic alumina-coated colloidal silica particles as the particles having the metal oxide, the antistatic property and the printability are improved as compared with the case where the anionic colloidal silica particles are used.

The colloidal silica particles contained in the colloidal silica sol may have a silanol group (≡Si—OH) on the surface. Moreover, the above-mentioned particles may be monodisperse particles. The CV value (Coefficient of Variation) [%] of the above particles is preferably 15% or less, more preferably 10% or less, still more preferably 5% or less. The above particles may be in the form of long chains.

Examples of the metal oxide particles include hafnium oxide particles, zirconium oxide particles, zinc oxide particles, titanium oxide particles, yttrium oxide particles, aluminum oxide particles, copper oxide particles, germanium oxide particles, tungsten oxide particles, indium oxide particles, and the like. Examples include tin oxide particles.
When forming the resin-containing layer, these metal oxide particles may be used, for example, in the state of a sol (hereinafter, may be referred to as “metal oxide sol”).
Examples of the metal oxide sol include hafnium oxide sol, zirconium oxide sol, zinc oxide sol, titanium oxide sol, yttrium oxide sol, aluminum oxide sol, copper oxide sol, germanium oxide sol, tungsten oxide sol, indium oxide sol, and oxidation. Examples include tin sol. For example, as a method for producing aluminum oxide sol, a method for producing aluminum alkoxide such as aluminum isopropoxide by hydrolyzing with an acid, and a method for introducing aluminum chloride into a flame such as hydrogen for synthesis (so-called ki). Phase method) and the like.

The metal oxide particles contained in the metal oxide sol may be monodisperse particles. The CV value (Coefficient of Variation) [%] of the above particles is preferably 15% or less, more preferably 10% or less, still more preferably 5% or less. The above particles may be in the form of long chains.

The colloidal silica particles having a metal oxide layer on the surface of the colloidal silica and the metal oxide used for the metal oxide particles preferably contain at least one metal selected from aluminum, zinc, tin, and indium, and aluminum. It is more preferable to include. The metal oxide may be alumina. When the metal oxide is alumina, the colloidal silica particles having a layer of the metal oxide on the surface of the colloidal silica and the surface of the metal oxide particles become cationic, and the antistatic property, printability and the like are improved.

The average primary particle size of the particles having a metal oxide is preferably 200 nm or less, more preferably 100 nm or less, still more preferably 25 nm or less. When the average particle size of the particles having the metal oxide is 200 nm or less, the surface glossiness of the resin-containing layer is likely to be exhibited, and the antistatic property of the resin-containing layer is likely to be exhibited. In addition, the strength of the resin-containing layer is further improved. On the other hand, the average primary particle size of the particles having a metal oxide is preferably 1 nm or more, more preferably 4 nm or more, still more preferably 7 nm or more. When the average primary particle size is 1 nm or more, the production of particles becomes easier. The average primary particle diameter of the above particles is calculated as an average value of the area equivalent circle diameters of the particles observed using a transmission electron microscope (TEM).

The content of the functional particles having an antistatic function in the resin-containing layer is not particularly limited, but is preferably 85% by mass or less, and more preferably 70% by mass or less. When the content of the functional particles having an antistatic function is 85% by mass or less, the printability is further improved. For the same reason, the ratio of the mass of the functional particles having an antistatic function in the coating liquid for forming the resin-containing layer to the mass of the thermoplastic resin (particles having a metal oxide: thermoplastic resin). Is preferably 30:70 to 85:15, more preferably 40:60 to 85:15, and even more preferably 40:60 to 70:30.

Examples of the functional particles having a printability improving function include olefin-based polymer particles. The olefin-based polymer particles exhibit hydrophobicity in the resin-containing layer and prevent excessive water from being absorbed into the resin-containing layer. By doing so, it is presumed that water loss during offset printing is suppressed. Further, it is presumed that it contributes to the stability of the printed matter over time for the same reason. On the other hand, in a printing method using heating such as a molten thermal transfer printing method and an electrophotographic printing method, some of the olefin-based copolymer particles existing on the surface of the laminate are melted at the time of printing and are phased with the molten thermal transfer ink or toner. It is presumed that the molten thermal transfer ink or toner is fixed by melting.

Examples of the olefins constituting the olefin-based polymer particles include ethylene, propylene, 1-butene, and butadiene.
The olefin-based polymer particles may be homopolymers of these olefins or copolymers.

When forming the resin-containing layer, the olefin-based polymer particles are preferably used in an emulsion state. As a result, particles having a metal oxide, which will be described later, can be adhered and solidified on the surface of the resin-containing layer. For the same reason, the weight average molecular weight of the olefin polymer particles is preferably 1000 or more, more preferably 3000 or more, and even more preferably 5000 or more.

Fused particles as described above for thermoplastic resin particles are excluded from the functional particles. Therefore, the minimum film-forming temperature of the organic particles as the functional particles is not particularly limited, but may be more than 40 ° C., 60 ° C. or higher, or 80 ° C. or higher. ..

Examples of the functional particles having a blocking prevention function include silica and calcium carbonate. In order to have the blocking prevention function, the average particle size of the functional particles is preferably 5 μm or more, more preferably 7 μm or more.

<< Water-soluble polymer >>
Examples of the water-soluble polymer include vinyl-based copolymers such as polyvinylpyrrolidone; partially saponified polyvinyl alcohol (hereinafter, may be referred to as “PVA”), fully saponified PVA, and isobutylene-maleic anhydride copolymer. Vinyl copolymer hydrolyzate such as alkali metal salt or ammonium salt; sodium poly (meth) acrylate and (meth) acrylic acid derivative such as poly (meth) acrylamide; modified polyamide; carboxymethyl cellulose, and carboxyethyl cellulose. Such as cellulose derivatives; ring-opening polymerization polymers such as polyethyleneimine, polyethylene oxide, and polyethylene glycol or modified products thereof; natural polymers such as gelatin and starch, or modified products thereof. Among these, it is preferable to use partially saponified PVA, fully saponified PVA, polyethyleneimine, and modified polyethyleneimine.

In the structure of the resin-containing layer, the water-soluble polymer is not included in the thermoplastic resin.

The water-soluble polymer dissolves in water in the coating agent for forming the resin-containing layer, the coating agent is applied to the surface of the thermoplastic resin layer in the sheet, and after drying, it is redissolved in water. It is preferable to have a property that does not.

When the resin-containing layer contains a water-soluble polymer, the content of the water-soluble polymer is not particularly limited, but from the viewpoint of adhesion between the thermoplastic resin and the functional particles in the resin-containing layer, the thermoplastic resin and the resin-containing layer are used. 5 parts by mass or more is preferable, 10 parts by mass or more is more preferable, and 20 parts by mass or more is further preferable with respect to 100 parts by mass in total with the functional particles. On the other hand, from the viewpoint of printability, processability and the like, the content is preferably 200 parts by mass or less, more preferably 150 parts by mass or less, based on 100 parts by mass of the total of the thermoplastic resin and the functional particles.

The thickness of the resin-containing layer is evaluated as the mass per unit area. The thickness of the resin-containing layer is not particularly limited, but is preferably ^{20 g / m 2} or less, more preferably ^{10 g / m 2} or less, from the viewpoint of further suppressing peeling of the printed matter when the printed matter is cut by punching or the like. 1 g / m ² or less is more preferable. Meanwhile, thickness, from the viewpoint of printability such as, 0.01 g / ^{m 2} or more preferably, 0.05 g / ^{m 2} or more preferably, 0.1 g / ^{m 2} or more is more preferable.

<< Method of forming resin-containing layer >>
The method for forming the resin-containing layer is not particularly limited, but a method in which a coating agent is applied to the surface of the thermoplastic resin layer in the sheet and dried is preferable because the compounding and forming methods are easy.
The coating agent contains, for example, thermoplastic resin particles and water. The coating agent may contain functional particles. For example, some or all of the thermoplastic resin particles are fused by being heated to a minimum film forming temperature or higher after coating.

In the coating agent manufacturing process, for example, when the solid concentration of the particles having a metal oxide and the olefin-based polymer particles is high, when the pH of the coating agent is near the isoelectric point of the olefin-based polymer particles, the metal Metal oxidation when the zeta potentials of the oxide-bearing particles and the olefin-based polymer particles are inversely related, or when a highly valence ionic substance (particularly, a polymer having a functional group) is added. At least one of the particles having a substance and the olefin polymer particles may agglomerate. Therefore, in the manufacturing process of the coating agent, each material is sequentially added to the diluted water, and the order and speed of addition are appropriately adjusted so that the concentration of each material does not increase locally. Is preferable. Further, in the manufacturing process of the coating agent, the pH of the coating agent may be adjusted or a dispersant may be added to increase the repulsive force between the particles. As a result, aggregation can be suppressed.

The solid content concentration of the coating agent can be appropriately adjusted according to the amount of the resin-containing layer applied after drying and the coating method of the coating agent, but is preferably 0.5% by mass or more, more preferably 3% by mass or more. .. Further, 35% by mass or less is preferable, 20% by mass or less is more preferable, and 15% by mass or less is further preferable. The pH of the coating agent needs to be such that each material contained in the coating agent does not agglomerate, but from the viewpoint of worker safety and prevention of machine corrosion, the pH is preferably pH 3 to 11. 10 is more preferable.

FIG. 1 shows a configuration example of a laminated body 1a as an embodiment of the present invention.
As shown in FIG. 1, the laminated body 1a has a sheet 2a and a resin-containing layer 5. The sheet 2a has a thermoplastic resin layer 4 on one surface. The sheet 2a further has a base material layer 3. The resin-containing layer 5 is provided on the surface of the thermoplastic resin layer 4 of the sheet 2a.
As measured by nano indendation test for the thermoplastic resin layer 4 side of the seat 2a, indentation hardness of the sheet 2a is 0N / mm ² Ultra-60N / mm ^2.

FIG. 2 shows a configuration example of the laminated body 1b as another embodiment of the present invention.
As shown in FIG. 2, the laminate 1b has a sheet 2b, a resin-containing layer 5, and a resin-containing layer 7. The sheet 2b has a thermoplastic resin layer 4 on one surface and a thermoplastic resin layer 6 on the other surface. The sheet 2b further has a base material layer 3 between the thermoplastic resin layer 4 and the thermoplastic resin layer 6. The resin-containing layer 5 is provided on the surface of the thermoplastic resin layer 4 of the sheet 2b. The resin-containing layer 7 is provided on the surface of the thermoplastic resin layer 6 of the sheet 2b.
As measured by nano indendation test for the thermoplastic resin layer 4 side of the seat 2b, indentation hardness of the sheet 2b is 0N / mm ² Ultra-60N / mm ^2.
As measured by nano indendation test for the thermoplastic resin layer 6 side of the seat 2b, indentation hardness of the sheet 2b is not particularly limited, it is preferable that 0N / mm ² Ultra-60N / mm ^2.

(label)
The label has an adhesive layer on one side of the laminate. The adhesive layer may be an adhesive layer having adhesiveness at room temperature, or may be a heat seal layer activated by heating. If the label has an adhesive layer, the label is an adhesive label. If the label has a heat seal layer, the label is a heat sensitive label.
For example, the label has an adhesive layer on the surface of the laminate opposite to the resin-containing layer side.

The adhesive layer is not particularly limited. Regarding the materials and compositions used for the adhesive layer, for example, the adhesive polymer described in JP-A-2002-169470, the adhesive polymer crosslinked by a cross-linking agent, and the removable adhesive described in JP-A-9-197972. Materials used in the agent layer, the pressure-sensitive adhesive layer described in JP-A-2004-216908, the pressure-sensitive adhesive layer described in JP-A-2009-275231, and the pressure-sensitive adhesive composition described in JP-A-2014-012808. And composition can be used as appropriate.

The adhesive layer is formed, for example, by applying a coating liquid having the above materials or compositions onto the laminate. The adhesive layer is provided on one surface of the laminate. When the laminate has a resin-containing layer on only one surface, the adhesive layer is preferably provided on the other surface of the laminate.
The thickness of the adhesive layer is, for example, ^{preferably 3 g / m 2} or more, and more preferably 10 g / m ² or more in terms of solid content. The thickness of the adhesive layer ^{is preferably 60 g / m 2} or less, and ^{more preferably 40 g / m 2} or less in terms of solid content.

The heat seal layer has a heat seal resin. The melting point of the heat-sealing resin is preferably 10 ° C. or higher, more preferably 15 ° C. or higher, lower than the melting point of the thermoplastic resin in the base material layer. The melting point of the heat-sealing resin is preferably 60 ° C. or higher, more preferably 70 ° C. or higher.

Examples of the heat-sealable resin include polyethylene, an ethylene-based copolymer, a propylene-based copolymer, a polyester-based copolymer, a styrene-based elastomer resin, and a polyamide-based copolymer. The heat-sealing layer may further contain additives such as dyes, nucleating agents, plasticizers, mold release agents, flame retardants, antioxidants, light stabilizers, and ultraviolet absorbers, as long as the heat-sealing properties are not impaired. ..

As a method for forming the heat seal layer, cast molding, calendar molding, rolling molding, inflation molding, etc., in which the molten resin is extruded into a sheet by a single-layer or multi-layer T-die or I-die connected to a screw type extruder, etc. are used. Can be mentioned. The heat seal layer is provided on one surface of the laminate. When the laminate has a resin-containing layer on only one surface, the heat seal layer is preferably provided on the other surface of the laminate.
The thickness of the heat seal layer is preferably 1.0 μm or more, and more preferably 2.0 μm or more. The thickness of the heat seal layer is preferably 10 μm or less, more preferably 5.0 μm or less.

(Printed matter)
The printed matter of the present invention has a laminated body of the present invention and a printed layer provided on the surface of the resin-containing layer of the laminated body. The printed matter may have a printed layer on one side or both sides. Further, the printed matter may be a printed label having an adhesive layer.

The printing layer is a layer formed by printing characters, borders, patterns, and the like.
The printing layer may be provided on the entire surface of the resin-containing layer, or may be provided on a part of the surface.

The printing method that is the method for forming the print layer is not particularly limited, and known printing methods such as gravure printing, offset printing, flexographic printing, sticker printing, and screen printing can be used. The printing layer may also include printing by various printers such as an inkjet method, an electrophotographic method, and a liquid toner method, foil stamping such as hot stamping and cold stamping, and conventionally known decorations such as transfer foil and hologram.

For printing, various inks such as oil-based ink, oxidative polymerization curable ink, ultraviolet curable ink, water-based ink, powder toner, and liquid toner (electro ink) can be used according to the printing method.

The printed matter may further have a release layer provided on the surface of the adhesive layer.
The release layer is not particularly limited, but for example, high-quality paper or kraft paper is used as it is, or high-quality paper or kraft paper is subjected to calendar processing, resin coating, film lamination, glassin paper, coated paper, plastic film, or the like. Those that have been subjected to silicone treatment can be used.

FIG. 3 shows a configuration example of the printed matter 10a as an embodiment of the present invention.
As shown in FIG. 3, the printed matter 10a has a laminate 1a and a printed layer 8. The laminated body 1a is the laminated body 1a shown in FIG. In the printed matter 10a, the printed layer 8 is provided on the surface of the resin-containing layer 5 of the laminated body 1a.

FIG. 4 shows a configuration example of the printed matter 10b as another embodiment of the present invention.
As shown in FIG. 4, the printed matter 10b has a laminated body 1a, a printed layer 8, and an adhesive layer 11. The laminated body 1a is the laminated body 1a shown in FIG. The printing layer 8 is provided on the surface of the resin-containing layer 5 of the laminated body 1a. The adhesive layer 11 is provided on the surface of the base material layer 3 of the laminated body 1a.

FIG. 5 shows a configuration example of the printed matter 10c as another embodiment of the present invention.
As shown in FIG. 5, the printed matter 10c has a laminate 1b, a print layer 8, and a print layer 9. The laminated body 1b is the laminated body 1b shown in FIG. The printing layer 8 is provided on the surface of the resin-containing layer 5 of the laminated body 1b. The printing layer 9 is provided on the surface of the resin-containing layer 7 of the laminated body 1b.

FIG. 6 shows a configuration example of the printed matter 10d as another embodiment of the present invention.
As shown in FIG. 6, the printed matter 10d has a laminate 1b, a printing layer 8, and an adhesive layer 11. The laminated body 1b is the laminated body 1b shown in FIG. The printing layer 8 is provided on the surface of the resin-containing layer 5 of the laminated body 1b. The adhesive layer 11 is provided on the surface of the resin-containing layer 7 of the laminated body 1b.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples as long as the gist of the present invention is not exceeded. In addition, the description of "part", "%", etc. in the Examples means the description of the mass standard unless otherwise specified.

(Preparation of coating agent for resin-containing layer)
A coating agent for a resin-containing layer was prepared using the raw materials shown in Table 1 below.

<Production Example 1-1: Coating Agent No. for Resin-Containing Layer 1>
3.0 parts by mass of the water-soluble polymer shown in Table 1 and 100 parts by mass of water were mixed and stirred for 5 minutes. Then, using 10% concentration of acetic acid, the pH was adjusted so that the pH of the mixture of the water-soluble polymer and water was 5.0.
Next, in the mixed solution obtained by adjusting the pH, the functional particles A shown in Table 1 [manufactured by Nissan Chemical Industry Co., Ltd., trade name: Snowtex ST-AK, alumina surface treatment with an average particle size of 15 nm Colloidal silica, solid content concentration 19%] 52.9 parts by mass, and thermoplastic resin particles A [manufactured by DIC Co., Ltd., product name: Hydran CP7050, urethane emulsion with an average particle size of 75 nm, minimum film formation Temperature: 0 ° C., solid content concentration 25%] 30.6 parts by mass was added, and the mixture was stirred for 5 minutes. As a result, the coating agent No. for the resin-containing layer becomes No. I got 1.
The obtained coating agent No. Table 2 shows the solid content ratio of each raw material in 1.

<Production Example 1-2: Coating Agent No. for Resin-Containing Layer 2>
2.7 parts by mass of the water-soluble polymer shown in Table 1 and 100 parts by mass of water were mixed and stirred for 5 minutes. Then, using 10% concentration of acetic acid, the pH was adjusted so that the pH of the mixture of the water-soluble polymer and water was 5.0.
Next, in the mixed solution obtained by adjusting the pH, 47.5 parts by mass of the functional particles A shown in Table 1 and the thermoplastic resin particles B [manufactured by DIC Co., Ltd., trade name] shown in Table 1 were added. : Boncoat VO8, acrylic emulsion with an average particle size of 300 nm, minimum film forming temperature 25 ° C., solid content concentration: 40%)] 17.2 parts by mass was added, and the mixture was stirred for 5 minutes. As a result, the coating agent No. for the resin-containing layer becomes No. I got 2.
The obtained coating agent No. Table 2 shows the solid content ratio of each raw material in 2.

<Production Example 1-3: Coating Agent No. for Resin-Containing Layer 3>
2.8 parts by mass of the water-soluble polymer shown in Table 1 and 100 parts by mass of water were mixed and stirred for 5 minutes. Then, using 10% concentration of acetic acid, the pH was adjusted so that the pH of the mixture of the water-soluble polymer and water was 5.0.
Next, in the mixed solution obtained by adjusting the pH, the functional particles B shown in Table 1 [manufactured by Nissan Chemical Industries, Ltd., trade name: alumina sol 520, alumina sol with an average particle size of 20 nm, solid content concentration 22 %] 42.6 parts by mass and 28.5 parts by mass of the thermoplastic resin particles A shown in Table 1 were added, and the mixture was stirred for 5 minutes. As a result, the coating agent No. for the resin-containing layer becomes No. I got 3.
The obtained coating agent No. Table 2 shows the solid content ratio of each raw material in 3.

<Production Example 1-4: Coating Agent No. for Resin-Containing Layer 4>
4.4 parts by mass of the water-soluble polymer shown in Table 1 and 100 parts by mass of water were mixed and stirred for 5 minutes. Then, using 10% concentration of acetic acid, the pH was adjusted so that the pH of the mixture of the water-soluble polymer and water was 5.0.
Next, 100.7 parts by mass of the functional particles A shown in Table 1 were added to the mixed solution obtained by adjusting the pH, and the mixture was stirred for 5 minutes. As a result, the coating agent No. for the resin-containing layer becomes No. I got 4.
The obtained coating agent No. The solid content ratio of each raw material in No. 4 is shown in Table 2.

<Production Example 1-5: Coating Agent No. for Resin-Containing Layer 5>
3.5 parts by mass of the water-soluble polymer shown in Table 1 and 100 parts by mass of water were mixed and stirred for 5 minutes. Then, using 10% concentration of acetic acid, the pH was adjusted so that the pH of the mixture of the water-soluble polymer and water was 5.0.
Next, in the mixed solution obtained by adjusting the pH, the functional particles C shown in Table 1 [manufactured by Chuo Rika Kogyo Co., Ltd., trade name: Aquatex AC-3100, ethylene-methacrylic acid copolymer emulsion The solution, average dispersed particle diameter 0.7 μm, minimum film forming temperature 100 ° C.)] 14.9 parts by mass, and 26.8 parts by mass of the thermoplastic resin particles A shown in Table 1 were added and stirred for 5 minutes. As a result, the coating agent No. for the resin-containing layer becomes No. I got 5.
The obtained coating agent No. Table 2 shows the solid content ratio of each raw material in 5.

<Production Example 1-6: Coating Agent No. for Resin-Containing Layer 6>
3.2 parts by mass of the water-soluble polymer shown in Table 1 and 100 parts by mass of water were mixed and stirred for 5 minutes. Then, using 10% concentration of acetic acid, the pH was adjusted so that the pH of the mixture of the water-soluble polymer and water was 5.0.
Next, 13.5 parts by mass of the functional particles C shown in Table 1 and 15.2 parts by mass of the thermoplastic resin particles B shown in Table 1 were added to the mixed solution obtained by adjusting the pH. The mixture was stirred for 5 minutes. As a result, the coating agent No. for the resin-containing layer becomes No. I got 6.
The obtained coating agent No. Table 2 shows the solid content ratio of each raw material in 6.

<Production Example 1-7: Coating Agent No. for Resin-Containing Layer 7>
3.5 parts by mass of the water-soluble polymer shown in Table 1 and 100 parts by mass of water were mixed and stirred for 5 minutes. Then, using 10% concentration of acetic acid, the pH was adjusted so that the pH of the mixture of the water-soluble polymer and water was 5.0.
Next, in the mixed solution obtained by adjusting the pH, the functional particles D shown in Table 1 [manufactured by Sumitomo Seika Co., Ltd., trade name: Seporjon G315, olefin resin emulsion, average dispersed particle diameter 1. 5 μm, minimum film forming temperature 85 ° C.)] 14.9 parts by mass and 26.8 parts by mass of the thermoplastic resin particles A shown in Table 1 were added and stirred for 5 minutes. As a result, the coating agent No. for the resin-containing layer becomes No. I got 7.
The obtained coating agent No. Table 2 shows the solid content ratio of each raw material in 7.

(Manufacturing of sheets)
Sheets were produced using the raw materials shown in Table 3 below.

<Production Example 2-1: Sheet No. 1>
<< Process (2-1A) >>
77 parts by mass of PP-1 (manufactured by Mitsui Chemicals Co., Ltd., trade name: toughmer PN0040, ethylene / propylene copolymer) shown in Table 3, CA-1 (manufactured by Bihoku Powder Industry Co., Ltd.) shown in Table 3, products Name: Softon # 1800, heavy calcium carbonate) 22 parts by mass, and TI-1 (manufactured by Ishihara Sangyo Co., Ltd., trade name: rutile type titanium dioxide, typake CR-60) shown in Table 3 are mixed by 1 part by mass. Obtained a mixture. The obtained mixture was kneaded in an extruder set at a temperature of 270 ° C., extruded into a sheet from the extruder, and cooled by a cooling device to obtain an unstretched sheet. The obtained unstretched sheet is reheated to a temperature of 150 ° C., and then stretched four times in the vertical direction (MD direction) by utilizing the difference in peripheral speed of the roll group to obtain a vertically stretched film. rice field.

<< Process (2-1B) >>
Separately from the step (2-1A), PP-1 shown in Table 3 was kneaded by an extruder set at a temperature of 270 ° C. and then extruded into a sheet to obtain an unstretched sheet. The obtained unstretched sheet was laminated on one side of the vertically quadrupled stretched film obtained in the step (2-1A) to obtain a laminated film having a two-layer structure.

<< Process (2-1C) >>
Next, the two-layer structure laminated film obtained in step (2-1B) is cooled to a temperature of 60 ° C., then heated to a temperature of 165 ° C. again, and laterally (TD direction) using a tenter. ) Was stretched 9 times. Then, an annealing treatment was performed at a temperature of 175 ° C., the film was cooled to a temperature of 60 ° C., and then the ears were slit to obtain a laminated stretched film having a two-layer structure.

The number of stretching axes of each layer (thermoplastic resin layer / base material layer) of the obtained two-layer structure laminated stretched film (sheet) was uniaxial stretching / biaxial stretching. The total thickness of the obtained two-layer structure laminated stretch film was 75 μm, and the thickness of each layer (thermoplastic resin layer / base material layer) was 4 μm / 71 μm.

<Manufacturing Example 2-2: Sheet No. 2>
In the same manner as in Production Example 2-1 except that the step (2-1B) was changed to the following step (2-2B) in Production Example 2-1. I got 2.

<< Process (2-2B) >>
After kneading PP-2 (manufactured by ExxonMobil, trade name: VISTAMAXX 3588FL, ethylene / propylene copolymer) shown in Table 3 in an extruder set at a temperature of 270 ° C. separately from the step (2-1A). , Extruded into a sheet to obtain an unstretched sheet. The obtained unstretched sheet was laminated on one side of the vertically quadrupled stretched film obtained in the step (2-1A) to obtain a laminated film having a two-layer structure.

<Production Example 2-3: Sheet No. 3>
In the same manner as in Production Example 2-1 except that the step (2-1B) was changed to the following step (2-3B) in Production Example 2-1. I got 3.

<< Process (2-3B) >>
Separately from the step (2-1A), PP-4 (manufactured by Japan Polypropylene Corporation, trade name: Novatec PP EG7F, ethylene / propylene copolymer) shown in Table 3 was used in an extruder set at a temperature of 270 ° C. After kneading, it was extruded into a sheet to obtain a non-stretched sheet. The obtained unstretched sheet was laminated on one side of the vertically quadrupled stretched film obtained in the step (2-1A) to obtain a laminated film having a two-layer structure.

<Manufacturing Example 2-4: Sheet No. 4>
In the same manner as in Production Example 2-1 except that the step (2-1B) was changed to the following step (2-4B) in Production Example 2-1. I got 4.

<< Process (2-4B) >>
Separately from the step (2-1A), PP-5 (manufactured by Japan Polypropylene Corporation, trade name: Wintech WFW4, ethylene / propylene copolymer) shown in Table 3 was used in an extruder set at a temperature of 270 ° C. After kneading, it was extruded into a sheet to obtain a non-stretched sheet. The obtained unstretched sheet was laminated on one side of the vertically quadrupled stretched film obtained in the step (2-1A) to obtain a laminated film having a two-layer structure.

<Manufacturing Example 2-5: Sheet No. 5>
In the same manner as in Production Example 2-1 except that the step (2-1B) was changed to the following step (2-5B) in Production Example 2-1. I got 5.

<< Process (2-5B) >>
Separately from the step (2-1A), PP-6 (manufactured by Japan Polypropylene Corporation, trade name: Novatec PP MG3F, ethylene / propylene copolymer) shown in Table 3 was used in an extruder set at a temperature of 270 ° C. After kneading, it was extruded into a sheet to obtain a non-stretched sheet. The obtained unstretched sheet was laminated on one side of the vertically quadrupled stretched film obtained in the step (2-1A) to obtain a laminated film having a two-layer structure.

<Manufacturing Example 2-6: Sheet No. 6>
In the same manner as in Production Example 2-1 except that the step (2-1B) was changed to the following step (2-6B) in Production Example 2-1. I got 6.

<< Process (2-6B) >>
Separately from the step (2-1A), PP-7 (manufactured by Japan Polypropylene Corporation, trade name: Novatec PP MA3, propylene homopolymer) shown in Table 3 is kneaded with an extruder set to a temperature of 270 ° C. Then, it was extruded into a sheet to obtain a non-stretched sheet. The obtained unstretched sheet was laminated on one side of the vertically quadrupled stretched film obtained in the step (2-1A) to obtain a laminated film having a two-layer structure.

<Manufacturing Example 2-7: Sheet No. 7>
In the same manner as in Production Example 2-1 except that the step (2-1B) was changed to the following step (2-7B) in Production Example 2-1. I got 7.

<< Process (2-7B) >>
Apart from step (2-1A), PP-5 and PP-7 shown in Table 3 were mixed at a mass ratio of 50:50 to obtain a mixture. The obtained mixture was kneaded in an extruder set at a temperature of 270 ° C. and then extruded into a sheet to obtain an unstretched sheet. The obtained unstretched sheet was laminated on one side of the vertically quadrupled stretched film obtained in the step (2-1A) to obtain a laminated film having a two-layer structure.

<Manufacturing Example 2-8: Sheet No. 8>
In the same manner as in Production Example 2-1 except that the step (2-1B) was changed to the following step (2-8B) in Production Example 2-1. 8 was obtained.

<< Process (2-8B) >>
Apart from step (2-1A), PP-5 and PP-7 shown in Table 3 were mixed at a mass ratio (PP-5: PP-7) of 40:60 to obtain a mixture. The obtained mixture was kneaded in an extruder set at a temperature of 270 ° C. and then extruded into a sheet to obtain an unstretched sheet. The obtained unstretched sheet was laminated on one side of the vertically quadrupled stretched film obtained in the step (2-1A) to obtain a laminated film having a two-layer structure.

<Manufacturing Example 2-9: Sheet No. 9>
In the same manner as in Production Example 2-1 except that the step (2-1B) was changed to the following step (2-9B) in Production Example 2-1. I got 9.

<< Process (2-9B) >>
Separately from the step (2-1A), PE-1 (manufactured by Japan Polypropylene Corporation, trade name: Novatec HD HJ362N, high-density polyethylene) shown in Table 3 was kneaded with an extruder set at a temperature of 270 ° C. Then, it was extruded into a sheet to obtain an unstretched sheet. The obtained unstretched sheet was laminated on one side of the vertically quadrupled stretched film obtained in the step (2-1A) to obtain a laminated film having a two-layer structure.

<Sheet indentation hardness>
One type of indentation test by load-unload test from the surface side of the thermoplastic resin layer on the sheet using the Nano Indentation Tester ENT-2100 manufactured by Elionix and the Berkovich indenter (tip triangular pyramid) under the following conditions. The indentation hardness of the surface layer was calculated from the average value of each layer. The results are shown in Table 4.
・ Temperature: 30 ℃
・ Maximum load: 0.05mN
・ Load speed: 0.005mN
・ Holding time at maximum load: 1 second ・ Surface detection method: Inclined method ・ Surface detection threshold coefficient: 2.0
・ Spring correction: None

(Example 1)
Sheet No. produced in Production Example 2-1. On the surface of the thermoplastic resin layer of No. 1, the coating agent No. 1 for the resin-containing layer produced in Production Example 1-1. 1 was painted. Coating Agent No. for Resin-Containing Layer No. 1 was coated so that the coating amount was 0.8 g in solid content after drying per ^{unit area (m 2).} A bar coater was used for coating. Coating Agent No. for Resin-Containing Layer The laminated body of Example 1 was obtained by drying the sheet coated with 1 in an oven at 60 ° C. to form a resin-containing layer.

(Examples 2 to 11 and Comparative Examples 1 to 4)
In Example 1, a laminate was obtained in the same manner as in Example 1 except that the sheet and coating agent were changed to the sheets and coating agents shown in Table 5.

<Label punching evaluation: Print layer peelability>
The presence or absence of peeling of the print layer was evaluated by the following method.
On the resin-containing layers of the laminates obtained in Examples 1 to 11 and Comparative Examples 1 to 4, an offset printing machine (manufactured by Ryobi Co., Ltd., equipment name: RYOBI3300CR), UV offset printing ink (T & K TOKA Co., Ltd.) 2000 sheets were printed using the product, product name: BC161). The printed surface was irradiated with UV (irradiation amount 100 mJ / cm ² ) to solidify the ink to form a print layer.
The obtained printed matter was punched out with a label size of 120 mm × 60 mm using a rotary cutting machine (MDT manufactured by Iwasaki Iron Works).
After punching to the label size, the peeled state of the printed layer at the edge of the label was visually observed and evaluated according to the following evaluation criteria. The results are shown in Table 5.
〔Evaluation criteria〕
A (good): No peeling is seen.
B (OK): There is no problem although some peeling is seen.
C (defective): Peeling is seen on the entire edge.

<Antistatic property>
The surface of the resin-containing layer of the laminates obtained in Examples 1 to 8 and Comparative Examples 1 to 4 was used in an environment of 23 ° C. and a relative humidity of 30%, using STATICHONESTMETER (manufactured by SHISHIDOERECTROSTACTIC. LTD, product name: TYPES5109). The measurement was carried out in accordance with the half-life measurement method described in JIS L1094: 1997 “Method for testing chargeability of woven fabrics and knitted fabrics”. At this time, the measurement time after the application was stopped was set to 300 seconds, and the charging half-life S (Sec) was determined. It was evaluated according to the following evaluation criteria. The results are shown in Table 5.
〔Evaluation criteria〕
A (good): The charge half-life S is 30 seconds or less.
B (possible): The charge half-life S exceeds 30 seconds and is 300 seconds or less.
C: (Defective) The charging half-life S exceeds 300 seconds.

<Aptitude for thermal transfer by melting>
(Evaluation of ink transferability)
The imprints on the laminates obtained in Examples 9 to 11 are a barcode printer (trade name: B-30-S5, manufactured by Tech Co., Ltd.) and a molten resin ink ribbon (trade name: B110C, manufactured by Tech Co., Ltd.). This was carried out by printing a CODE39 barcode on the surface of the resin-containing layer of the laminate in an atmosphere of 35 ° C. and 85% relative humidity using a Ricoh Co., Ltd.).

The ink transfer property evaluation was carried out by measuring the ANSI grade of the barcode printed on the laminate using a barcode verification machine (trade name: LASERCHEKII, manufactured by Fuji Electric Refrigerator Co., Ltd.). The evaluation criteria for ink transferability are as follows, and ANSI grades A to C were accepted.
〔Evaluation criteria〕
A (good): ANSI grade A or B (clear image is obtained)
B (possible): ANSI grade C (bar code is slightly faint, but maintains a practical level.)
C (defective): ANSI grades D to F (line breaks occur due to faint barcodes)
D (impossible): ANSI grade N / G (cannot be recognized as a CODE39 barcode)

When the pressing hardness of the sheet was 60 N / mm ² or less, peeling of the print layer could be suppressed. The peeling of the print layer was further suppressed when it was ^{50 N / mm 2 or less.}
High density polyethylene tends to be more brittle than random polypropylene. Therefore, in Example 6 in which high-density polyethylene was used for the thermoplastic resin layer instead of random polypropylene, a part of the thermoplastic resin layer was peeled off during sheet molding, and the surface of the laminate was contaminated.
Regarding the stickiness of the sheet, the sheet No. Sheet No. 1 rather than sheet 1. 2-No. Sheet 9 was less sticky. That is, from the viewpoint of sheet stickiness, the pressing hardness of the sheet ^{is preferably 10 N / mm 2} or more.

1a, 1b ... Laminated body, 2a, 2b ... Sheet, 3 ... Base material layer, 4 ... Thermoplastic resin layer, 5 ... Resin-containing layer, 6 ... Thermoplastic resin layer , 7 ... Resin-containing layer, 8 ... Printing layer, 9 ... Printing layer, 10a, 10b, 10c, 10d ... Printed matter, 11 ... Adhesive layer

Claims (14)

A laminate having a sheet having a thermoplastic resin layer on one surface and a resin-containing layer provided on the surface of the thermoplastic resin layer of the sheet.
The resin-containing layer contains a thermoplastic resin that covers the sheet.
The indentation hardness of the sheet is not more than 0N / mm ² Ultra-60N / mm ^2, laminate. The laminate according to claim 1, wherein the indentation hardness of the sheet is 0.1 N / mm ² or more and 60 N / mm ^{2 or less.} The laminate according to claim 1 or 2, wherein the indentation hardness of the sheet is 10 N / mm ² or more and 60 N / mm ^{2 or less.} The laminate according to any one of claims 1 to 3, wherein the thermoplastic resin in the resin-containing layer contains a polyurethane resin. The laminate according to any one of claims 1 to 4, wherein the thermoplastic resin layer contains random polypropylene. The laminate according to claim 5, wherein the random polypropylene has a tensile elastic modulus of 30 to 1200 N / mm ^2. The laminate according to claim 5 or 6, wherein the random polypropylene has a melting point of 100 to 145 ° C. The laminate according to any one of claims 5 to 7, wherein the content of the random polypropylene in the thermoplastic resin layer is 60% by mass or more. The laminate according to any one of claims 1 to 8, wherein the resin-containing layer contains functional particles. The laminate according to claim 9, wherein the functional particles contain particles having a cationic metal oxide. The laminate according to claim 9, wherein the functional particles contain olefin polymer particles. The laminate according to any one of claims 1 to 11, wherein the sheet has a base material layer and the thermoplastic resin layer provided on the surface of the base material layer. The laminate according to any one of claims 1 to 12, and the laminate.
An adhesive layer provided on a surface of the laminate opposite to the resin-containing layer side,
Has a label. The laminate according to any one of claims 1 to 12, and the laminate.
A printing layer provided on the surface of the resin-containing layer of the laminate, and
Have a printed matter.

Images