JP7561510B2 - Laminates, labels and printed matter - Google Patents

Description

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

Traditionally, printed matter with a printing layer on a print medium has been widely used for outdoor advertisements, books, calendars, display labels, etc.

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

JP 2011-116125 A

However, when a resin-containing layer formed from thermoplastic resin particles is provided on the surface of a thermoplastic resin layer contained in a print medium, the printability is improved due to the relationship between the resin-containing layer and the printed layer provided on the surface of the resin-containing layer, but the inventors have discovered a problem in which the printed layer peels off when the printed matter provided with the printed layer is cut by punching or the like. This is thought to be because the adhesion between the resin-containing layer and the thermoplastic resin layer that serves as the base for the resin-containing layer was insufficient to withstand stress in the thickness direction, such as from cutting.

The present invention aims to provide a laminate that can prevent the printed layer from peeling off when the printed material is cut by punching or the like.

As a result of extensive research by the inventors to solve the above problems, they discovered that the above problems can be solved by adjusting the indentation hardness of a sheet having on one surface a thermoplastic resin layer that serves as a base for a resin-containing layer containing a thermoplastic resin that covers the sheet, and thus 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 thereof 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 laminate, wherein the indentation hardness of the sheet is greater than 0 N/ ^mm2 and ^not greater than 60 N/mm2.
[2] The laminate according to [1], wherein the indentation hardness of the sheet is 0.1 N/mm2 or ^more and 60 N/ ^mm2 or less.
[3] The laminate according to [1] or [2], wherein the indentation hardness of the sheet is 10 N/ ^mm2 or more and 60 N/ ^mm2 or less.
[4] The laminate according to any one of [1] to [3], wherein the thermoplastic resin in the resin-containing layer contains a polyurethane resin.
[5] The laminate according to any one of [1] to [4], wherein the thermoplastic resin layer contains random polypropylene.
[6] The laminate described in [5], wherein the random polypropylene has a tensile modulus of 30 to 1200 N/ ^mm2 .
[7] The laminate according to [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], wherein the resin-containing layer contains functional particles.
[10] The laminate according to [9], wherein the functional particles contain particles having a cationic metal oxide.
[11] The laminate according to [9], wherein the functional particles contain olefin-based polymer particles.
[12] The laminate according to any one of [1] to [11], wherein the sheet has a base layer and the thermoplastic resin layer provided on a surface of the base layer.
[13] A laminate according to any one of [1] to [12] above,
an adhesive layer provided on a surface of the laminate opposite to the resin-containing layer;
A label having
[14] A laminate according to any one of [1] to [12] above,
a printed layer provided on a surface of the resin-containing layer of the laminate;
A printed matter having the above-mentioned features.

The present invention provides a laminate that can suppress peeling of the printed layer when the printed material is cut by punching or the like.

FIG. 2 is a cross-sectional view showing an example of the configuration of a laminate according to the present embodiment. FIG. 4 is a cross-sectional view showing another example of the configuration of the laminate of the present embodiment. FIG. 2 is a cross-sectional view showing an example of the configuration of a printed matter according to the present embodiment. FIG. 11 is a cross-sectional view showing another example of the configuration of the printed matter of the present embodiment. FIG. 11 is a cross-sectional view showing another example of the configuration of the printed matter of the present embodiment. FIG. 11 is a cross-sectional view showing another example of the configuration of the printed matter of the present embodiment.

The laminate and printed matter of the present invention are described in detail below, but the description of the constituent elements described below is one example (representative example) of one embodiment of the present invention, and is not limited to these contents. In addition, the dimensional ratios of the drawings are not limited to the ratios shown in the drawings.

In this specification, for example, a numerical range such as "1 to 100" includes both the lower limit "1" and the upper limit "100".
In addition, the term "(meth)acrylic" refers to both acrylic and methacrylic.

(Laminate)
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.
The sheet has an indentation hardness of more than 0 N/ ^mm2 and not more than 60 N/ ^mm2 .

The resin-containing layer can improve the wettability when forming the printed layer, and the adhesion between the printed layer and the laminate, etc. On the other hand, the resin-containing layer does not have sufficient adhesion to the underlying thermoplastic resin layer against stress such as punching, and peeling of the printed layer may occur.
Therefore, as a result of intensive research, the inventors have found that by setting the indentation hardness of a sheet having a thermoplastic resin layer on one surface that serves as a base for a resin-containing layer to more than 0 N/ ^mm2 and not more than 60 N/ ^mm2 , peeling of the printed layer when the printed material is cut by punching or the like can be suppressed, and have completed the present invention.

The laminate is used, for example, as printing paper, wrapping paper, wallpaper, etc.

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

The indentation hardness (HIT) of the sheet is more than 0 N/ ^mm2 and 60 N/mm2 ^or less. The indentation hardness of the sheet is measured by a nanoindentation test on the thermoplastic resin layer side of the sheet (i.e., the surface on which the resin-containing layer is provided) as shown in the examples described later. The nanoindentation test for measuring the indentation hardness (HIT) is established by the international standard ISO14577. It is considered that by providing a flexible thermoplastic resin layer having an indentation hardness of 60 N/mm2 or ^less on the surface of the sheet, the stress generated at the interface between the thermoplastic resin layer and the resin-containing layer provided on the surface of the thermoplastic resin layer can be dispersed (mitigated), 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 laminate from the outside by punching after printing, peeling of the printed layer can be suppressed. The above-mentioned effect can be sufficiently obtained even when the thermoplastic resin in the resin-containing layer is formed in a layer shape and the resin-containing layer is provided with a mass per unit area of 0.05 g/m2 or ^more (even 0.1 g/ ^m2 or more).

The indentation hardness of the sheet is preferably as small as possible from the viewpoint of providing a strong adhesive force between the resin-containing layer and the thermoplastic resin layer and suppressing peeling of the printed layer when the printed material is cut by punching or the like, and is not particularly limited as long as it is 60 N/mm2 or ^less , but is preferably 50 N/mm2 ^or less. The indentation hardness of the sheet may be, for example, 0.1 N/ ^mm2 or more, or 10 N/ ^mm2 or more. From the viewpoint of suppressing stickiness of the sheet, the indentation hardness of the sheet is preferably 10 N/mm2 or ^more .
Here, the stickiness of the sheet refers to the adhesive feeling of the thermoplastic resin layer to an object. If the sheet is sticky, blocking between the sheets is likely to occur when the sheets are wound into a roll or stored in a pile.

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

The thickness of the sheet is not particularly limited, but is preferably 20 μm or more, more preferably 40 μm or more, and even more preferably 60 μm or more from the viewpoints of ease of handling and prevention of wrinkles, etc. On the other hand, from the viewpoints of ease of handling and productivity, it is preferably 250 μm or less, and even more preferably 200 μm or less.
The thickness of the sheet is measured, for example, in accordance with JIS K7130:1999 using a constant pressure thickness gauge.

<<Thermoplastic resin layer>>
The sheet has a thermoplastic resin layer on one surface.
The sheet may have a thermoplastic resin layer on each side of the substrate layer. In this case, the two thermoplastic resin layers on both sides may be the same in material, thickness, etc., or may be different. It may be possible.
The thermoplastic resin layer contains a thermoplastic resin.
The thermoplastic resin layer is made of, for example, a thermoplastic resin. In this case, the thermoplastic resin is, for example, a matrix resin.
When the sheet has a thermoplastic resin layer on each of both sides of the base material layer, the indentation hardness of the sheet satisfies more than 0 N/ ^{mm2 and} 60 N/mm2 or ^less on at least one side, and 0 N/mm2 or less on both sides. It is preferable that the strength satisfy the range of more than ² and 60 N/ ^mm2 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 with a sheet indentation hardness of 60 N/ ^mm2 or less. Examples of low-elasticity thermoplastic resins include low-elasticity polyolefin resins. Note that even polyolefin resins have different tensile modulus depending on the type of olefin, molecular weight, branching degree, crystallinity, copolymerization ratio, etc. Therefore, it is preferable to select and use a low-elasticity polyolefin resin (i.e., a low tensile modulus).
Examples of polyolefin resins include polyethylene resins, polypropylene resins, polybutene, and 4-methyl-1-pentene (co)polymers.
Examples of polyethylene resins include low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, low-crystalline or amorphous ethylene-α-olefin copolymers, and ethylene-cyclic olefin copolymers.
Examples of polypropylene-based resins include crystalline polypropylene, low crystalline polypropylene, amorphous polypropylene, propylene-ethylene copolymers (random copolymers or block copolymers), propylene-α-olefin copolymers, and propylene-ethylene-α-olefin copolymers.
The α-olefin constituting the propylene-α-olefin copolymer and the propylene-ethylene-α-olefin copolymer is not particularly limited as long as it is copolymerizable with ethylene and propylene, and examples thereof include 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, and 1-octene.
Among these, random polypropylene is preferred because it is easy to obtain a predetermined elastic modulus and because it prevents a part of the thermoplastic resin layer from peeling off during sheet molding and contaminating the laminate surface. Random polypropylene is a random copolymer of propylene and ethylene, which is a type of propylene-ethylene copolymer, and in this specification 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 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. By having a tensile modulus of 1200 MPa or less, the indentation hardness of the sheet surface can be reduced, and peeling of the printed layer when the printed matter is cut by punching or the like tends to be more suppressed. On the other hand, by having a tensile modulus of 30 MPa or more, 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 less, more preferably 145°C or less, and even more preferably 140°C or less. When the melting point is equal to or less than the upper limit temperature, the amount of voids generated in the resin-containing layer during stretching during the sheet manufacturing process tends to be reduced. As a result, the smoothness of the sheet surface is improved, excellent cosmetic properties are obtained, and dot skips are less likely to occur in gravure printing. In addition, the melting point is preferably 60°C or more, more preferably 75°C or more, and even more preferably 90°C or more. When the melting point is 60°C or more, 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 modulus of the low-elasticity thermoplastic resin, but is preferably 40% by mass or more, more preferably 50% by mass or more, and even more preferably 60% by mass or more. By having a content of 40% by mass or more, it becomes easier to reduce the indentation hardness of the sheet surface, and there is a tendency that peeling of the printed layer when the printed material is cut by punching or the like can be more suppressed. The content of the low-elasticity thermoplastic resin in the thermoplastic resin layer may be 100% by mass or less. For example, from the viewpoint of balance with the shrinkage rate of other layers, the content may be 95% by mass or less, or may be 90% by mass or less.

When the low-elasticity thermoplastic resin is not compatible with the resin material contained in the layer adjacent to the thermoplastic resin layer, it is preferable that the low-elasticity thermoplastic resin is used in the thermoplastic resin layer together with a resin that is compatible with the resin material. For example, when a polypropylene-based resin is used in the base layer and a polyethylene-based resin is selected as the low-elasticity thermoplastic resin that constitutes the thermoplastic resin layer, it is preferable that the polyethylene-based resin is used in the thermoplastic resin layer together with a polypropylene-based resin.

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

The thermoplastic resin layer may or may not contain particles such as inorganic particles and organic particles, but it is preferable that it does. When the thermoplastic resin layer contains these particles, the surface is appropriately roughened by the pores and particles, and the adhesion to the printing layer is easily improved by the anchoring effect. When the thermoplastic resin layer contains particles, the particle content in the thermoplastic resin layer is, for example, 10 to 50 mass %. When the content is 50 mass % or less, the indentation hardness of the sheet is easily reduced.

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

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

<<<Thermoplastic resin>>>
In the base material layer, the thermoplastic resin is, for example, a matrix resin, and imparts mechanical strength to the sheet.
Examples of the thermoplastic resin contained in the base layer include polyolefin resins such as polyethylene resins, polypropylene resins, polybutene, and 4-methyl-1-pentene (co)polymers; ethylene-vinyl acetate copolymers; copolymers, ethylene-(meth)acrylic acid copolymers, metal salts of ethylene-(meth)acrylic acid copolymers (ionomers), ethylene-(meth)acrylic acid alkyl ester copolymers (the alkyl group has 1 carbon atom functional group-containing olefin resins such as maleic acid modified polyethylene and maleic acid modified polypropylene; aromatic polyesters (polyethylene terephthalate, polybutylene polyester resins such as poly(ethylene terephthalate), poly(ethylene naphthalate), and aliphatic polyesters (polybutylene succinate, poly(lactic acid), etc.); nylon-6, nylon-6,6, nylon-6,10, and nylon- Polyamide resins such as styrene-butadiene-styrene (SBR) copolymers, styrene-butadiene-styrene (ABS) copolymers, and styrene-butadiene-styrene (SBR) copolymers. styrene-based resins such as styrene-based resins; polyvinyl chloride resins; polycarbonate resins; and polyphenylene sulfide.

Examples of polyethylene resins include low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, low-crystalline or amorphous ethylene-α-olefin copolymers, and ethylene-cyclic olefin copolymers.
Examples of polypropylene-based resins include crystalline polypropylene, low crystalline polypropylene, amorphous polypropylene, propylene-ethylene copolymers (random copolymers or block copolymers), propylene-α-olefin copolymers, and propylene-ethylene-α-olefin copolymers.
The α-olefin constituting the propylene-α-olefin copolymer and the propylene-ethylene-α-olefin copolymer is not particularly limited as long as it is copolymerizable with ethylene and propylene, and examples thereof include 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, and 1-octene.
Among these thermoplastic resins, polyolefin-based resins are preferred because they can provide water resistance and chemical resistance at low cost, and polypropylene-based resins are preferred because they can provide the laminate with appropriate stiffness as a printing medium.

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

<<<Filler>>>
The filler, for example, contributes to the formation of pores when forming the base layer. The formation of pores in the base layer allows the laminate to obtain the desired whiteness and opacity. On the other hand, when a transparent laminate is produced, the base layer does not need to contain a filler.
Examples of the filler contained in the base layer include inorganic fillers and organic fillers.

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

Inorganic fillers are preferred because they are available commercially in a wide variety of products with different particle sizes at low cost. Examples of inorganic fillers include, but are not limited to, heavy calcium carbonate, light calcium carbonate, calcined clay, silica, diatomaceous earth, white clay, talc, titanium oxide, barium sulfate, alumina, zeolite, mica, sericite, bentonite, sepiolite, vermiculite, dolomite, wollastonite, and glass fiber. Among these, heavy calcium carbonate, light calcium carbonate, and titanium oxide are preferred from the viewpoint of pore formation and cost, and heavy calcium carbonate is more preferred.
These inorganic fillers may be used alone or in combination of two or more.

The filler content in the base layer is not particularly limited, but from the viewpoint of forming sufficient pores in the base layer, it is preferably 2% by mass or more, more preferably 4% by mass or more, even more preferably 10% by mass or more, and particularly preferably 14% by mass or more. On the other hand, from the viewpoint of suppressing a decrease in the strength of the base layer, the content is preferably 50% by mass or less, more preferably 40% by mass or less, even more 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 layer is not particularly limited, but from the viewpoint of imparting appropriate stiffness to the laminate, it is preferably 20 μm or more, more preferably 40 μm or more, and even more preferably 60 μm or more. On the other hand, from the viewpoint of production costs, etc., it is preferably 250 μm or less, and more preferably 200 μm or less.

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

The sheets may be oriented or unoriented.
The method for stretching the sheet is not particularly limited, and examples thereof include longitudinal (MD) stretching utilizing the difference in peripheral speed between a group of rolls, transverse (TD) stretching using a tenter oven, rolling, simultaneous biaxial stretching using a combination of a tenter oven and a linear motor, simultaneous biaxial stretching using a combination of a tenter and a pantograph, or combinations of these.

When the sheet has a multi-layer structure, the number of times and the direction of stretching of each layer may be the same or different. For example, when the sheet has a base layer and a thermoplastic resin layer, the sheet may be manufactured by stacking a vertically stretched base layer and an unstretched thermoplastic resin layer and stretching them horizontally. In this case, the base 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.

The 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 in 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 in each layer is a crystalline resin, the stretching temperature is preferably in a range equal to or higher than the glass transition temperature of the non-crystalline portion of the thermoplastic resin and equal to or lower than the melting point of the crystalline portion of the thermoplastic resin. Specifically, the stretching temperature of each layer is preferably 2 to 60°C lower than the melting point of the thermoplastic resin used in each layer.

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

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

<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 laminate, 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 that constitutes the resin-containing layer.
The thermoplastic resin is present in the resin-containing layer in a layered form, for example, and covers the sheet. By covering the sheet with the thermoplastic resin, water resistance is easily obtained, but when the printed matter is cut by punching or the like, the thermoplastic resin may cause water resistance. The printed layer is likely to peel off. Therefore, the present invention solves this problem.
The thermoplastic resin is, for example, a fused product of thermoplastic resin particles. The fused product of thermoplastic resin particles is a product in which thermoplastic resin particles are fused by heating. The fusion is, for example, This occurs due to the heating during formation. This causes the thermoplastic resin to be formed in layers, making it easier to obtain water resistance. In addition, functional particles are incorporated into the thermoplastic resin formed in layers and fixed to the laminate. In the fused product, the interfaces between the thermoplastic resin particles may be eliminated, or the interfaces may remain to the extent that the effects of the present invention are 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 more likely to fuse due to 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 that constitutes the resin-containing layer include vinyl resins and polyurethane resins.

The vinyl monomer constituting the vinyl resin may be one or more selected from the group consisting of olefins; vinyl esters; unsaturated carboxylic acids and their alkali metal salts or acid anhydrides; esters of alkyl groups that may have a branched or cyclic structure with up to 12 carbon atoms; (meth)acrylamide, derivatives that simultaneously have an alkyl group with 1 to 4 carbon atoms and an alkylene group with 1 or 2 carbon atoms; and dimethyldiallylammonium salts. The above salts are acid residues, and the acid ions are preferably methyl sulfate ions and chloride ions.

Olefins include ethylene, propylene, 1-butene, and butadiene.
An example of the vinyl esters is vinyl acetate.
Examples of the unsaturated carboxylic acids include (meth)acrylic acid and maleic acid.
Examples of (meth)acrylamide and derivatives having simultaneously an alkyl group having 1 to 4 carbon atoms and an alkylene group having 1 or 2 carbon atoms include N-alkylaminoalkylene (meth)acrylates, N-alkylaminoalkylene (meth)acrylamides, N,N-dialkylaminoalkylene (meth)acrylates, N,N-dialkylaminoalkylene (meth)acrylamides, (meth)acryloyloxyalkylene trialkylammonium salts, and (meth)acryloylaminoalkylene trialkylammonium salts.

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 from among the above may be directly copolymerized as an essential component, a copolymer may be obtained using a monomer having a tertiary amine structure from among the above as an essential component, and then the tertiary amine may be quaternized with a quaternizing agent such as dimethyl sulfate, 3-chloro-2-hydroxypropyltrimethylammonium chloride, or glycidyltrimethylammonium chloride, or a copolymer may be obtained using only nitrogen-free monomers, and then a monomer having a quaternary ammonium salt structure may be grafted.

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 may be obtained, for example, by reacting a tertiary amino group-containing polyol, which is obtained by reacting a compound having two epoxy groups in one molecule with a secondary amine, with a polyisocyanate, and then quaternizing the urethane resin obtained by the reaction with the quaternizing agent. The copolymer may also be obtained by adding one or more selected from the group consisting of N,N-dialkylalkanolamines; N-alkyl-N,N-dialkanolamines such as N-methyl-N,N-diethanolamine and N-butyl-N,N-diethanolamine; and trialkanolamines to a part of the polyol, and then quaternizing the urethane resin obtained by the reaction with the polyisocyanate with the quaternizing agent.

For example, when forming a resin-containing layer, the thermoplastic resin is used in the form of an emulsion of thermoplastic resin particles. Methods for obtaining an emulsion include a method of emulsifying and dispersing the monomers constituting the target polymer in water and polymerizing them, and a method of obtaining the target polymer by bulk polymerization or the like, and then melt-kneading and emulsifying the raw resins sequentially using a twin-screw extruder. The amount of cations introduced into a vinyl resin having a quaternary ammonium salt structure in the molecule, or a copolymer having a cationic hydrophilic group introduced into a polyurethane resin skeleton, is evaluated, for example, by the colloid equivalent obtained by colloid titration using a potassium polyvinyl sulfate solution of the thermoplastic resin. In order for particles having a metal oxide to be dispersed and stably present 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, more preferably 0.6 meq/g or more, and even more preferably 1.0 meq/g or more. On the other hand, if the cationic equivalent of a vinyl resin having a quaternary ammonium salt structure in the molecule or a copolymer having a cationic hydrophilic group introduced into a polyurethane resin skeleton is too high, the re-dissolution rate of the resin-containing layer in water tends to increase. Therefore, the cationic 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 from the viewpoint of suppressing blocking, it may be 30° C. or higher, or 50° C. or higher. On the other hand, the softening point is preferably 300° C. or lower.
The softening point can be measured by a Koka type 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, more preferably 30% by mass or more. By having a content of 15% by mass or more, 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. By having a content of 65% by mass or less, antistatic properties are easily exhibited.
The content here means the content of all thermoplastic resins in the resin-containing layer. For example, when the resin-containing layer contains both a fused thermoplastic resin particle and a particulate thermoplastic particle, the content here is the total content of them.

<<Functional particles>>
The functional particles are inorganic or organic particles that can impart various functions to the surface of the laminate.
Such functions include an antistatic function, a function for improving printability, and a function for preventing blocking.
The functional particles are fixed to the resin-containing layer by the thermoplastic resin constituting the resin-containing layer. The functional particles are distributed, for example, in 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 functional particles having an antistatic function include particles having a metal oxide.
Examples of particles having a metal oxide include cationic compound particles and particles coated with a cationic compound.
Examples of particles having a metal oxide include inorganic particles having a metal oxide layer on the surface thereof, 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 in the form of, for example, a sol containing colloidal silica particles (hereinafter, sometimes referred to as "colloidal silica sol"). There are no particular limitations on the method for producing colloidal silica sol, but examples include a method in which an aqueous solution of an alkali metal silicate salt (e.g., water glass) is used as a raw material, the alkali metal salt is removed by ion exchange resin or electrophoresis to obtain an anhydrous silicate sol, and an acid or alkali is added to adjust and stabilize the pH, a method in which an alkoxide such as tetraethoxide orthosilicate (TEOS) is hydrolyzed with an acid or alkali (the so-called sol-gel method), and a method in which an organosilicon compound such as silicon tetrachloride is introduced into a flame of hydrogen or the like to synthesize the compound (the so-called gas-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 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 anionic colloidal silica is coated with a metal oxide. The cationic compound-coated colloidal silica sol is obtained, for example, by adding a cationic compound or a precursor thereof to the colloidal silica sol in a step subsequent to the dispersion step in which silica is dispersed in the dispersion medium. The metal oxide-coated colloidal silica sol is obtained, for example, by adding a metal oxide or a precursor thereof to the colloidal silica sol in a step subsequent to the dispersion step of silica. For example, an alumina-coated colloidal silica sol is obtained by treating the surface of colloidal silica by adding an aluminum water-soluble salt to the colloidal silica sol. By using cationic alumina-coated colloidal silica particles as particles containing metal oxide, the antistatic properties and printability are improved compared to when anionic colloidal silica particles are used.

The colloidal silica particles contained in the colloidal silica sol may have silanol groups (≡Si-OH) on the surface. The above 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, and even more preferably 5% or less. The above particles may be long-chain.

Examples of 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 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, sometimes referred to as a "metal oxide sol").
Examples of metal oxide sols 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 tin oxide sol. For example, methods for producing aluminum oxide sol include a method of producing it by hydrolyzing aluminum alkoxide such as aluminum isopropoxide with an acid, and a method of synthesizing it by introducing aluminum chloride into a flame of hydrogen or the like (so-called gas phase method).

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, and even more preferably 5% or less. The above particles may be long-chain.

The metal oxide used in the colloidal silica particles having a metal oxide layer on the surface of the colloidal silica and the metal oxide particles preferably contains at least one metal selected from aluminum, zinc, tin, and indium, and more preferably contains aluminum. The metal oxide may be alumina. When the metal oxide is alumina, the surfaces of the colloidal silica particles having a metal oxide layer on the surface of the colloidal silica and the metal oxide particles become cationic, improving antistatic properties, printability, etc.

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

The content of the functional particles having 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 antistatic function is 85% by mass or less, printability is further improved. For the same reason, the ratio of the mass of the functional particles having antistatic function to the mass of the thermoplastic resin in the coating liquid for forming the resin-containing layer (particles having 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 functional particles that have a printability improving function include olefin-based polymer particles. Olefin-based polymer particles exhibit hydrophobicity in the resin-containing layer, preventing excessive moisture from being absorbed into the resin-containing layer. This is believed to suppress water damage during offset printing. For the same reason, it is also believed to contribute to the stability of printed matter over time. On the other hand, in printing methods that utilize heat, such as thermal melting printing and electrophotographic printing, it is believed that the olefin-based copolymer particles present on the laminate surface melt partially during printing and become compatible with the thermal melting ink or toner, thereby fixing the thermal melting ink or toner.

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

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

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

Examples of functional particles having anti-blocking properties include silica and calcium carbonate. To have anti-blocking properties, the average particle size of the functional particles is preferably 5 μm or more, and more preferably 7 μm or more.

<<Water-soluble polymer>>
Examples of the water-soluble polymer include vinyl copolymers such as polyvinylpyrrolidone; partially saponified polyvinyl alcohol (hereinafter sometimes referred to as "PVA"), fully saponified PVA, and vinyl copolymer hydrolysates such as alkali metal salts or ammonium salts of isobutylene-maleic anhydride copolymers; (meth)acrylic acid derivatives such as sodium poly(meth)acrylate and poly(meth)acrylamide; modified polyamides; cellulose derivatives such as carboxymethyl cellulose and carboxyethyl cellulose; 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 addition, in the composition of the resin-containing layer, the water-soluble polymer is not included in the thermoplastic resin.

It is preferable that the water-soluble polymer dissolves in water in the coating agent used to form the resin-containing layer, and does not re-dissolve in water after the coating agent is applied to the surface of the thermoplastic resin layer in the sheet and dried.

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 content is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and even more preferably 20 parts by mass or more, per 100 parts by mass of the thermoplastic resin and the functional particles in total. On the other hand, from the viewpoint of printability, processability, etc., the content is preferably 200 parts by mass or less, more preferably 150 parts by mass or less, per 100 parts by mass of the thermoplastic resin and the functional particles in total.

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 from the viewpoint of further suppressing peeling of the printed layer when the printed matter is cut by punching or the like, it is preferably 20 g/m ² or less, more preferably 10 g/m ² or less, and even more preferably 1 g/m ² or less. On the other hand, from the viewpoint of printability, etc., the thickness is preferably 0.01 g/m ² or more, more preferably 0.05 g/m ² or more, and even more preferably 0.1 g/m ² or more.

<<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 then dried is preferred because it is easy to compound and form.
The coating agent contains, for example, thermoplastic resin particles and water. The coating agent may contain functional particles. For example, a part or all of the thermoplastic resin particles are fused by heating to a minimum film-forming temperature or higher after coating.

In the manufacturing process of the coating agent, for example, when the solid concentration of the particles having a metal oxide and the olefin polymer particles is high, when the pH of the coating agent is close to the isoelectric point of the olefin polymer particles, when the zeta potentials of the particles having a metal oxide and the olefin polymer particles are in a relationship of opposite signs, or when an ionic substance with a high valence (especially a polymer having a functional group) is added, at least one of the particles having a metal oxide and the olefin polymer particles may aggregate. Therefore, in the manufacturing process of the coating agent, it is preferable to add each material to the dilution water sequentially or to appropriately adjust the order and speed of addition so that the concentration of each material does not become locally high. In addition, 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. This can suppress aggregation.

The solids concentration of the coating agent can be adjusted as appropriate depending on the coating amount after drying of the resin-containing layer and the coating method of the coating agent, but is preferably 0.5% by mass or more, and more preferably 3% by mass or more. Also, it is preferably 35% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less. The pH of the coating agent must be such that the materials contained in the coating agent do not aggregate, but from the viewpoints of worker safety and prevention of machine corrosion, it is preferably pH 3 to 11, and more preferably pH 4 to 10.

FIG. 1 shows an example of the configuration of a laminate 1a according to an embodiment of the present invention.
As shown in Fig. 1, the laminate 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 layer 3. The resin-containing layer 5 is provided on the surface of the thermoplastic resin layer 4 of the sheet 2a.
The indentation hardness of the sheet 2a, measured by a nanoinden- tation test on the thermoplastic resin layer 4 side of the sheet 2a, is greater than 0 N/ ^mm2 and greater than 60 N/ ^mm2 .

FIG. 2 shows an example of the configuration of a laminate 1b as another embodiment of the present invention.
As shown in Fig. 2, laminate 1b has sheet 2b, resin-containing layer 5, and resin-containing layer 7. Sheet 2b has thermoplastic resin layer 4 on one surface and thermoplastic resin layer 6 on the other surface. Sheet 2b further has substrate layer 3 between thermoplastic resin layer 4 and thermoplastic resin layer 6. Resin-containing layer 5 is provided on the surface of thermoplastic resin layer 4 of sheet 2b. Resin-containing layer 7 is provided on the surface of thermoplastic resin layer 6 of sheet 2b.
The indentation hardness of the sheet 2b measured by a nanoinden- tation test on the thermoplastic resin layer 4 side of the sheet 2b is greater than 0 N/ ^mm2 and greater than 60 N/ ^mm2 .
The indentation hardness of the sheet 2b measured by a nanoindentation test on the thermoplastic resin layer 6 side of the sheet 2b is not particularly limited, but is preferably greater than 0 N/ ^mm2 and greater than 60 N/ ^mm2 .

(label)
The label has an adhesive layer on one side of the laminate. The adhesive layer may be an adhesive layer that has adhesiveness at room temperature, or a heat seal layer that is activated by heating. When the label has an adhesive layer, the label is an adhesive label. When 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 the resin-containing layer.

The adhesive layer is not particularly limited. The material and composition used for the adhesive layer may be, for example, the adhesive polymer and the adhesive polymer crosslinked with a crosslinking agent described in JP-A-2002-169470, the removable adhesive layer described in JP-A-9-197972, the adhesive layer described in JP-A-2004-216098, the adhesive layer described in JP-A-2009-275231, and the adhesive composition described in JP-A-2014-012808.

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

The heat seal layer contains a heat sealable resin. The melting point of the heat sealable resin is preferably at least 10°C lower than the melting point of the thermoplastic resin in the base layer, and more preferably at least 15°C lower. The melting point of the heat sealable resin is preferably at least 60°C, and more preferably at least 70°C.

Examples of heat-sealable resins include polyethylene, ethylene-based copolymers, propylene-based copolymers, polyester-based copolymers, styrene-based elastomer resins, and polyamide-based copolymers. The heat-sealable layer may further contain additives such as dyes, nucleating agents, plasticizers, release agents, flame retardants, antioxidants, light stabilizers, and ultraviolet absorbers, to the extent that the heat-sealability is not impaired.

The method for forming the heat seal layer includes cast molding, calendar molding, rolling molding, inflation molding, etc., in which molten resin is extruded into a sheet shape using a single-layer or multi-layer T-die, I-die, etc. connected to a screw-type extruder. The heat seal layer is provided on one surface of the laminate. When the laminate has a resin-containing layer only on one surface, it is preferable that the heat seal layer is 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, and is preferably 10 μm or less, and more preferably 5.0 μm or less.

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

The print layer is a layer formed by printing characters, borders, pictures, etc.
The print layer may be provided on the entire surface of the resin-containing layer, or may be provided on only a part of the surface.

The printing method for forming the printed layer is not particularly limited, and known printing methods such as gravure printing, offset printing, flexographic printing, seal printing, and screen printing can be used. The printed layer can also include conventionally known decorations such as printing by various printers such as inkjet type, electrophotographic type, and liquid toner type, foil stamping such as hot stamping and cold stamping, transfer foil, and holograms.

Depending on the printing method, various types of ink can be used, such as oil-based ink, oxidative polymerization curing ink, ultraviolet curing ink, water-based ink, powder toner, and liquid toner (electroink).

The printed matter may further have a release layer provided on the surface of the adhesive layer.
The release layer is not particularly limited, and examples thereof include fine paper or craft paper as is, fine paper or craft paper that has been calendared, resin-coated, or film-laminated, or glassine paper, coated paper, plastic film, or the like that has been silicone-treated.

FIG. 3 shows an example of the configuration of a printed matter 10a according to 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 laminate 1a is the laminate 1a shown in Fig. 1. In the printed matter 10a, the printed layer 8 is provided on the surface of the resin-containing layer 5 of the laminate 1a.

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

FIG. 5 shows an example of the configuration of a printed matter 10c as another embodiment of the present invention.
As shown in Fig. 5, the printed matter 10c has a laminate 1b, a printed layer 8, and a printed layer 9. The laminate 1b is the laminate 1b shown in Fig. 2. The printed layer 8 is provided on the surface of the resin-containing layer 5 of the laminate 1b. The printed layer 9 is provided on the surface of the resin-containing layer 7 of the laminate 1b.

FIG. 6 shows an example of the configuration of a printed matter 10d as another embodiment of the present invention.
As shown in Fig. 6, the printed matter 10d has a laminate 1b, a printed layer 8, and an adhesive layer 11. The laminate 1b is the laminate 1b shown in Fig. 2. The printed layer 8 is provided on the surface of the resin-containing layer 5 of the laminate 1b. The adhesive layer 11 is provided on the surface of the resin-containing layer 7 of the laminate 1b.

The present invention will be explained in more detail below with reference to examples, but the present invention is not limited to the following examples as long as it does not deviate from the gist of the invention. In the examples, the terms "parts", "%", etc. are based on mass unless otherwise specified.

(Preparation of Coating Agent for Resin-Containing Layer)
Using the raw materials shown in Table 1 below, a coating agent for the resin-containing layer was prepared.

<Production Example 1-1: Coating agent for resin-containing layer No. 1>
3.0 parts by mass of a water-soluble polymer shown in Table 1 and 100 parts by mass of water were mixed and stirred for 5 minutes. Thereafter, the pH of the mixture of the water-soluble polymer and water was adjusted to 5.0 using 10% acetic acid.
Next, 52.9 parts by mass of functional particles A (manufactured by Nissan Chemical Industries, Ltd., product name: Snowtex ST-AK, alumina surface-treated colloidal silica with an average particle size of 15 nm, solid content concentration of 19%) and 30.6 parts by mass of thermoplastic resin particles A (manufactured by DIC Corporation, product name: Hydran CP7050, urethane emulsion with an average particle size of 75 nm, minimum film-forming temperature: 0° C., solid content concentration of 25%) were added to the mixture obtained by adjusting the pH, and the mixture was stirred for 5 minutes. This gave coating agent No. 1 for resin-containing layer.
The solid content of each raw material in the obtained Coating Agent No. 1 is shown in Table 2.

<Production Example 1-2: Coating agent for resin-containing layer No. 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. Thereafter, the pH of the mixture of the water-soluble polymer and water was adjusted to 5.0 using acetic acid having a concentration of 10%.
Next, 47.5 parts by mass of functional particles A shown in Table 1 and 17.2 parts by mass of thermoplastic resin particles B shown in Table 1 (manufactured by DIC Corporation, product name: Boncoat VO8, acrylic emulsion with average particle size of 300 nm, minimum film-forming temperature 25° C., solid content concentration: 40%)) were added to the mixture obtained by adjusting the pH, and the mixture was stirred for 5 minutes. This gave coating agent No. 2 for resin-containing layer.
The solid content of each raw material in the obtained Coating Agent No. 2 is shown in Table 2.

<Production Example 1-3: Coating agent for resin-containing layer No. 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. Thereafter, the pH of the mixture of the water-soluble polymer and water was adjusted to 5.0 using 10% acetic acid.
Next, 42.6 parts by mass of functional particles B (manufactured by Nissan Chemical Industries, Ltd., product name: Aluminasol 520, alumina sol with an average particle size of 20 nm, solid content concentration of 22%) and 28.5 parts by mass of thermoplastic resin particles A were added to the mixture obtained by adjusting the pH and stirred for 5 minutes. This gave coating agent No. 3 for resin-containing layer.
The solid content ratio of each raw material in the obtained Coating Agent No. 3 is shown in Table 2.

<Production Example 1-4: Coating agent for resin-containing layer No. 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. Thereafter, the pH of the mixture of the water-soluble polymer and water was adjusted to 5.0 using 10% acetic acid.
Next, 100.7 parts by mass of functional particles A shown in Table 1 was added to the mixed liquid obtained by adjusting the pH, and the mixture was stirred for 5 minutes to obtain coating agent No. 4 for resin-containing layer.
The solid content of each raw material in the obtained Coating Agent No. 4 is shown in Table 2.

<Production Example 1-5: Coating agent for resin-containing layer No. 5>
3.5 parts by mass of a water-soluble polymer shown in Table 1 and 100 parts by mass of water were mixed and stirred for 5 minutes. Thereafter, the pH of the mixture of the water-soluble polymer and water was adjusted to 5.0 using 10% acetic acid.
Next, 14.9 parts by mass of functional particles C (manufactured by Chuo Rika Kogyo Co., Ltd., product name: Aquatex AC-3100, ethylene-methacrylic acid copolymer emulsion solution, average dispersed particle size 0.7 μm, minimum film formation temperature 100° C.) shown in Table 1 and 26.8 parts by mass of thermoplastic resin 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. This gave coating agent No. 5 for resin-containing layer.
The solid content of each raw material in the obtained Coating Agent No. 5 is shown in Table 2.

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

<Production Example 1-7: Coating agent for resin-containing layer No. 7>
3.5 parts by mass of a water-soluble polymer shown in Table 1 and 100 parts by mass of water were mixed and stirred for 5 minutes. Thereafter, the pH of the mixture of the water-soluble polymer and water was adjusted to 5.0 using 10% acetic acid.
Next, 14.9 parts by mass of functional particles D (manufactured by Sumitomo Seika Chemicals Co., Ltd., product name: Sepolsion G315, olefin resin emulsion, average dispersed particle size 1.5 μm, minimum film formation temperature 85° C.) described in Table 1 and 26.8 parts by mass of thermoplastic resin particles A described in Table 1 were added to the mixture obtained by adjusting the pH, and the mixture was stirred for 5 minutes. This gave coating agent No. 7 for resin-containing layer.
The solid content of each raw material in the obtained Coating Agent No. 7 is shown in Table 2.

(Seat manufacturing)
Sheets were manufactured using the raw materials shown in Table 3 below.

<Production Example 2-1: Sheet No. 1>
<<Step (2-1A)>>
77 parts by mass of PP-1 (manufactured by Mitsui Chemicals, Inc., trade name: Tafmer PN0040, ethylene-propylene copolymer) shown in Table 3, 22 parts by mass of CA-1 (manufactured by Bihoku Funka Kogyo Co., Ltd., trade name: Softon #1800, heavy calcium carbonate) shown in Table 3, and 1 part by mass of TI-1 (manufactured by Ishihara Sangyo Kaisha, Ltd., trade name: rutile titanium dioxide, Typeque CR-60) shown in Table 3 were mixed to obtain a mixture. The resulting mixture was kneaded in an extruder set at a temperature of 270 ° C., extruded from the extruder into a sheet, and cooled by a cooling device to obtain an unstretched sheet. The obtained unstretched sheet was heated again to a temperature of 150 ° C., and then stretched 4 times in the longitudinal direction (MD direction) using the difference in peripheral speed of the roll group to obtain a longitudinal 4-times stretched film.

<<Process (2-1B)>>
Separately from the step (2-1A), PP-1 shown in Table 3 was kneaded in an extruder set at a temperature of 270° C., and then extruded into a sheet to obtain an unstretched sheet. The sheet was laminated on one side of the longitudinally 4-fold stretched film obtained in step (2-1A) to obtain a laminated film having a two-layer structure.

<<Step (2-1C)>>
Next, the two-layer laminate film obtained in step (2-1B) was cooled to a temperature of 60° C., and then heated again to a temperature of 165° C., and stretched in the transverse direction (TD direction) using a tenter. The film was then annealed at 175° C., cooled to 60° C., and the edge portions were slit to obtain a laminated stretched film having a two-layer structure.

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

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

<<Process (2-2B)>>
Separately from the step (2-1A), PP-2 (manufactured by ExxonMobil, trade name: VISTAMAXX 3588FL, ethylene-propylene copolymer) shown in Table 3 was kneaded in an extruder set at a temperature of 270°C. The resulting unstretched sheet was laminated on one side of the longitudinally 4-fold stretched film obtained in step (2-1A) to obtain a two-layer laminate film. obtained.

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

<<Process (2-3B)>>
Separately from the step (2-1A), PP-4 (manufactured by Japan Polypropylene Corporation, product name: Novatec PP EG7F, ethylene-propylene copolymer) shown in Table 3 was fed to an extruder set at a temperature of 270°C. The mixture was kneaded and then extruded into a sheet to obtain a non-stretched sheet. The non-stretched sheet obtained was laminated on one side of the longitudinally 4-fold stretched film obtained in step (2-1A) to obtain a two-layered film. A laminated film having the structure was obtained.

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

<<Process (2-4B)>>
Separately from the step (2-1A), PP-5 (trade name: Wintec WFW4, ethylene-propylene copolymer, manufactured by Japan Polypropylene Corporation) shown in Table 3 was fed to an extruder set at a temperature of 270°C. The mixture was kneaded and then extruded into a sheet to obtain a non-stretched sheet. The non-stretched sheet obtained was laminated on one side of the longitudinally 4-fold stretched film obtained in step (2-1A) to obtain a two-layered film. A laminated film having the structure was obtained.

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

<<Process (2-5B)>>
Separately from the step (2-1A), PP-6 (manufactured by Japan Polypropylene Corporation, product name: Novatec PP MG3F, ethylene-propylene copolymer) shown in Table 3 was fed to an extruder set at a temperature of 270°C. The mixture was kneaded and then extruded into a sheet to obtain a non-stretched sheet. The non-stretched sheet obtained was laminated on one side of the longitudinally 4-fold stretched film obtained in step (2-1A) to obtain a two-layered film. A laminated film having the structure was obtained.

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

<<Process (2-6B)>>
Separately from the step (2-1A), PP-7 (manufactured by Japan Polypropylene Corporation, product name: Novatec PP MA3, propylene homopolymer) shown in Table 3 was kneaded in an extruder set at a temperature of 270°C. The resulting unstretched sheet was laminated on one side of the longitudinally 4-fold stretched film obtained in step (2-1A) to obtain a two-layer structure. A laminated film was obtained.

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

<<Process (2-7B)>>
Separately from step (2-1A), PP-5 and PP-7 shown in Table 3 were mixed in a mass ratio of 50:50 to obtain a mixture. The obtained mixture was subjected to an extrusion process set at a temperature of 270° C. The mixture was kneaded in a mixing machine, and then extruded into a sheet to obtain a non-stretched sheet. The non-stretched sheet obtained was laminated on one side of the longitudinally 4-fold stretched film obtained in step (2-1A). A laminated film having a two-layer structure was obtained.

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

<<Process (2-8B)>>
Separately from the step (2-1A), PP-5 and PP-7 shown in Table 3 were mixed in a mass ratio (PP-5:PP-7) of 40:60 to obtain a mixture. The 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 unstretched sheet obtained was stretched 4 times in the longitudinal direction in the step (2-1A). By laminating it on one side of the film, a laminated film with a two-layer structure was obtained.

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

<<Process (2-9B)>>
Separately from the step (2-1A), PE-1 (manufactured by Japan Polypropylene Corporation, product name: Novatec HD HJ362N, high density polyethylene) shown in Table 3 was kneaded in an extruder set at a temperature of 270°C. The resulting unstretched sheet was then laminated on one side of the longitudinally 4-fold stretched film obtained in step (2-1A) to form a two-layer laminate. The film was obtained.

<Sheet compression hardness>
Using a nanoindentation tester ENT-2100 manufactured by Elionix, a load-unload indentation test was performed five times for each type of layer from the surface side of the thermoplastic resin layer of the sheet using a Berkovich indenter (triangular pyramid tip) under the following conditions, and the indentation hardness of the surface layer was calculated from the average value of each. The results are shown in Table 4.
Temperature: 30°C
・Maximum load: 0.05mN
・Load speed: 0.005mN
Maximum load holding time: 1 second Surface detection method: Inclined method Surface detection threshold coefficient: 2.0
Spring compensation: None

Example 1
Coating agent No. 1 for resin-containing layer produced in Production Example 1-1 was applied to the surface of the thermoplastic resin layer of sheet No. 1 produced in Production Example 2-1. Coating agent No. 1 for resin-containing layer was applied 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. The sheet coated with coating agent No. 1 for resin-containing layer was dried in an oven at 60°C to form a resin-containing layer, thereby obtaining a laminate of Example 1.

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

<Label punching evaluation: Printed layer peelability>
The presence or absence of peeling of the printed layer was evaluated by the following method.
On the resin-containing layer of the laminate obtained in Examples 1 to 11 and Comparative Examples 1 to 4, 2000 sheets were printed using an offset printing machine (manufactured by Ryobi Ltd., machine name: RYOBI3300CR) and UV offset printing ink (manufactured by T&K TOKA Corporation, product name: BC161). The printed surface was irradiated with UV (irradiation amount 100 mJ/cm ² ) to solidify the ink and form a printed layer.
The obtained print was punched out into a label size of 120 mm x 60 mm using a rotary cut machine (MDT manufactured by Iwasaki Iron Works, Ltd.).
After punching out the labels to the size required for the labels, the state of peeling of the printed layer at the edge of the labels was visually observed and evaluated according to the following criteria. The results are shown in Table 5.
[Evaluation Criteria]
A (good): No peeling was observed.
B (Acceptable): Some peeling is observed, but no problems.
C (poor): Peeling is observed over the entire edge.

<Antistatic properties>
The surface of the resin-containing layer of the laminate obtained in Examples 1 to 8 and Comparative Examples 1 to 4 was measured in an environment of 23°C and 30% relative humidity using a STATICHO NEST METER (manufactured by SHISHIDO ELECTROSTATIC.LTD., product name: TYPES5109) in accordance with the half-life measurement method described in JIS L1094:1997 "Test method for electrostatic charge of woven and knitted fabrics". At this time, the measurement time from the end of the application was set to 300 seconds, and the electrostatic charge half-life S (Sec) was obtained. Evaluation was performed according to the following evaluation criteria. The results are shown in Table 5.
[Evaluation Criteria]
A (good): The charging half-life S is 30 seconds or less.
B (Acceptable): The charge half-life S is greater than 30 seconds and less than 300 seconds.
C: (poor) The charging half-life S exceeds 300 seconds.

<Suitability for thermal melt transfer>
(Ink transfer evaluation)
Printing on the laminates obtained in Examples 9 to 11 was carried out by printing a CODE39 barcode on the surface of the resin-containing layer of the laminate in an atmosphere at a temperature of 35° C. and a relative humidity of 85% using a barcode printer (product name: B-30-S5, manufactured by Tec Corporation) and a melt-type resin ink ribbon (product name: B110C, manufactured by Ricoh Co., Ltd.).

The ink transferability was evaluated by measuring the ANSI grade of the barcode printed on the laminate using a barcode verification machine (product name: LASERCHEK II, manufactured by Fuji Electric Refrigeration Co., Ltd.) The evaluation criteria for ink transferability are as follows, with ANSI grades A to C being considered acceptable.
[Evaluation Criteria]
A (Good): ANSI grade A or B (clear image is obtained)
B (Acceptable): ANSI grade C (the barcode is slightly faded, but still in working condition)
C (Poor): ANSI grade D to F (barcode is faint and line breaks occur)
D (Not acceptable): ANSI grade N/G (Cannot be recognized as a CODE39 barcode.)

When the indentation hardness of the sheet was 60 N/mm2 or ^less , peeling of the printed layer could be suppressed. When the indentation hardness of the sheet was 50 N/mm2 ^or less, peeling of the printed layer was further suppressed.
High density polyethylene tends to be more brittle than random polypropylene, so in Example 6, in which high density polyethylene was used instead of random polypropylene for the thermoplastic resin layer, part of the thermoplastic resin layer peeled off during sheet molding, contaminating the laminate surface.
Regarding stickiness of the sheets, the sheets No. 2 to No. 9 were less sticky than the sheet No. 1. In other words, from the viewpoint of stickiness of the sheets, the indentation hardness of the sheets is preferably 10 N/mm2 or ^more .

1a, 1b... Laminate, 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 (8)

A laminate comprising a sheet having a thermoplastic resin layer on one surface thereof, 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 thermoplastic resin of the resin-containing layer contains thermoplastic resin particles or a fused product of thermoplastic resin particles,
The minimum film-forming temperature of the thermoplastic resin particles is 40° C. or less,
The laminate, wherein the indentation hardness of the sheet is greater than 0 N/ ^mm2 and ^not greater than 60 N/mm2. The laminate according to claim 1 , wherein the thermoplastic resin in the resin-containing layer contains a polyurethane resin. The laminate according to claim 1 or 2 , wherein the thermoplastic resin layer contains random polypropylene. The laminate according to claim 3 , 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 4 , wherein the resin-containing layer contains functional particles. The laminate according to claim 5 , wherein the functional particles contain particles having a cationic metal oxide. The laminate according to claim 5 , wherein the functional particles contain olefin-based polymer particles. The laminate according to any one of claims 1 to 7 , wherein the sheet has a base layer and the thermoplastic resin layer provided on a surface of the base layer.

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