JP2023129232A - Laminate including ink and matte laminated film - Google Patents

Abstract

To provide a matte laminated film which has excellent film-forming property even when a plant-derived resin is used, and can obtain sufficient mat feeling, a laminate which is excellent in adhesion between the matte laminated film and a printing layer, and a packaging material composed of the laminated film or laminate.SOLUTION: A laminate is provided, formed by laminating at least a first base material layer and a printing layer, wherein the first base material layer is a matte laminated film of a surface resin layer (A) including a plant-derived high density polyethylene (a1), and a propylene-based resin (a2) including a propylene homopolymer (a2-1) and a propylene-ethylene block copolymer (a2-2), and a resin layer (B) containing a polyolefin-based resin (b1), and the printing layer is a layer formed by printing liquid printing ink.SELECTED DRAWING: None

Description

The present invention relates to a laminate in which at least a first base layer and a printed layer are laminated. Furthermore, the present invention relates to a packaging product including the laminate.

Packaging materials with a variety of designs are used in the packaging of foods such as bread and sweets, miscellaneous goods, magazines, etc. Among these, there is a growing need for matte packaging materials with matte surfaces. The matte packaging material has a texture similar to that of Japanese paper compared to general transparent packaging materials, so it brings out the luxurious feel of the contents. The matte packaging material is manufactured from a laminate including a matte multilayer film and a plurality of other layers.

In addition, in recent years, global demand for biomass raw materials has increased due to calls for building a recycling-oriented society that develops sustainably (sustainability) with consideration for the global environment, ecosystem, social economy, etc. In particular, major domestic distributors and food manufacturers are working hard to respond to COP21 and to achieve the goal of "ensuring sustainable production and consumption patterns," which is one of the Sustainable Development Goals (SDGs). As part of our efforts, we are actively promoting environmental impact reduction packages. Traditionally, efforts have been made to promote the "3Rs" (volume reduction, reuse, and recycling) in packaging to reduce environmental impact, but in recent years, from the perspective of saving petroleum resources, the use of mainly petroleum-derived ingredients has been promoted. In place of resin as a component, resins whose main raw materials are plant-derived components (hereinafter sometimes referred to as "plant-derived resins" or "biomass resins") are increasingly being adopted.

Biomass is reusable organic resources derived from plants and living things, excluding fossil resources. Biomass resin manufactured from plant-derived raw materials is produced by plants through a photosynthetic reaction using carbon dioxide and water in the atmosphere as raw materials, and even if such resin is incinerated and carbon dioxide is generated, The so-called ``carbon neutral'' concept is based on the idea that the balance of carbon dioxide in the atmosphere is positive, negative, or zero. Based on this idea, studies are actively being conducted in various fields to use carbon-neutral plant-derived biomass raw material-manufactured resins in various materials instead of fossil resource-derived resins. There is.

As biomass resins derived from plants, there are biodegradable resins represented by polylactic acid (PLA), but these resins have problems in general use in terms of cost and processability. On the other hand, as a general-purpose resin, demand for plant-based polyethylene, which is a renewable resource derived from sugarcane, is increasing worldwide, and as production volume increases, the cost is also becoming more general-purpose. General-purpose plant-based resins are often used in sanitary and food packaging containers, miscellaneous goods, and plastic bags for packaging that reduces environmental impact, but recently, they have been used in food packaging films. Recruitment is expanding.

As a resin film using a plant-derived resin, for example, a multilayer film containing a propylene-based resin as a main component and containing a plant-derived resin in some layers is disclosed (Patent Document 1). However, in the past, in laminates in which the first base layer and printing layer were laminated, each layer was formed mainly of petroleum-derived materials, so the biomass content of the laminate was low, and improvements were needed. . Furthermore, it has not been possible to achieve both a matte-like design with a matte surface.

Japanese Patent Application Publication No. 2021-175607

Although plant-derived biomass resins are highly environmentally friendly, they often exhibit properties different from petroleum-derived resins, and in some cases cannot simply be replaced. For example, when a film is produced by replacing a petroleum-derived resin with a plant-derived resin, various physical properties of the film such as impact resistance, rigidity, film formability, gloss, and haze may be impaired. In particular, increasing the proportion of plant-derived resin increases the influence on the physical properties of the film. Therefore, in a laminate in which the first base layer and the printed layer are laminated, it is necessary to increase the biomass level of the entire laminate while maintaining the function of the laminate.

The object of the present invention is to provide a matte laminated film that has excellent film formability even when the degree of biomass is increased using a plant-derived resin and provides a sufficient matte feel, and a matte laminated film that can be printed with the matte laminated film. It is an object of the present invention to provide a laminate having excellent adhesion to the layers, and a packaging material comprising a laminate film or a laminate thereof.

In an aspect of the invention,
A laminate in which at least a first base layer and a printing layer are laminated,
(1) The first base layer is
Plant-derived high-density polyethylene (a1) with a melt flow rate of 1 g/10 minutes or less (temperature 190 ° C., load 2.16 kg),
Containing propylene homopolymer (a2-1) and propylene-ethylene block copolymer (a2-2), melt flow rate is 0.5 g/10 minutes to 30 g/10 minutes (temperature 230°C, load a surface resin layer (A) containing a propylene resin (a2) of 2.16 kg);
A matte laminated film with a resin layer (B) containing a polyolefin resin (b1),
(2) A laminate is provided, wherein the printing layer is a layer formed by printing liquid printing ink.

Moreover, in an aspect of the present invention, the laminate is provided, wherein the printing layer is a layer formed by printing a liquid printing ink containing a plant-derived raw material. Further, the above-mentioned laminate is provided, in which the printing layer is on the surface resin layer (A) side of the first base layer.

In another aspect of the present invention, a packaging material including the laminate is provided. Moreover, it is preferable that the said packaging material is a packaging material for foods.

The laminate according to the present invention uses a matte laminate film that can provide a sufficient matte feel, and has a texture similar to that of Japanese paper, so it can bring out the luxurious feel of the contents. Furthermore, since the adhesion between the printed layer and the base material layer made of the matte laminate film is good, it is possible to provide a laminate with an excellent appearance and a packaging material including the same.

(definition of word)
In the present invention, "biomass" refers to "renewable organic resources derived from plants or organisms, excluding fossil resources." Furthermore, biomass resin refers to resin derived from plants.
Furthermore, in the present invention, "plant-derived" means that a plant or the like is used as a raw material, and "petroleum-derived" means that a fossil fuel such as petroleum is used as a raw material.
Furthermore, in the present invention, "liquid printing ink" refers to liquid ink, such as gravure printing ink or flexographic printing ink, which is applied to a printing method using a printing plate, and preferably gravure printing ink or flexographic printing ink. It's ink. Further, the liquid printing ink of the present invention does not contain an active energy curable component, that is, it is a liquid printing ink that is non-reactive with active energy rays.
Moreover, in the present invention, all "ink" refers to "printing ink". In addition, all "parts" refer to "parts by mass."

<Biomass degree>
In the present invention, "biomass degree" refers to the ratio of plant-derived components contained in a product to the total amount of the product.
<Laminated body>
The laminate of the present invention is a laminate in which at least a matte laminated film as a first base layer and a printed layer are laminated, and (1) the first base layer is
Plant-derived high-density polyethylene (a1) with a melt flow rate of 1 g/10 minutes or less (temperature 190 ° C., load 2.16 kg),
Containing propylene homopolymer (a2-1) and propylene-ethylene block copolymer (a2-2), melt flow rate is 0.5 g/10 minutes to 30 g/10 minutes (temperature 230°C, load a surface resin layer (A) containing a propylene resin (a2) of 2.16 kg);
A matte laminated film with a resin layer (B) containing a polyolefin resin (b1),
(2) The printing layer is a layer formed by printing liquid printing ink.

More specific configurations of the laminate of the present invention include:
(1) Matte laminated film/printed layer (2) Matte laminated film/printed layer/overcoat layer, etc., but are not limited thereto.
Further, the laminate of the present invention may include one or more other layers. Examples of the other layers include, but are not limited to, a base layer, an adhesive layer, a barrier layer, a second printed layer, and the like.
The base material layer may be a sealant film, an unstretched film, a stretched film, a metallized unstretched film, a metallized stretched film, or a transparent deposited film. When there are multiple base material layers, the multiple base material layers may have the same composition or different compositions. Further, there may be a plurality of adhesive layers, and the plurality of adhesive layers may have the same composition or different compositions.

In the present invention, the biomass degree of the laminate is preferably 5% or more, more preferably 5% or more and 60% or less, and even more preferably 10% or more and 60% or less. If the biomass degree is within the above range, the amount of petroleum-derived plastic used can be reduced, and the environmental load can be reduced.

The thickness of the laminate of the present invention is preferably 10 μm or more and 500 μm or less, more preferably 20 μm or more and 300 μm or less, and even more preferably 25 μm or more and 200 μm or less.

In addition to the first base layer and the printed layer, the laminate of the present invention includes other layers such as an overcoat layer, a barrier layer, an adhesive layer, other base layers, a second printed layer, and a third printed layer. It may contain layers. When there are two or more such other layers, they may have the same composition or different compositions.
Each layer constituting the laminate will be described below.

<First base layer>
The first base layer of the present invention is a matte laminated film having at least a surface resin layer (A) and a resin layer (B).

(Surface resin layer (A) of matte laminated film)
The surface resin layer (A) in the laminated film, which is the first base layer of the present invention, is made of plant-derived high-density polyethylene with a melt flow rate of 1 g/10 minutes or less (temperature 190°C, load 2.16 kg). (a1) and
Containing propylene homopolymer (a2-1) and propylene-ethylene block copolymer (a2-2), melt flow rate is 0.5 g/10 minutes to 30 g/10 minutes (temperature 230°C, load 2.16 kg) of propylene resin (a2).

The plant-derived high-density polyethylene (a1) used in the present invention is a biomass polyethylene resin produced from plant-derived ethylene using sugar cane, corn, beet, etc. as starting materials. Examples of the plant-derived high-density polyethylene (a1) include linear high-density polyethylene (LHDPE) and high-density polyethylene (HDPE), which may be used alone or in combination. Among these, high density polyethylene (HDPE) is particularly preferred.
The plant-derived high-density polyethylene (a1) preferably has a melt flow rate (temperature 190° C., load 2.16 kg) of 1 g/10 minutes or less. When the melt flow rate is 1 g/10 minutes or less, a matte film with a texture similar to Japanese paper can be obtained. A particularly preferred melt flow rate is in the range of 0.05 to 0.8 g/10 minutes.

Furthermore, the density of the above-mentioned plant-derived high-density polyethylene (a1) is in the range of 0.935 to 0.970 g/ ^cm3 , but the matte feel, mechanical strength, uniformity of the film, etc. of the resulting laminated film, etc. From this point of view, the range is more preferably 0.940 to 0.965 g/cm ³ .

The propylene resin (a2) used in the present invention contains a propylene homopolymer (a2-1) and a propylene-ethylene block copolymer (a2-2). By containing a propylene homopolymer (a2-1) and a propylene-ethylene block copolymer (a2-2) as the propylene resin, film forming properties can be improved, and the matte feel and surface roughness can be improved. This makes it easy to adjust the height.
As the propylene resin (a2) used in the present invention, resins other than the propylene homopolymer (a2-1) and the propylene-ethylene block copolymer (a2-2), such as propylene-ethylene random copolymer, propylene - Contains α-olefin copolymer (propylene-1-butene random copolymer, propylene-1-hexene random copolymer, etc.), propylene-ethylene-1-butene random copolymer, and metallocene catalyst-based polypropylene. You can leave it there.

The propylene resin (a2) used in the present invention preferably has an MFR (temperature 230° C., load 2.16 kg) of 0.5 g/10 minutes or more and 30 g/10 minutes or less. From the viewpoint of reducing shrinkage of the film during bag making and further improving the film formability of the film, it is preferably 4 g/10 minutes or more and 20 g/10 minutes or less, and 5 g/10 minutes or more and 15 g/10 minutes or less. It is more preferable that there be.
Further, the propylene resin (a2) used in the present invention preferably has a melting point of 120 to 172°C, more preferably 125 to 170°C. When the MFR and melting point are within these ranges, shrinkage of the film during bag making can be further reduced, and the film formability of the film is further improved.

In the surface resin layer (A) used in the present invention, the content of the plant-derived high density polyethylene (a1) used in the present invention is preferably 45% by mass or more, and preferably 50% by mass or more. preferable.

The ratio of the above-mentioned plant-derived high-density polyethylene (a1) and propylene resin (a2) is determined in order to give the resulting film a sufficient matte feel (high haze and low gloss). The mass ratio (a1)/(a2) of the density polyethylene (a1) and the propylene resin (a2) is preferably in the range of 60/40 to 40/60. When the usage ratio of the plant-derived high-density polyethylene (a1) is within the range, it is easier to obtain the desired matte feel, and it is possible to obtain a packaging bag with a film that has sufficient mechanical strength, especially impact strength, for practical use. can.

Furthermore, the mass ratio (a2-1)/(a2-2) of the propylene homopolymer (a2-1) and the propylene-ethylene block copolymer (a2-2) is in the range of 45/55 to 30/70. It is preferable that there be.

The total content of the plant-derived high-density polyethylene (a1) and propylene resin (a2) in the surface resin layer (A) used in the present invention is 80% by mass in the surface resin layer (A). It is preferably at least 85% by mass, more preferably at least 90% by mass. By setting it as the said range, it becomes easy to obtain a film with suitable mechanical strength. More preferably, the total content of the plant-derived high-density polyethylene (a1), the propylene homopolymer (a2-1), and the propylene-ethylene block copolymer (a2-2) is the same as that of the surface resin layer ( It is preferably 80% by mass or more, 85% by mass or more, and more preferably 90% by mass or more in A).

The surface resin layer (A) used in the present invention contains other components other than the above-mentioned plant-derived high-density polyethylene (a1) and propylene resin (a2) within a range that does not impair the effects of the present invention. You may. Examples of the other components include polystyrene resins, polyurethane resins, polyester resins, polyamide resins, and the like. Furthermore, a petroleum-derived ethylene resin may be used in combination with a plant-derived ethylene resin.

Further, in the laminated film used in the present invention, the surface roughness (Ra) of the surface resin layer (A) based on JIS B-0601 is preferably 0.5 to 2.0. When the surface roughness is within this range, a suitable matte film having the texture of Japanese paper can be obtained, so that the design can be improved.

In order to adjust the range of the surface roughness (Ra), the mass ratio of the plant-derived high-density polyethylene (a1) and the propylene resin (a2) used in the present invention must be adjusted as described above. It is sufficient to use the ratio a1)/(a2) of 60/40 to 40/60, and no particular adjustment is required.

The difference in MFR between the plant-derived high-density polyethylene (a1) and the propylene resin (a2) used in the present invention is preferably 5 g/10 minutes or more, more preferably 6 g/10 minutes or more. . By setting it as the said range, it becomes easy to obtain a suitable matte-like surface resin layer (A).

(Resin layer (B) of matte laminated film)
The laminated film used in the present invention is formed by laminating the above-mentioned surface resin layer (A) on a resin layer (B) containing a polyolefin resin (b1). By forming a film with such a multilayer structure, it can have a matte feel even when used alone, and can also exhibit strength etc. for use in packaging bags.

As the polyolefin resin (b1), various polyolefin resins used for packaging films can be used, such as propylene homopolymer, propylene-ethylene random copolymer, propylene-ethylene block copolymer, propylene-α - Propylene resins such as olefin copolymers, (propylene-1-butene random copolymers, propylene-1-hexene random copolymers, etc.), propylene-ethylene-1-butene random copolymers, metallocene catalyst-based polypropylene, etc. (b1-2), polyethylene resins such as very low density polyethylene (VLDPE), linear low density polyethylene (LLDPE), and low density polyethylene (LDPE), ethylene-vinyl acetate copolymer (EVA), ethylene-methyl Methacrylate copolymer (EMMA), ethylene-ethyl acrylate copolymer (EEA), ethylene-methyl acrylate (EMA) copolymer, ethylene-ethyl acrylate-maleic anhydride copolymer (E -EA-MAH), ethylene-based copolymers such as ethylene-acrylic acid copolymer (EAA), and ethylene-methacrylic acid copolymer (EMAA), as well as ionomers of ethylene-acrylic acid copolymer, ethylene- Ionomers such as methacrylic acid copolymers can be used. Among these, it is preferable to use a propylene resin because it can easily improve the adhesion with the surface resin layer (A). In this way, by using resins of the same type for the surface resin layer (A) and the resin layer (B), the interlayer strength of the laminated film can be strengthened. Particularly preferably used is a propylene-ethylene copolymer.

Moreover, in order to increase the degree of biomass, it is preferable to use a plant-derived resin as the polyolefin resin (b1). The plant-derived resin may be the same resin as the plant-derived high-density polyethylene (a1) used in the surface resin layer (A) or the same type of ethylene because it can easily improve the adhesion with the surface resin layer (A). It is preferable to use a resin based on the resin. Specifically, it is a polyethylene resin produced from plant-derived ethylene starting from sugarcane, corn, beet, etc., such as linear low-density polyethylene (LLDPE), linear medium-density polyethylene, etc. (LMDPE), linear high-density polyethylene (LHDPE), low-density polyethylene (LDPE), medium-density polyethylene (MDPE), high-density polyethylene (HDPE), etc. These can be used alone or in combination of two or more. You may also use it. Among these, linear low density polyethylene (b1-1) is particularly preferred.
The linear low density polyethylene preferably has a density of 0.925 g/cm ³ or less, more preferably 0.920 g/cm ³ or less. By setting the density of the linear low-density polyethylene used within the above range, it becomes easy to have suitable fusing strength, high impact resistance, and bag breakage resistance.

The MFR of the plant-derived polyethylene used for the resin layer (B) used in the present invention is preferably 0.1 to 30 g/10 minutes, particularly preferably 0.5 to 20 g/10 minutes. By setting it as 1 g/10 minutes or more, it becomes easy to obtain suitable film formability, and by setting it as 20 g/10 minutes or less, it becomes easy to obtain suitable moldability.

(biomass resin)
In order to improve the biomass degree of the laminate of the present invention, it is preferable to use a biomass resin, that is, a resin derived from plants, for the matte laminate film used in the present invention. In particular, it is preferable to use plant-derived high-density polyethylene (a1) for the surface resin layer (A) used in the present invention, and to use plant-derived ethylene resin for the resin layer (B).
Plant-derived resins are produced using plants such as sugarcane, and the production method is different from that of petroleum-derived resins, except for the production of monomers. There are no particular restrictions on the manufacturing method, and any known method can be used. Examples include production methods using Ziegler-Natta catalysts and metallocene catalysts.

Specifically, the catalyst system uses a titanium-containing compound itself or a titanium-containing compound supported on a carrier such as a magnesium compound as the main catalyst, and an organic aluminum compound as a co-catalyst. - A method in which polymerization is carried out by adding an olefin can be mentioned. This polymerization may be carried out by any process such as slurry polymerization, solution polymerization, or gas phase polymerization.

Further, a homogeneous catalyst may be used, such as a conventionally used catalyst consisting of a vanadium compound and an organoaluminum compound, or a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, etc. A metallocene system consisting of a transition metal compound such as zirconium, titanium, or hafnium having one or two ligands, a transition metal compound in which the ligand is geometrically controlled, and a cocatalyst such as aluminoxane or an ionic compound. Mention may also be made of homogeneous catalyst systems such as catalysts. The metallocene catalyst may be subjected to any process such as homogeneous polymerization in the presence of a solvent, slurry polymerization method, gas phase polymerization method, etc. using an organic aluminum compound if necessary.

Examples of commercial products of such plant-derived polyethylene include SGM9450F, SLL118, SLL118/21, SLL218, SLL318, SLH118, SLH218, and SLH0820 manufactured by Braskem.

The resin layer (B) used in the present invention is derived from plants, from the viewpoint of increasing the strength and rigidity of the laminated film, emphasizing the matte feel with the surface resin layer (A), and further increasing the biomass level of the laminated film. It is preferable to use a combination of linear low density polyethylene (b1-1) and one or more propylene resins (b1-2). In this case, the usage ratio is more preferably in the range of plant-derived linear low-density polyethylene (b1-1)/propylene resin (b1-2) = 5/95 to 30/70.

In the resin layer (B) used in the present invention, the content of the plant-derived linear low density polyethylene (b1-1) is 10% by mass or more from the viewpoint of high impact resistance and bag breakage resistance. The amount is preferably 15% by mass, and more preferably 15% by mass.

The total content of the polyolefin resin (b1) in the resin layer (B) used in the present invention is preferably 80% by mass or more, and preferably 85% by mass or more. It is more preferable that the amount is 90% by mass or more. By setting it as the said range, it becomes easy to obtain a film with suitable mechanical strength. Furthermore, the total content of the plant-derived linear low-density polyethylene (b1-1) and propylene resin (b1-2) is 80% by mass or more in the resin layer (B). The content is preferably 85% by mass or more, more preferably 90% by mass or more.

The resin layer (B) used in the present invention may contain a colored pigment. As the coloring pigment used in the resin layer (B), various coloring pigments that can be kneaded with the above-mentioned resin can be appropriately used. If you want the resulting laminated film to have a white Japanese paper-like appearance, you can use white pigments, and titanium oxide is particularly preferred because it is low cost, easy to handle, and easy to impart a suitable degree of whiteness. .

When the resin layer (B) contains a colored pigment, the content of the colored pigment in the resin layer (B) per unit area of the resin layer (B) is 1.2×10 ^{- 4} to 10×10 ⁻⁴ g/cm ² is preferable. By setting this content, suitable whiteness can be imparted, and it becomes easy to obtain a suitable Japanese paper-like design.

(Other layers of matte laminated film)
The matte laminated film in which the surface resin layer (A) and the resin layer (B) used in the present invention are laminated has an excellent balance between mechanical strength and heat sealability when used as a packaging bag. From this point of view, it is preferable to further have a sealing layer (C) on the resin layer (B) side.

The above sealing layer (C) is designed to easily provide sealing strength when heat-sealing the sealing layers (C) of laminated films to each other or to containers made of other materials. The type of resin can be selected depending on the use of the resulting laminated film. In particular, when used as a packaging bag and heat-sealing the sealing layers (C), it should contain a propylene-ethylene random copolymer in order to obtain appropriate sealing strength. is preferred. Furthermore, in order to adjust the seal strength, it is also possible to use an ethylene-α-olefin copolymer.

When the matte laminated film used in the present invention has a sealing layer (C), in order to adjust the physical property balance of the laminated film, a support layer (D) is provided between the resin layer (B) and the sealing layer (C). It is also preferable to provide. As the resin that can be used for the support layer (D), resins similar to the polyolefin resin (b1) exemplified in the resin layer (B) described above can be preferably exemplified, and the resins can be used alone or in a mixture of multiple types. . Among these, propylene resin, linear low density polyethylene (LLDPE), low density polyethylene (LDPE), etc. can be preferably used. It is also preferable to use a plant-derived polyolefin resin for the support layer (D) because the biomass degree of the laminate can be improved.

The matte laminated film used in the present invention has one or more other layers in addition to the surface resin layer (A), resin layer (B), seal layer (C), and support layer (D). You may do so. The other layers can be made of various resin materials used for packaging films, and are preferably provided between the resin layer (B) and the seal layer (C).

Each of the above layers contains ingredients such as an antifogging agent, an antistatic agent, a heat stabilizer, a nucleating agent, an antioxidant, a lubricant, an anti-blocking agent, a mold release agent, an ultraviolet absorber, a coloring agent, etc., as necessary. can be added within a range that does not impair the purpose of the present invention.

(Matt-like laminated film)
The total mass of polyethylene contained in the matte laminated film used in the present invention is preferably 20% by mass or more, more preferably 23% by mass or more, based on the mass of the matte laminated film, More preferably, the content is 24% by mass or more. In order to increase the biomass content by increasing the amount of plant-derived components in the matte laminated film, it is preferable that the total mass of the plant-derived polyethylene is 20% by mass or more, based on the mass of the matte laminated film, and 23% by mass or more. % or more, and even more preferably 24% by mass or more.
Furthermore, the total mass of polyethylene, preferably the total mass of plant-derived polyethylene, should be 24% by mass or more with respect to the total mass of the surface resin layer (A) and the resin layer (B) adjacent to the surface resin layer. It is preferably 27% by mass or more, and even more preferably 28% by mass.

The matte laminated film used in the present invention preferably has a total thickness in the range of 20 to 50 μm in order to obtain sufficient strength as a single film, especially for packaging relatively lightweight contents such as bread. When used for commercial purposes, the thickness is preferably 25 to 40 μm.

In order to give a sufficient matte feel (high haze and low gloss) to the matte laminated film used in the present invention, the thickness of the surface resin layer (A) should be 10 to 40% of the total thickness. It is preferable to do so. The thickness of the surface resin layer (A) is preferably 2 to 20 μm, more preferably 4 to 16 μm, since it is easy to obtain a suitable design.
Further, the thickness of the resin layer (B) is preferably 30 to 90% of the total thickness. The thickness of the resin layer (B) is preferably 6 to 45 μm, more preferably 10 to 30 μm.
Further, when a seal layer (C) is provided, it is preferable that the seal layer (C) accounts for 10 to 25% of the total thickness. The thickness of the seal layer (C) is preferably 2 to 12.5 μm, more preferably 3 to 10 μm.
When the support layer (D) is provided, the total thickness of the resin layer (B) and the support layer (D) is preferably 6 to 45 μm, and preferably 30 to 90% of the total thickness.

The haze of the matte laminated film used in the present invention is preferably 50% or more, more preferably 70% or more, particularly 80% or more in order to obtain a sufficient matte feel. preferable.

The gloss of the matte laminated film used in the present invention is preferably 20% or less, more preferably 10% or less, and 5% or less in order to suppress surface gloss and create a texture similar to Japanese paper. It is more preferable that it is the following.
Further, the rigidity of the matte laminated film is preferably 500 MPa or more, more preferably 600 MPa or more, and preferably 650 MPa or more in order to maintain suitable strength when applied as a packaging material. More preferred.
Further, the impact strength of the matte laminated film is preferably 0.15 J (23°C) or more, more preferably 0.17 J (23°C) or more. The impact strength is determined by holding the sample of the laminated film in a thermostatic chamber adjusted to 23° C. for 6 hours, and then measuring it by the film impact method using a spherical impact head with a diameter of 25.4 mm.

(Method for producing matte laminated film)
The method for producing the matte laminated film used in the present invention is not particularly limited, but for example, each resin or resin mixture used for the surface resin layer (A), resin layer (B), and seal layer (C) is , are heated and melted in separate extruders, and laminated in the order of (A)/(B)/(C) in the molten state by a method such as a coextrusion multilayer die method or a feed block method, followed by inflation. For example, a coextrusion method in which the film is formed by a T-die chill roll method or the like can be mentioned. When the matte laminated film includes a support layer (D), it may be laminated in the order of (A)/(B)/(D)/(C). This coextrusion method is preferable because it allows the ratio of the thickness of each layer to be adjusted relatively freely, and a coextruded laminated film with excellent hygiene and cost performance can be obtained. Furthermore, since there is a large difference in melting point between the high density polyethylene (a1) and the propylene resin (a2) used in the present invention, the appearance of the film may deteriorate during coextrusion processing. In order to suppress such deterioration, it is preferable to use the T-die chill roll method, which allows melt extrusion to be performed at a relatively high temperature.

Since the matte laminated film used in the present invention is obtained as a substantially unstretched laminated film by the above-described manufacturing method, secondary forming such as deep drawing by vacuum forming is also possible.

Furthermore, when printing etc. are performed on the surface resin layer (A) of the matte laminated film used in the present invention, surface treatment is applied to the resin layer (A) in order to improve adhesion with printing ink, etc. It is preferable. When pasting other films on the surface of the resin layer (B) or seal layer (C), in order to improve the adhesion with the adhesive, ) is preferably subjected to surface treatment. Examples of such surface treatments include surface oxidation treatments such as corona treatment, plasma treatment, chromic acid treatment, flame treatment, hot air treatment, ozone/ultraviolet treatment, and surface roughening treatments such as sandblasting. Corona treatment is preferred.

The seal layer (C) of the matte laminated film used in the present invention is used as a heat seal layer, and the seal layers (C) are overlapped and heat sealed, or the surface resin layer (A) is By overlapping and heat-sealing the seal layer (C) and the seal layer (C), a packaging bag having the seal layer (C) on the inside can be produced. For example, cut two pieces of the matte laminated film into the desired packaging bag size, overlap them and heat seal the three sides to form a bag, and then It can be used as a packaging bag by filling it with contents from one side and sealing it by heat sealing. Furthermore, it is also possible to form a packaging bag by sealing the ends of a roll of film into a cylindrical shape using an automatic packaging machine and then sealing the top and bottom.

Furthermore, the matte laminated film used in the present invention and other films may be laminated to form a composite film. Other films may be provided on the surface resin layer (A) side, or on the resin layer (B) or seal layer (C) side; ) side is preferably provided with a sealant film.

<Print layer>
The printing layer used in the present invention is a layer in which a desired pattern is formed using liquid printing ink in order to impart cosmetic properties, various information regarding the contents, and functionality to the printed material. The printing layer is formed by printing a gravure printing ink or a flexographic printing ink (hereinafter referred to as liquid printing ink) containing a binder resin and a colorant.

The printed layer used in the present invention may be a single layer or may have multiple printed layers. When there are multiple printing layers, the liquid printing ink used for each printing layer may be the same, the same composition with different colorants, or the liquid printing ink with different compositions. Also good.

(liquid printing ink)
The liquid printing ink used in the present invention is used as a gravure printing ink or a flexographic printing ink, and is roughly divided into organic solvent-based liquid printing ink that uses an organic solvent as its main solvent, and water-based liquid printing ink that uses water as its main solvent. be done. Here, we will mainly explain the commonly used organic solvent type liquid printing ink.

(Organic solvent-based liquid printing ink)
For organic solvent type liquid printing ink, a pigment dispersion is obtained by dispersing a mixture containing a binder resin, an organic solvent medium, a dispersant, an antifoaming agent, etc. using a dispersing machine. It is obtained by adding a resin, an aqueous medium, and optionally additives such as a leveling agent to the obtained pigment dispersion, and stirring and mixing. As a dispersing machine, a bead mill, an Eiger mill, a sand mill, a gamma mill, an attritor, etc., which are commonly used in the production of gravure and flexo printing inks, are used.

The ink viscosity of the above-mentioned organic solvent-based liquid printing ink is 10 mPa. From the viewpoint of work efficiency during ink production and printing, it is preferably in the range of 1000 mPa·s or more. Note that the above viscosity is a viscosity measured at 25° C. using a B-type viscometer manufactured by Tokimec.

The viscosity of the ink can be adjusted by appropriately selecting the type and amount of raw materials, binder resin, pigment, organic solvent, etc. used. Furthermore, the viscosity of the ink can also be adjusted by adjusting the particle size and particle size distribution of the pigment in the ink.

(Creation of printed matter)
The above organic solvent-based liquid printing ink has excellent adhesion to various substrates and can be used for printing on paper, synthetic paper, thermoplastic resin film, plastic products, steel plates, etc. The ink is useful as an ink for gravure printing using a gravure printing plate made by et al., or for flexography printing using a flexo printing plate made of a resin plate or the like.

The film thickness of a liquid printing ink formed by a gravure printing method or a flexographic printing method using the organic solvent type liquid printing ink is, for example, 10 μm or less, preferably 5 μm or less.

(Binder resin (A))
Binder resins (A) used in the liquid printing ink used in the present invention include nitrified cotton, cellulose resins such as cellulose acetate propionate (CAP) and cellulose acetate butyronate (CAB), Vinyl chloride resins such as polyamide resins, urethane resins, acrylic resins, vinyl chloride-vinyl acetate copolymer resins, chlorinated polypropylene resins, ethylene-vinyl acetate copolymer resins, vinyl acetate resins, polyvinyl chloride resins, Examples include polyester resin, alkyd resin, rosin resin, rosin-modified maleic acid resin, ketone resin, cyclized rubber, chlorinated rubber, butyral, petroleum resin, and the like.

(cellulose resin)
Examples of cellulose resins include cellulose acetate propionate, cellulose acetate butyrate and other cellulose ester resins, nitrocellulose (also referred to as nitrified cotton), hydroxyalkylcellulose, and carboxyalkylcellulose. The cellulose ester resin preferably has an alkyl group, and examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, and a hexyl group. may have a substituent.
Among the cellulose resins mentioned above, cellulose acetate propionate, cellulose acetate butyrate, and nitrocellulose are preferred. Particularly preferred is nitrocellulose. The weight average molecular weight is preferably 5,000 to 200,000, more preferably 10,000 to 50,000. Further, those having a glass transition temperature of 120°C to 180°C are preferable.
Nitrocellulose (nitrocellulose) is a nitric acid ester obtained by reacting natural cellulose with nitric acid and replacing three hydroxyl groups in the six-membered ring of the anhydrous glucopyranose group in natural cellulose with nitric acid groups. preferable.

The amount of nitrocellulose (nitrified cotton) added is preferably 0.15 to 40% by mass, more preferably 1.0 to 35% by mass, based on the total amount of liquid printing ink.

(Polyamide resin)
The polyamide resin is, for example, an organic solvent-soluble thermoplastic polyamide obtained by polycondensation of a polybasic acid and a polyvalent amine. In particular, it is preferably a polyamide resin containing a reaction product of an acid component containing a polymerized fatty acid and/or a dimer acid and an aliphatic and/or aromatic polyamine, and further containing a portion of primary and secondary monoamines. is preferred.
Polybasic acids used as raw materials for the polyamide resin include, but are not limited to, adipic acid, sebacic acid, azelaic acid, phthalic anhydride, isophthalic acid, suberic acid, glutaric acid, fumaric acid, Examples include pimelic acid, oxalic acid, malonic acid, succinic acid, maleic acid, terephthalic acid, 1,4-cyclohexyldicarboxylic acid, trimellitic acid, dimer acid, hydrogenated dimer acid, and polymerized fatty acids. A polyamide resin containing a structure derived from a polymerized fatty acid as a main component (50% by mass or more in the polyamide resin) is preferable. Here, the polymerized fatty acid is obtained by a cyclization reaction of an unsaturated fatty acid, and includes monobasic fatty acids, dimerized fatty acids, trimerized fatty acids, and the like. The fatty acids constituting the dimer acid or polymerized fatty acid include those derived from natural oils such as soybean oil, palm oil, and rice bran oil, and those derived from oleic acid and linoleic acid are preferred.
A monocarboxylic acid can also be used in combination with the polybasic acid. Examples of monocarboxylic acids used in combination include acetic acid, propionic acid, lauric acid, palmitic acid, benzoic acid, and cyclohexanecarboxylic acid.

Examples of polyvalent amines include polyamines, primary or secondary monoamines, and the like. Examples of polyamines used in polyamide resins include aliphatic diamines such as ethylene diamine, propylene diamine, hexamethylene diamine, and methylaminopropylamine, and aliphatic polyamines such as diethylene triamine and triethylene tetramine. , cyclohexylene diamine, isophorone diamine, and the like. Furthermore, examples of the aromatic aliphatic polyamine include xylylene diamine, and examples of the aromatic polyamine include phenylene diamine and diaminodiphenylmethane. Furthermore, examples of primary and secondary monoamines include n-butylamine, octylamine, diethylamine, monoethanolamine, monopropanolamine, diethanolamine, dipropanolamine, and the like.
The amount of the polyamide resin added is preferably 0.15 to 40% by mass, more preferably 1.0 to 35% by mass, based on the total amount of the liquid printing ink.

(Urethane resin)
The urethane resin is not particularly limited as long as it is a polyurethane resin obtained by reacting a polyol and a polyisocyanate. As the polyol, for example, various known polyols commonly used in the production of polyurethane resins can be used, and one type or two or more types may be used in combination. For example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, 1,3-butanediol , 1,4-butanediol, neopentyl glycol, pentanediol, 3-methyl-1,5pentanediol, hexanediol, octanediol, 1,4-butynediol, 1,4-butylenediol, diethylene glycol, triethylene glycol , dipropylene glycol, glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, 1,2,4-butanetriol, sorbitol, pentaesthritol, and other saturated or unsaturated low-molecular polyols (1), These low molecular weight polyols (1), sebacic acid, adipic acid, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, glutaric acid, pimelic acid Polyester polyols (2) obtained by dehydration condensation or polymerization of polyhydric carboxylic acids such as , superic acid, azelaic acid, trimellitic acid, pyromellitic acid, and dimer acid, or their anhydrides; cyclic ester compounds, e.g. Polyester polyols (3) obtained by ring-opening polymerization of lactones such as polycaprolactone, polyvalerolactone, poly(β-methyl-γ-valerolactone); Polycarbonate polyols (4) obtained by reaction with dimethyl carbonate, diphenyl carbonate, ethylene carbonate, phosgene, etc.; polybutadiene glycols (5); glycols obtained by adding ethylene oxide or propylene oxide to bisphenol A (6) ; By copolymerizing one or more hydroxyethyl, hydroxypropyl acrylate, acrylic hydroxybutyl, etc., or their corresponding methacrylic acid derivatives, etc. in one molecule with, for example, acrylic acid, methacrylic acid, or an ester thereof. Examples include the resulting acrylic polyol (7).

Examples of the polyisocyanate include various known aromatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, etc. that are commonly used in the production of polyurethane resins. For example, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 1-methyl-2,4-phenylene diisocyanate, 1-methyl-2,6-phenylene diisocyanate, 1-methyl-2,5-phenylene diisocyanate, 1 -Methyl-2,6-phenylene diisocyanate, 1-methyl-3,5-phenylene diisocyanate, 1-ethyl-2,4-phenylene diisocyanate, 1-isopropyl-2,4-phenylene diisocyanate, 1,3-dimethyl-2 , 4-phenylene diisocyanate, 1,3-dimethyl-4,6-phenylene diisocyanate, 1,4-dimethyl-2,5-phenylene diisocyanate, diethylbenzene diisocyanate, diisopropylbenzene diisocyanate, 1-methyl-3,5-diethylbenzene diisocyanate, 3-Methyl-1,5-diethylbenzene-2,4-diisocyanate, 1,3,5-triethylbenzene-2,4-diisocyanate, naphthalene-1,4-diisocyanate, naphthalene-1,5-diisocyanate, 1-methyl -Naphthalene-1,5-diisocyanate, naphthalene-2,6-diisocyanate, naphthalene-2,7-diisocyanate, 1,1-dinaphthyl-2,2'-diisocyanate, biphenyl-2,4'-diisocyanate, biphenyl-4 , 4'-diisocyanate, 3-3'-dimethylbiphenyl-4,4'-diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, diphenylmethane-2,4-diisocyanate, etc. ; Tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, trimethylhexamethylene diisocyanate, 1,3-cyclopentylene diisocyanate, 1,3-cyclohexylene diisocyanate, 1,4-cyclohexylene diisocyanate, 1,3-di(isocyanate) methyl)cyclohexane, 1,4-di(isocyanatomethyl)cyclohexane, lysine diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 2,4'-dicyclohexylmethane diisocyanate, 2,2'-dicyclohexylmethane diisocyanate, 3, Aliphatic or alicyclic polyisocyanates such as 3'-dimethyl-4,4'-dicyclohexylmethane diisocyanate can be used. These polyisocyanates may be used alone or in combination of two or more. Among these, these diisocyanate compounds can be used alone or in combination of two or more.

Chain extenders can also be used. Examples of chain extenders include ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, isophoronediamine, dicyclohexylmethane-4,4'-diamine, 2-hydroxyethylethylenediamine, 2-hydroxyethylpropyldiamine, etc. , 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropyruethylenediamine, di-2-hydroxypropyleethylenediamine, di- Amines having a hydroxyl group in the molecule such as 2-hydroxypropylethylenediamine can also be used. These chain extenders can be used alone or in combination of two or more.

Moreover, a monovalent active hydrogen compound can also be used as a terminal capping agent for the purpose of stopping the reaction. Examples of such compounds include dialkylamines such as di-n-butylamine, and alcohols such as ethanol and isopropyl alcohol. Furthermore, especially when it is desired to introduce a carboxyl group into the polyurethane resin, amino acids such as glycine and L-alanine can be used as a reaction terminator. These terminal capping agents can be used alone or in combination of two or more.
The weight average molecular weight of the urethane resin is preferably in the range of 10,000 to 100,000, more preferably in the range of 15,000 to 80,000.

The urethane resin is particularly preferably a polyester polyol made of a polycarboxylic acid having 7 or more carbon atoms and two or more carboxyl groups, and a compound having two or more hydroxyl groups, which is reacted with a polyisocyanate. This is a urethane resin (A).

Examples of polycarboxylic acids having 7 or more carbon atoms and two or more carboxyl groups include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, and anhydrides of these acids, pimelic acid, and suberin. acids, aliphatic dicarboxylic acids such as azelaic acid, sebacic acid and dimer acid, tricarboxylic acids such as trimellitic acid and its anhydrides, benzenetetracarboxylic acid, benzenepentacarboxylic acid, benzenehexacarboxylic acid and anhydrides of these acids etc. can be used. These polybasic acids may be used alone or in combination of two or more. Among these, it is preferable to use sebacic acid and dimer acid in that they provide good adhesion to a wide variety of film substrates, and these may be used alone or in combination.

The above-mentioned polyester polyol may use other polycarboxylic acids as needed, and various known polycarboxylic acids commonly used in the production of polyester polyols may be used, and one or two types of polycarboxylic acids may be used. The above may be used in combination. Examples include adipic acid, maleic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, and glutaric acid.

In addition, as global awareness of environmental issues has increased in recent years, attention has been increasing to raw materials derived from biomass resources such as plants, rather than petroleum-derived raw materials that have an impact on global warming, and the use of these raw materials is also increasing. It is possible. Examples of polycarboxylic acids derived from biomass resources include sebacic acid, dimer acid, succinic acid, succinic anhydride, and adipic acid.

Examples of the above compounds having two or more hydroxyl groups include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, Glycols such as ethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol; 2-methyl-1,5-pentanediol, 3-methyl-1, 5-pentanediol, 1,2-butanediol, 1,3-butanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,2-propanediol, 2-methyl-1,3-propane Diol, neopentyl glycol, 2-isopropyl-1,4-butanediol, 2,4-dimethyl-1,5-pentanediol 2,4-diethyl-1,5-pentanediol, 2-ethyl-1,3- Glycols with branched structures such as hexanediol, 2-ethyl-1,6-hexanediol, 3,5-heptanediol, 2-methyl-1,8-octanediol; glycerin, trimethylolpropane, trimethylolethane, penta Erythritol, sorbitol, etc. can be used. These compounds may be used alone or in combination of two or more.

Further, like polyhydric carboxylic acids, it is also possible to use raw materials derived from biomass resources such as plants for compounds having two or more hydroxyl groups. Examples of compounds having two or more hydroxyl groups derived from biomass resources include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, diethylene glycol, and glycerin.

The number average molecular weight of the polyester polyol is preferably in the range of 500 to 8,000, more preferably in the range of 800 to 7,000, even more preferably in the range of 900 to 6,000. .

Furthermore, it is more preferable that the polyurethane resin (A) contains polyether polyol in an amount of 1 to 40% by mass based on the polyurethane resin. As the polyether polyol, various known ether polyols commonly used in the production of polyurethane resins can be used, and one type or two or more types may be used in combination. Examples include polyether polyols of polymers or copolymers of ethylene oxide, propylene oxide, tetrahydrofuran, and the like. The number average molecular weight of the polyether polyol is more preferably from 100 to 3,500.

The concomitant polyol, polyisocyanate compound, chain extender, terminal capping agent, etc. used as necessary in the polyurethane resin (A) used in the liquid printing ink composition used in the present invention can be used as described above. .
The weight average molecular weight of the polyurethane resin (A) is preferably within the range of 10,000 to 100,000, more preferably within the range of 15,000 to 95,000.

The amount of the urethane resin added is preferably 0.15 to 40% by mass, more preferably 1.0 to 35% by mass, based on the total amount of the liquid printing ink.

(acrylic resin)
The acrylic resin is not particularly limited as long as it is copolymerized with a polymerizable monomer containing (meth)acrylic acid ester as a main component. Examples of polymerizable monomers include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, iso-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n -Octyl (meth)acrylate, iso-octyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, iso-nonyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, methoxyethyl ( Examples include meth)acrylate, ethoxyethyl (meth)acrylate, phenoxyethyl (meth)acrylate, and the like. The polymerization method is not particularly limited, and those obtained by known bulk polymerization, solution polymerization, emulsion polymerization, suspension polymerization, etc. can be used.
The weight average molecular weight of the acrylic resin is preferably in the range of 5,000 to 200,000, more preferably in the range of 10,000 to 100,000.
Further, the amount of acrylic resin added is preferably 0.15 to 40% by mass, more preferably 1.0 to 35% by mass, based on the total amount of liquid printing ink.

(polyester resin)
The polyester resin is not particularly limited as long as it is a polyester resin obtained by reacting alcohol and carboxylic acid using a known esterification polymerization reaction.
Alcohols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, 1,3-butane Diol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,2-pentanediol, 3-methyl-1,5-pentanediol, hexanediol, octanediol, 1,4-butynediol , 1,4-butylene diol, diethylene glycol, triethylene glycol, dipropylene glycol, glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, 1,2,4-butanetriol, sorbitol, pentaes Examples include litol, 1,4-cyclohexanediol, 1,2-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, spiroglycol, and isosorbide. These can be used alone or in combination of two or more. Among these, polyfunctional alcohols are preferred.
Carboxylic acids include formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oleic acid, linoleic acid, oxalic acid, and malonic acid. , succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, 1,4-cyclohexanedicarboxylic acid, and the like. These can be used alone or in combination of two or more. Among these, polyfunctional carboxylic acids are preferred.
The weight average molecular weight of the polyester resin is preferably 500 to 6,000. The amount of the polyester resin added is preferably 0.15 to 40% by mass, more preferably 1.0 to 35% by mass based on the total amount of liquid printing ink. .

(vinyl chloride-vinyl acetate copolymer resin)
As the vinyl chloride resin, vinyl chloride-vinyl acetate copolymer resin is widely used and preferred. The vinyl chloride-vinyl acetate copolymer resin is not particularly limited as long as it is a copolymer of vinyl chloride and vinyl acetate. The weight average molecular weight is preferably 5,000 to 100,000, more preferably 10,000 to 70,000. In 100% by mass of the solid content of the vinyl chloride-vinyl acetate copolymer resin, the structure derived from the vinyl acetate monomer is preferably 1 to 30% by mass, and the structure derived from the vinyl chloride monomer is preferably 70 to 95% by mass. In this case, the solubility in organic solvents is improved, and furthermore, the adhesion to the substrate, the physical properties of the coating, the scratch resistance, etc. are improved.
Also preferred are those containing a hydroxyl group derived from a vinyl alcohol structure from the viewpoint of solubility in organic solvents. The hydroxyl value is preferably 20 to 200 mgKOH/g. Further, the glass transition temperature is preferably 50°C to 90°C.
The amount of vinyl chloride-vinyl acetate copolymer resin added is preferably 0.15 to 40% by weight, more preferably 1.0 to 35% by weight based on the total amount of the ink.

(rosin resin)
The rosin-based resin is not particularly limited as long as it has a rosin skeleton, but rosin-modified maleic acid resins, rosin esters, rosin phenols, polymerized rosins, and the like are preferred. It is preferable that the softening point (according to the ring and ball method) is 90 to 200°C. Among these, cellulose resins, polyamide resins, urethane resins, acrylic resins, and vinyl chloride resins are preferred. In particular, it is preferable that the binder resin contains at least two types of resins.
Preferably, it is selected from urethane resin/vinyl chloride resin, urethane resin/cellulose resin, polyamide resin/cellulose resin, acrylic resin/cellulose resin, and vinyl chloride resin/cellulose resin. It is a combination in which the two resins preferably contain a total of 80 to 100% by mass, and most preferably 90 to 100% by mass, based on 100% by mass of the binder resin (A).

Furthermore, urethane resin/vinyl chloride resin, urethane resin/cellulose resin, polyamide resin/cellulose resin, acrylic resin/cellulose resin, vinyl chloride resin/cellulose resin, The mass ratio of each is preferably 95/5 to 20/80. More preferably, the mass ratio is 90/10 to 50/50. This combination provides excellent basic properties desired for coating agents such as abrasion resistance, blocking resistance, heat resistance, and oil resistance.

(hardening agent)
Further, a curing agent may be used in combination with the binder resin (A). As the curing agent, any general-purpose curing agent for organic solvent-based gravure printing inks may be used, but isocyanate-based curing agents are most commonly used.
The amount of the isocyanate compound added is preferably in the range of 0.3% by mass to 10.0% by mass based on the solid content of the liquid printing ink from the viewpoint of curing efficiency, and if it is 1.0% by mass to 7.0% by mass. More preferred.

The binder resin (A) is preferably used in an amount of 0.15 to 50% by weight, most preferably 1 to 40% by weight, based on the liquid printing ink.

(Organic solvent)
The organic solvent used in the liquid printing ink used in the present invention is not particularly limited, but includes aromatic hydrocarbon organic solvents such as toluene, xylene, Solvesso #100 and Solvesso #150, hexane, methylcyclohexane, and heptane. , aliphatic hydrocarbon organic solvents such as octane and decane, various ester organic solvents such as methyl acetate, ethyl acetate, isopropyl acetate, n-propyl acetate, butyl acetate, amyl acetate, ethyl formate, and butyl propionate. . In addition, water-miscible organic solvents include alcohols such as methanol, ethanol, propanol, butanol, and isopropyl alcohol, ketones such as acetone, methyl ethyl ketone, and cyclohaxanone, ethylene glycol (mono, di) methyl ether, and ethylene glycol (mono, di) ethyl. Ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, monobutyl ether, diethylene glycol (mono, di) methyl ether, diethylene glycol (mono, di) ethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, triethylene glycol (mono, di) Examples include various glycol ether-based organic solvents such as di)methyl ether, propylene glycol (mono,di)methyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and dipropylene glycol (mono,di)methyl ether. These can be used alone or in combination of two or more.

In addition, from the viewpoint of both work hygiene during printing and the toxicity of packaging materials, use ethyl acetate, propyl acetate, isopropanol, normal propanol, etc., and do not use aromatic solvents such as toluene or ketone solvents such as methyl ethyl ketone. is more preferable.

(colorant)
The liquid printing ink used in the present invention contains a colorant, and can be used as a liquid printing ink containing a colorant used for design printing and the like for the purpose of imparting cosmetic properties. Examples of the colorant include inorganic pigments, organic pigments, and dyes used in general inks, paints, recording materials, etc., with pigments being preferred. Examples of organic pigments include soluble azo, insoluble azo, azo, phthalocyanine, halogenated phthalocyanine, anthraquinone, anthanthrone, dianthraquinonyl, anthrapyrimidine, perylene, perinone, quinacridone, Examples include thioindigo-based, dioxazine-based, isoindolinone-based, quinophthalone-based, azomethineazo-based, flavanthrone-based, diketopyrrolopyrrole-based, isoindoline-based, indanthrone-based, and carbon black-based pigments. Also, for example, Carmine 6B, Lake Red C, Permanent Red 2B, Disazo Yellow, Pyrazolone Orange, Carmine FB, Chromophthal Yellow, Chromophthal Red, Phthalocyanine Blue, Phthalocyanine Green, Dioxazine Violet, Quinacridone Magenta, Quinacridone Red, Indance. Examples include lon blue, pyrimidine yellow, thioindigo bordeaux, thioindigo magenta, perylene red, perinone orange, isoindolinone yellow, aniline black, diketopyrrolopyrrole red, and daylight fluorescent pigments. Furthermore, both non-acid-treated pigments and acid-treated pigments can be used. Specific examples of preferred organic pigments are listed below.

Examples of black pigments include C.I. I. Pigment Black 1, C. I. Pigment Black 6, C. I. Pigment Black 7, C. I. Pigment Black 9, C. I. Pigment Black 20 and the like.

Examples of indigo pigments include C.I. I. Pigment Blue 15, C. I. Pigment Blue 15:1, C. I. Pigment Blue 15:2, C. I. Pigment Blue 15:3, C. I. Pigment Blue 15:4, C. I. Pigment Blue 15:5, C. I. Pigment Blue 15:6, C. I. Pigment Blue 16, C. I. Pigment Blue 17:1, C. I. Pigment Blue 22, C. I. Pigment Blue 24:1, C. I. Pigment Blue 25, C. I. Pigment Blue 26, C. I. Pigment Blue 60, C. I. Pigment Blue 61, C. I. Pigment Blue 62, C. I. Pigment Blue 63, C. I. Pigment Blue 64, C. I. Pigment Blue 75, C. I. Pigment Blue 79, C. I. Pigment Blue 80 and the like.

Examples of green pigments include C.I. I. Pigment Green 1, C. I. Pigment Green 4, C. I. Pigment Green 7, C. I. Pigment Green 8, C. I. Pigment Green 10, C. I. Pigment Green 36 and the like.

Examples of red pigments include C.I. I. Pigment Red 1, C. I. Pigment Red 2, C. I. Pigment Red 3, C. I. Pigment Red 4, C. I. Pigment Red 5, C. I. Pigment Red 6, C. I. Pigment Red 7, C. I. Pigment Red 8, C. I. Pigment Red 9, C. I. Pigment Red 10, C. I. Pigment Red 11, C. I. Pigment Red 12, C. I. Pigment Red 15, C. I. Pigment Red 16, C. I. Pigment Red 17, C. I. Pigment Red 18, C. I. Pigment Red 19, C. I. Pigment Red 20, C. I. Pigment Red 21, C. I. Pigment Red 22, C. I. Pigment Red 23, C. I. Pigment Red 31, C. I. Pigment Red 32, C. I. Pigment Red 38, C. I. Pigment Red 41, C. I. Pigment Red 43, C. I. Pigment Red 46, C. I. Pigment Red 48, C. I. Pigment Red 48:1, C.I. I. Pigment Red 48:2, C. I. Pigment Red 48:3, C.I. I. Pigment Red 48:4, C.I. I. Pigment Red 48:5, C.I. I. Pigment Red 48:6, C. I. Pigment Red 49, C. I. Pigment Red 49:1, C.I. I. Pigment Red 49:2, C. I. Pigment Red 49:3, C.I. I. Pigment Red 52, C. I. Pigment Red 52:1, C.I. I. Pigment Red 52:2, C. I. Pigment Red 53, C. I. Pigment Red 53:1, C.I. I. Pigment Red 53:2, C. I. Pigment Red 53:3, C.I. I. Pigment Red 54, C. I. Pigment Red 57, C. I. Pigment Red 57:1, C.I. I. Pigment Red 58, C. I. Pigment Red 58:1, C.I. I. Pigment Red 58:2, C.I. I. Pigment Red 58:3, C. I. Pigment Red 58:4, C. I. Pigment Red 60:1, C.I. I. Pigment Red 63, C. I. Pigment Red 63:1, C.I. I. Pigment Red 63:2, C.I. I. Pigment Red 63:3, C.I. I. Pigment Red 64:1, C.I. I. Pigment Red 68, C. I. Pigment Red 68, C. I. Pigment Red 81:1, C.I. I. Pigment Red 83, C. I. Pigment Red 88, C. I. Pigment Red 89, C. I. Pigment Red 95, C. I. Pigment Red 112, C. I. Pigment Red 114, C. I. Pigment Red 119, C. I. Pigment Red 122, C. I. Pigment Red 123, C. I. Pigment Red 136, C. I. Pigment Red 144, C. I. Pigment Red 146, C. I. Pigment Red 147, C. I. Pigment Red 149, C. I. Pigment Red 150, C. I. Pigment Red 164, C. I. Pigment Red 166, C. I. Pigment Red 168, C. I. Pigment Red 169, C. I. Pigment Red 170, C. I. Pigment Red 171, C. I. Pigment Red 172, C. I. Pigment Red 175, C. I. Pigment Red 176, C. I. Pigment Red 177, C. I. Pigment Red 178, C. I. Pigment Red 179, C. I. Pigment Red 180, C. I. Pigment Red 181, C. I. Pigment Red 182, C. I. Pigment Red 183, C. I. Pigment Red 184, C. I. Pigment Red 185, C. I. Pigment Red 187, C. I. Pigment Red 188, C. I. Pigment Red 190, C. I. Pigment Red 192, C. I. Pigment Red 193, C. I. Pigment Red 194, C. I. Pigment Red 200, C. I. Pigment Red 202, C. I. Pigment Red 206, C. I. Pigment Red 207, C. I. Pigment Red 208, C. I. Pigment Red 209, C. I. Pigment Red 210, C. I. Pigment Red 211, C. I. Pigment Red 213, C. I. Pigment Red 214, C. I. Pigment Red 216, C. I. Pigment Red 215, C. I. Pigment Red 216, C. I. Pigment Red 220, C. I. Pigment Red 221, C. I. Pigment Red 223, C. I. Pigment Red 224, C. I. Pigment Red 226, C. I. Pigment Red 237, C. I. Pigment Red 238, C. I. Pigment Red 239, C. I. Pigment Red 240, C. I. Pigment Red 242, C. I. Pigment Red 245, C. I. Pigment Red 247, C. I. Pigment Red 248, C. I. Pigment Red 251, C. I. Pigment Red 253, C. I. Pigment Red 254, C. I. Pigment Red 255, C. I. Pigment Red 256, C. I. Pigment Red 257, C. I. Pigment Red 258, C. I. Pigment Red 260, C. I. Pigment Red 262, C. I. Pigment Red 263, C. I. Pigment Red 264, C. I. Pigment Red 266, C. I. Pigment Red 268, C. I. Pigment Red 269, C. I. Pigment Red 270, C. I. Pigment Red 271, C. I. Pigment Red 272, C. I. Pigment Red 279, etc.

As the purple pigment, for example, C.I. I. Pigment Violet 1, C. I. Pigment Violet 2, C. I. Pigment Violet 3, C. I. Pigment Violet 3:1, C.I. I. Pigment Violet 3:3, C.I. I. Pigment Violet 5:1, C.I. I. Pigment Violet 13, C. I. Pigment Violet 19 (γ type, β type), C.I. I. Pigment Violet 23, C. I. Pigment Violet 25, C. I. Pigment Violet 27, C. I. Pigment Violet 29, C.I. I. Pigment Violet 31, C. I. Pigment Violet 32, C. I. Pigment Violet 36, C. I. Pigment Violet 37, C. I. Pigment Violet 38, C. I. Pigment Violet 42, C. I. pigment violet 50, and the like.

Examples of yellow pigments include C.I. I. Pigment Yellow 1, C. I. Pigment Yellow 3, C. I. Pigment Yellow 12, C. I. Pigment Yellow 13, C. I. Pigment Yellow 14, Pigment Yellow 17, C. I. Pigment Yellow 24, C. I. Pigment Yellow 42, C. I. Pigment Yellow 55, C. I. Pigment Yellow 62, C. I. Pigment Yellow 65, C. I. Pigment Yellow 74, C. I. Pigment Yellow 83, C. I. Pigment Yellow 86, C. I. Pigment Yellow 93, C. I. Pigment Yellow 94, C. I. Pigment Yellow 95, C. I. Pigment Yellow 109, C. I. Pigment Yellow 110, C. I. Pigment Yellow 117, C. I. Pigment Yellow 120, Pigment Yellow 125, C.I. I. Pigment Yellow 128, C. I. Pigment Yellow 129, C. I. Pigment Yellow 137, C. I. Pigment, Yellow 138, C. I. Pigment Yellow 139, C. I. Pigment Yellow 147, C. I. Pigment Yellow 148, C. I. Pigment Yellow 150, C. I. Pigment Yellow 151, C. I. Pigment Yellow 153, C. I. Pigment Yellow 154, C. I. Pigment Yellow 155, C. I. Pigment Yellow 166, C. I. Pigment Yellow 168, C. I. Pigment Yellow 174, C. I. Pigment Yellow 180, C. I. Pigment Yellow 185 and C.I. I. Pigment Yellow 213 and the like.

Examples of orange pigments include C.I. I. Pigment Orange 5, C. I. Pigment Orange 13, C. I. Pigment Orange 16, C. I. Pigment Orange 34, C. I. Pigment Orange 36, C. I. Pigment Orange 37, C. I. Pigment O Orange 38, C. I. Pigment Orange 43, C. I. Pigment Orange 51, C. I. Pigment Range 55, C. I. Pigment Orange 59, C. I. Pigment Orange 61, C. I. Pigment Orange 64, C. I. Pigment Orange 71 or C.I. I. Pigment Orange 74 and the like.

Examples of brown pigments include C.I. I. Pigment Brown 23, C. I. Pigment Brown 25 or C.I. I. Pigment Brown 26 and the like.

Among them, as a preferable pigment, C.I. I. pigment black 7,
C. as an indigo pigment. I. Pigment Blue 15, C. I. Pigment Blue 15:1, C. I. Pigment Blue 15:2, C. I. Pigment Blue 15:3, C. I. Pigment Blue 15:4, C. I. pigment blue 15:6,
C. as a green pigment. I. pigment green 7,
C. as a red pigment. I. Pigment Red 57:1, C.I. I. Pigment Red 48:1, C.I. I. Pigment Red 48:2, C. I. Pigment Red 48:3, C.I. I. Pigment Red 146, C. I. Pigment Red 242, C. I. Pigment Red 185, C. I. Pigment Red 122, C. I. Pigment Red 178, C. I. Pigment Red 149, C. I. Pigment Red 144, C. I. pigment red 166,
C. as a purple pigment. I. Pigment Violet 23, C. I. pigment violet 37,
C. as a yellow pigment. I. Pigment Yellow 83, C. I. Pigment Yellow 14, C. I. Pigment Yellow 180, C. I. pigment yellow 139,
C. as an orange pigment. I. Pigment Orange 38, C. I. Pigment Orange 13, C. I. Pigment Orange 34, C. I. pigment orange 64,
It is preferable to use at least one kind or two or more kinds selected from these groups.

Examples of inorganic pigments include white inorganic pigments such as titanium oxide, zinc oxide, zinc sulfide, barium sulfate, calcium carbonate, chromium oxide, silica, lithobon, antimony white, and gypsum. Among the inorganic pigments, use of titanium oxide is particularly preferred. Titanium oxide is white and is preferred from the viewpoint of coloring power, hiding power, chemical resistance, and weather resistance. From the viewpoint of printing performance, the titanium oxide is preferably treated with silica and/or alumina.

Examples of inorganic pigments other than white include aluminum particles, mica (mica), bronze powder, chrome vermilion, yellow lead, cadmium yellow, cadmium red, ultramarine blue, deep blue, red iron oxide, yellow iron oxide, iron black, and zircon. Aluminum is in the form of powder or paste, but it is preferable to use it in paste form from the viewpoint of handling and safety, and whether to use leafing or non-leafing is selected as appropriate from the viewpoint of brightness and density.

The above pigment is used in an amount sufficient to ensure the concentration and coloring power of the liquid printing ink, that is, 1 to 60% by weight based on the total weight of the liquid printing ink, and 10 to 90% by weight of the solid content in the liquid printing ink. It is preferable that it is contained in a proportion of %. Further, these pigments can be used alone or in combination of two or more.

Organic solvent-based liquid printing inks may also contain wax, chelate crosslinking agents, extender pigments, leveling agents, antifoaming agents, plasticizers, infrared absorbers, ultraviolet absorbers, fragrances, flame retardants, etc., as necessary. You can also do it.

(golden ink)
The laminate of the present invention, especially when printed with gold-tone ink, becomes a laminate with a luxurious feel in which the gold printing stands out well. As described in Japanese Patent Application Laid-Open No. 2021-98284, the inventors found that the mechanism by which the gold printing shines is that in the method for measuring the spectral reflectance of a laminate, the direction in which the reflected light from the laminate is received has a reception zenith angle of 0°. ~30°, and when the receiving azimuth is 180° with respect to the incident azimuth, the average value of relative spectral reflectance in 400 nm to 460 nm is 0.25 or more and 0.45 or less, and 540 nm It is assumed that it is important that the average value of relative spectral reflectance at ~700 nm is 0.85 or more and 1.00 or less, and that the arithmetic surface roughness (Sa) of the laminate is close to that of gold foil. are doing.
There is no particular restriction on the gold-tone ink for performing such gold printing, and any known gold-tone ink can be used.

(Biomass liquid printing ink)
In the liquid printing ink used in the present invention, it is preferable to use a liquid printing ink that uses plant-derived raw materials, taking into consideration the construction of a recycling-oriented society that should be continuously developed (sustainability).
Examples of plant-derived raw materials include cellulose resins such as cellulose acetate propionate resin and nitrified cotton, and polyamides using dimer acids or polymerized fatty acids derived from natural oils such as soybean oil, palm oil, and rice bran oil. Resins, polycarboxylic acids such as succinic acid, succinic anhydride, adipic acid, azelaic acid, sebacic acid, dimer acid, glutaric acid, malic acid, etc.; polyols such as ethylene glycol, 1,2-propanediol, 1,3 - Propanediol, 1,4-butanediol, neopentyl glycol, pentylene glycol, 1,10-dodecanediol, dimer diol, isosorbide, etc.; as a polyisocyanate, plant-derived polyisocyanates such as 1,5-pentamethylene diisocyanate, dimer diisocyanate, etc. Examples include biomass polyurethane synthesized from raw materials and rosin resin.

Commercial products can also be used as the biomass liquid printing ink. As commercially available products, inks listed by the Japan Organic Resources Association, etc. can be used.

<Other layers>
(overcoat layer)
In the laminate of the present invention, an overcoat layer may be further provided on the printed layer in order to improve gloss, scratch resistance, and heat resistance. The overcoat agent for forming the overcoat layer is not particularly limited, but may be an ink composition that has the same composition as the ink composition used for the above-mentioned printing layer and does not contain pigments for the purpose of coloring (extender pigments, etc.). ) or an active energy ray-curable ink. Further, the overcoat agent may be a resin coating agent such as acrylic resin, urethane resin, acrylic urethane resin, or epoxy resin.

Commercially available products can also be used as the overcoat agent.

In consideration of sustainability, it is preferable that the overcoat agent also contains a plant-derived raw material. As such an overcoat agent, those commercially available as biomass certified products can be used. Specifically, varnishes and the like listed by the Japan Organic Resources Association can be used.

(Other base material layers)
The laminate of the present invention may further include other base material layers. The other base layer is not particularly limited, and may be a matte laminated film similar to the first base layer, a laminated film different from the first base layer, a sealant film, or other materials. It may be a paper base material such as plain paper or coated paper, a plastic film such as an unstretched film or a stretched film, or a nonwoven fabric, but it is preferably formed of a thermoplastic resin. Further, it is preferable that the sealant film has a heat sealing function.

Examples of the plastic film include OPP film, PET film, and nylon film (hereinafter also referred to as Ny film). Furthermore, a plastic film coated with a gas barrier property and a coating for improving ink receptivity when providing a printing layer described later may be used. Commercially available coated plastic films include K-OPP film and K-PET film.
Furthermore, examples of the sealant film include CPP film, LLDPE film, and the like.

Moreover, the second base material layer used in the present invention may be formed of biomass polyolefin. The biomass polyolefin refers to a polyolefin resin using a plant-derived olefin as a raw material monomer. The raw material monomers may contain petroleum-derived monomers, and may not contain 100% plant-derived monomers.

Commercially available products can also be used as the biomass polyolefin. Examples of commercially available products include SGM9450F, SLL118, SLL118/21, SLL218, SLL318, SLH118, SLH218, and SLH0820 manufactured by Braskem.

(barrier layer)
The laminate of the present invention may further include a barrier layer in order to provide or improve gas barrier properties that block the transmission of oxygen gas, water vapor, etc., and light shielding properties that block the transmission of visible light, ultraviolet rays, etc. Preferably, the barrier layer is made of a metal vapor deposited film or a metal foil. The type of vapor deposited layer is not particularly limited as long as it can provide gas barrier properties. Preferred examples include metal vapor deposition or metal oxide vapor deposition, which are currently widely used for packaging. Although various metals can be used as the metal vapor deposition, aluminum is particularly preferred because it is inexpensive and widely used. Furthermore, a transparent vapor-deposited film may be used as the barrier layer.

There are no particular limitations on the vapor deposition method, and examples include a vacuum vapor deposition method that is a physical vapor deposition method, a sputtering method, an ion plating method, and a CVD method that is a chemical vapor deposition method. The thickness of the vapor deposited layer is not particularly limited as long as the vapor deposited layer alone can exhibit a certain gas barrier function. The preferred range of thickness varies depending on the type of metal or metal oxide to be deposited, but is preferably 0.05 to 70 nm, more preferably 0.1 to 70 nm, more preferably 3 to 70 nm, and even more preferably 5 to 60 nm. preferable.

As the metal vapor-deposited film, a VM-CPP film in which a metal such as aluminum is vapor-deposited on a CPP film, and a VM-OPP film in which a metal such as aluminum or the like is vapor-deposited on an OPP film can be used. Examples of the transparent vapor-deposited film include OPP films, PET films, nylon films, etc., on which silica or alumina is vapor-deposited. For the purpose of protecting the inorganic vapor-deposited layer of silica or alumina, a film coated on the vapor-deposited layer may be used.

Further, the laminate of the present invention may have two or more barrier layers. When there are two or more barrier layers, they may have the same composition or different compositions.

(Adhesive layer)
The laminate of the present invention may further include an adhesive layer as another layer. The adhesive layer has a function of bonding any two layers constituting the laminate, for example, the first base layer and other base layers. The adhesive layer is preferably a cured coating film of a two-part curable adhesive of a polyol composition and a polyisocyanate composition, but is not limited thereto.

<Method for manufacturing laminate>
The method for manufacturing the laminate of the present invention is not particularly limited, and for example, gravure printing using a gravure printing plate using an electronic engraving intaglio or the like, or flexographic printing using a resin plate, etc., on the surface resin layer (A) side of the matte-like laminate film. It can be manufactured by laminating printed layers by a known printing method such as flexographic printing using a plate. The printing layer may be laminated on the entire surface of the surface resin layer (A) side, or may be laminated only on a part of the surface of the surface resin layer (A) side.
In addition, for laminating other layers, for example, known methods such as dry lamination, wet lamination, non-solvent lamination, extrusion lamination, etc. are used to form adhesive layers, second base material layers, and barrier layers. It can be manufactured by laminating layers. In addition, it can also be manufactured by further laminating an overcoat layer using a known printing method. The order of laminating other layers and laminating the printed layer is not particularly limited. For example, the printed layer may be laminated on the matte laminated film, and then the second base layer may be laminated by dry lamination, or The printed layer may be laminated after the second base layer is laminated on the laminated film by dry lamination.

The laminate of the present invention has excellent adhesion between the matte laminate film and the ink serving as the printing layer. Therefore, the ink is difficult to peel off from the matte laminated film, and a good appearance can be obtained.

The laminate of the present invention has secondary functions in order to impart functions such as mechanical function, chemical function, electric function, magnetic function, sliding function to control friction/wear/lubrication, optical function, thermal function, and biocompatibility. It can also be processed. Examples of secondary processing include surface treatment (corona discharge treatment, antistatic treatment, plasma treatment, photochromism treatment, physical vapor deposition, chemical vapor deposition, coating, etc.), embossing, painting, adhesion, printing, metallization (plating, etc.) , machining, etc. Moreover, a molded product can also be manufactured by subjecting the laminate of the present invention to lamination processing (dry lamination or extrusion lamination), bag making processing, and other post-processing processing.

<Packaging material>
The laminate of the present invention can be used as a packaging material. Examples of such packaging materials include packaging bags, containers, and lid materials for containers used for foods, medicines, industrial parts, miscellaneous goods, magazines, and the like. In particular, since it has an unprecedented matte feel, it is possible to provide a packaging material similar to Japanese paper, etc., and it can be suitably used for food products, etc., which are used to bring out a luxurious feel.

The above-mentioned package can be heat-sealed or printed by overlapping the sealing layers (C) with the sealing layer (C) of the matte laminated film used in the present invention as a heat-sealing layer. By overlapping and heat-sealing the exposed surface resin layer (A) and sealing layer (C), the matte laminated film sealing layer (C) was formed as an inner layer. Packaging bags can be made. For example, cut two pieces of the matte laminated film into the desired packaging bag size, overlap them and heat seal the three sides to form a bag, and then It can be used as a packaging bag by filling it with contents from one side and sealing it by heat sealing. Furthermore, it is also possible to form a packaging bag by sealing the ends of a roll of film into a cylindrical shape using an automatic packaging machine and then sealing the top and bottom.

EXAMPLES The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to the following Examples.

(Manufacture of matte laminated film (1))
As the surface resin layer (A), 20 parts of propylene homopolymer (density: 0.90 g/cm ³ , MFR: 7.0 g/10 minutes) and sugarcane-derived high-density polyethylene (Braskem SGM9450F density: 0.952 g) /cm ³ , MFR: 0.05 g/10 minutes) and 25 parts of propylene-ethylene block copolymer (density: 0.90 g/cm ³ , MFR: 7.0 g/10 minutes). As the resin layer (B), 85 parts of propylene-ethylene block copolymer (density: 0.90 g/cm ³ , MFR: 7.0 g/10 minutes) and sugarcane-derived linear low A mixture consisting of 15 parts of density polyethylene (Braskem SLH218, density: 0.916 g/cm ³ , MFR: 2.3 g/10 minutes) was used as the seal layer (C), and a propylene-ethylene random copolymer ( density: 0.90 g/cm ³ , MFR: 5.0 g/10 minutes) and 80 parts of propylene-ethylene random copolymer (density: 0.90 g/cm ³ , MFR: 8.0 g/10 Using a mixture consisting of 20 parts (min.), coextrude the surface resin layer (A), resin layer (B), and seal layer (C) so that the average thickness is 7:10:3. It was made into a three-layer film with a thickness of 30 μm. The surface resin layer (A) side of this film was subjected to a corona discharge treatment so that the surface energy was 36 mN/m to produce a matte laminated film (1).

(Manufacture of matte laminated film (2))
A matte laminated film (2) was produced in the same manner as the matte laminated film (1) except that the coextrusion was carried out to a thickness of 25 μm.

(Manufacture of matte laminated film (3))
As the surface resin layer (A), 15 parts of propylene homopolymer (density: 0.90 g/cm ³ , MFR (measurement temperature 230°C): 7.0 g/10 minutes) and sugarcane-derived high-density polyethylene (Braskem SGM9450F) were used. density: 0.952 g/cm ³ , MFR: 0.05 g/10 minutes) and 50 parts of propylene-ethylene block copolymer (density: 0.90 g/cm ³ , MFR: 7.0 g/10 minutes) ) was used. In addition, as the intermediate layer (B), 80 parts of propylene-ethylene block copolymer (density: 0.90 g/cm ³ , MFR (measurement temperature 230°C): 7.0 g/10 minutes) and sugarcane-derived linear Masterbatch based on propylene-ethylene copolymer with 15 parts of density polyethylene (Braskem SLH218 density: 0.916 g/cm ³ , MFR: 2.3 g/10 min) and titanium oxide (TiO2) at 70% concentration. A mixture consisting of 5 parts (hereinafter referred to as titanium oxide masterbatch) was used. Furthermore, as a support layer (D), 40 parts of ethylene/1-butene copolymer (density: 0.880 g/cm ³ , MFR (measurement temperature 190°C): 4.0 g/10 minutes) and low density polyethylene (density: : 0.920 g/cm ³ , MFR (measurement temperature: 190° C.): 5.0 g/10 minutes) 60 parts was used. Furthermore, 100 parts of a propylene-ethylene copolymer (density: 0.90 g/cm ³ , MFR (measurement temperature 230° C.): 7.0 g/10 minutes) was used as the sealing layer (C). These are supplied to four extruders so that they are laminated in the order of surface resin layer (A)/intermediate layer (B)/support layer (D)/seal layer (C), (A): (B): Coextrusion was performed so that the average thickness ratio of (D):(C) was 6:21:1.5:1.5 to form a 4-layer film with a thickness of 30 μm. Next, the surface resin layer (A) of the obtained four-layer film was subjected to a corona discharge treatment so that the surface energy became 36 mN/m to obtain a matte laminated film (3).

<Example 1>
A printed layer formed by printing liquid printing ink Glosser BM Indigo (manufactured by DIC Graphics Corporation) was formed on the surface resin layer (A) of the matte laminated film (1) to obtain the laminate of Example 1. I got it.

<Example 2>
A laminate of Example 2 was obtained in the same manner as in Example 1 except that the liquid printing ink was changed to Raijin Ai (manufactured by DIC Graphics Corporation).

<Example 3>
A laminate of Example 3 was obtained in the same manner as in Example 1 except that the liquid printing ink was changed to Ultima NT Indigo (manufactured by DIC Graphics Corporation).

<Example 4>
A laminate of Example 4 was obtained in the same manner as in Example 1 except that the matte-like laminated film (1) was changed to the matte-like laminated film (2).

<Example 5>
A laminate of Example 5 was obtained in the same manner as in Example 2, except that the matte-like laminated film (1) was changed to the matte-like laminated film (2).

<Example 6>
A laminate of Example 6 was obtained in the same manner as in Example 3 except that the matte-like laminated film (1) was changed to the matte-like laminated film (2).

<Example 7>
A printing layer of liquid printing ink Glosser BM Indigo (manufactured by DIC Graphics Corporation) was formed on the surface resin layer (A) of the matte-like laminated film (3) to form the laminate of Example 7. Obtained.

<Example 8>
A laminate of Example 8 was obtained in the same manner as Example 7 except that the liquid printing ink was changed to Raijin Ai (manufactured by DIC Graphics Corporation).

<Example 9>
A laminate of Example 9 was obtained in the same manner as Example 7 except that the liquid printing ink was changed to Ultima NT Indigo (manufactured by DIC Graphics Corporation).

<Example 10>
A laminate of Example 10 was obtained in the same manner as in Example 1 except that the liquid printing ink was changed to gold tone ink (Ultima LT Sungold Y manufactured by DIC Graphics Co., Ltd.).

<Example 11>
A laminate of Example 11 was obtained in the same manner as in Example 4 except that the liquid printing ink was changed to gold tone ink (Ultima LT Sungold Y manufactured by DIC Graphics Co., Ltd.).

<Comparative example 1>
The same procedure as in Example 1 was carried out except that the matte laminated film (1) was changed to a CPP film (thickness 30 μm) and the liquid printing ink was changed to gold tone ink (Ultima LT Sun Gold Y manufactured by DIC Graphics Co., Ltd.). , a laminate of Comparative Example 1 was obtained.

<Ink adhesion evaluation method>
A laminate using a matte laminated film that has a texture similar to that of Japanese paper and can bring out the luxurious feel of the contents, requires ink adhesion that does not peel between the printing layer and the matte laminated film to obtain a good appearance. be. If the ink peels off from the matte laminated film, the good appearance may be impaired. Therefore, ink adhesion was evaluated.
After applying cellophane tape (manufactured by Nichiban Co., Ltd.) to the printed surface of the laminates of Examples 1 to 11, the tape was quickly peeled off and the condition of the printed surface was visually evaluated. An evaluation of 4 or higher is within the practical range.
(Evaluation criteria)
5: The printed film does not peel off from the film at all.
4: Less than 20% of the area ratio of the printed film peels off from the film.
3: The area ratio of the printed film is 20% or more and less than 50% peeled off from the film.
2: The area ratio of the printed film is 50% or more and less than 80% peeled off from the film.
1: 80% or more of the printed surface area is peeled off from the film.

<Evaluation method of gold printing (1)>
In order for the gold printing to stand out, as described in JP-A-2021-98284, in the method for measuring the spectral reflectance of the laminate, the direction in which the reflected light from the laminate is received must have a reception zenith angle of 0° to 30°. degree, and when the receiving azimuth is 180° with respect to the incident azimuth, the average value of relative spectral reflectance in 400 nm to 460 nm is 0.25 or more and 0.45 or less, and 540 nm to 700 nm It is necessary that the average value of the relative spectral reflectance in is 0.85 or more and 1.00 or less. Therefore, regarding the laminates of Examples 10 to 11 and Comparative Example 1, in the method for measuring spectral reflectance described in JP-A No. 2021-98284, relative spectral measurements were performed when the receiving zenith angle was 0°, 20°, and 30°. The reflectance of each was measured.
〇: The average value of relative spectral reflectance in each wavelength region is within the above range ×: The average value of relative spectral reflectance in each wavelength region is outside the above range

<Evaluation method of gold printing (2)>
Furthermore, it has been found that in order for the gold printing to stand out, in addition to the spectral reflectance, it is preferable that the arithmetic mean height (Sa) be equal to that of gold foil. Therefore, using a confocal microscope (manufactured by Keyence Corporation), the arithmetic mean heights of the laminates and gold foil No. 3 color of Examples 10 to 11 and Comparative Example 1 were measured.
〇: Arithmetic mean height (Sa) of gold foil - Absolute value of arithmetic mean height (Sa) of laminate of example is within 1.0 ×: Arithmetic mean height (Sa) of gold foil - laminate of example The absolute value of the arithmetic mean height (Sa) of exceeds 1.0.

Table 1 shows the structure of the laminates of Examples 1 to 6 and the evaluation results of ink adhesion.

Table 2 shows the structure of the laminates of Examples 7 to 9 and the evaluation results of ink adhesion.

Table 3 shows the evaluation results of the structure, ink adhesion, and gold printing of the laminates of Examples 10 to 11 and Comparative Example 1.

The products used for the printing layers listed in Tables 1 and 2 are as follows.
Ultima NT 507 Primary Color Indigo Y Made by DIC Graphics Co., Ltd. Raijin 507 Primary Color Indigo Made by DIC Graphics Co., Ltd. Glosser 507 Primary Color Indigo S2 Made by DIC Graphics Co., Ltd. Goldtone Ink Ultima LT Sun Gold Y Made by DIC Graphics Co., Ltd.

The laminates of Examples 1 to 9, which are the laminates of the present invention, use a matte laminated film with an excellent matte feel, and have a texture similar to Japanese paper, so they were able to bring out the luxurious feel of the contents. . In addition, it had excellent ink adhesion. Furthermore, each layer uses a large amount of plant-derived raw materials, so the overall laminate has a high degree of biomass.
In addition, the laminates of Examples 10 to 11, which are laminates of the present invention, have a texture similar to that of Japanese paper, have an excellent balance between the glossiness and matteness of gold-tone printing, and have a surface roughness similar to that of gold leaf. Therefore, it can give an impression that is more similar to real gold leaf. This resulted in a laminate with a high-quality design and a high-class feel. On the other hand, the laminate of Comparative Example 1 did not have a matte finish, and the gold printing did not stand out.

Claims (5)

A laminate in which at least a first base layer and a printing layer are laminated,
(1) The first base layer is
Plant-derived high-density polyethylene (a1) with a melt flow rate of 1 g/10 minutes or less (temperature 190 ° C., load 2.16 kg),
Containing propylene homopolymer (a2-1) and propylene-ethylene block copolymer (a2-2), melt flow rate is 0.5 g/10 minutes to 30 g/10 minutes (temperature 230°C, load a surface resin layer (A) containing a propylene resin (a2) of 2.16 kg);
A matte laminated film with a resin layer (B) containing a polyolefin resin (b1),
(2) A laminate, characterized in that the printing layer is a layer formed by printing liquid printing ink.
The laminate according to claim 1, wherein the printing layer is a layer formed by printing a liquid printing ink containing a plant-derived raw material.
The laminate according to claim 1 or 2, wherein the printing layer is on the surface resin layer (A) side of the first base layer.
A packaging material using the laminate according to any one of claims 1 to 3.
The packaging material according to claim 4, which is a food packaging bag.