Laminate having a removable primer composition layer

Abstract

To provide a laminate which enables a printing layer to be more simply separated and desorbed from a resin base material and a sealant layer, and is excellent in laminate suitability.SOLUTION: There is provided a laminate in which a resin base material, a primer layer for desorption, a printing layer and a sealant layer are formed in this order, wherein the primer composition for desorption forming the primer layer for desorption contains a polyethyleneimine-based compound having an amine value of 5.0-25.0 mmol / g and / or a polybutadiene-based compound.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a laminate having a release primer composition layer. [Background technology]

[0002] Packaging materials using various plastic films are used for food, confectionery, household goods, pet food, etc., from the viewpoints of design, economy, content protection, transportability, etc. Furthermore, gravure printing or flexographic printing is applied to many packaging materials with the intention of adding designs and messages that will appeal to consumers. In order to obtain these packaging materials, printing is performed by printing directly onto the surface of the base film of the packaging material, or by applying an adhesive or anchor agent to the printed surface printed on the surface of the base film of the packaging material as necessary and laminating the base film. In printing for lamination, a colored ink composition and a white ink composition are printed in that order on various substrate films such as polyester, nylon, and aluminum foil, and then a polyethylene film or polypropylene film for heat sealing is laminated on the printed layer of the white ink composition by dry lamination using an adhesive or extrusion lamination using an anchor coating agent (see Patent Document 1).

[0003] In recent years, packaging made from plastic film, plastic bottles, and other plastic products have been discarded and dumped into the ocean as garbage, causing environmental pollution. These plastic products break down in seawater and become submicron-sized fragments (microplastics), which float in the seawater. If marine organisms such as fish ingest this plastic, it will accumulate in their bodies. This could have an impact on the health of seabirds and humans who consume the marine organisms as food.

[0004] As one of various efforts to reduce microplastics in order to improve such problems, a recycling method has been proposed in which the plastic substrate of a laminate is removed from a laminate on which a printing ink composition is laminated. As a method for removing the plastic substrate of a laminate, a removing ink composition (for example, see Patent Document 2), a removing adhesive (for example, see Patent Document 3), a removing anchor coat agent, etc. (for example, see Patent Documents 4 to 6), and a removing liquid (for example, see Patent Document 7) have been proposed. However, in these methods, the removing liquid is not sufficient to remove the substrate with hot water, and when used in a laminate printing ink composition, there is a problem that the lamination suitability and retort suitability are insufficient. In addition, in the laminates described in these patents, when a non-stretched plastic film is used as the sealant layer, there is a problem that the removal of the printing layer and the non-stretched plastic film is insufficient. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 5-97959 [Patent Document 2] Patent No. 6631964 [Patent Document 3] Patent No. 6642688 [Patent Document 4] Patent No. 6388131 [Patent Document 5] JP 2020-175620 A [Patent Document 6] International Publication No. 2021 / 090690 [Patent Document 7] Patent No. 6690806 Summary of the Invention [Problem to be solved by the invention]

[0006] An object of the present invention is to obtain a laminate having a removal primer composition layer which enables a printed layer to be more easily separated and removed from a resin substrate or a sealant layer using a remover liquid and has excellent suitability for lamination. [Means for solving the problem]

[0007] The present inventors have found that the above problems can be solved by forming the laminate described below, and have arrived at the present invention described below. 1. A laminate comprising a resin substrate, a detachable primer layer, a printed layer, a detachable primer layer, and a sealant layer laminated in that order, in which the detachable primer composition for forming the detachable primer layer is a detachable primer composition containing a polyethyleneimine-based compound having an amine value of 5.0 to 25.0 mmol / g and / or a polybutadiene-based compound. 2. The laminate according to 1, wherein the detachment primer composition containing a polyethyleneimine-based compound and / or a polybutadiene-based compound having an amine value of 5.0 to 25.0 mmol / g contains one or more compounds selected from the following a. to d. a. Polybutadiene compounds b. Polyethyleneimine compounds c. A mixture containing a polyethyleneimine compound and a glycidyl group-containing silane coupling agent and / or an isocyanate group-containing silane coupling agent. d. Siloxane-modified polyethyleneimine compound 3. The laminate according to 1 or 2, which is any one of the following (1) to (3): (1) A laminate having, in order, a resin substrate, a removable primer layer, a printed layer, an adhesive layer, a removable primer layer, and a sealant layer formed by dry lamination. (2) In the case of extrusion lamination: a laminate having, in order, a resin substrate, a removable primer layer, a printed layer, a removable primer layer, an anchor coating agent, and a sealant layer formed by extrusion lamination. (3) In the case of extrusion lamination: a laminate having, in order, a resin substrate, a removable primer layer, a printed layer, a removable primer layer, and a sealant layer formed by extrusion lamination. 4. The laminate according to any one of 1 to 3, wherein the number average molecular weight of the polyethyleneimine compound and the number average molecular weight of the siloxane-modified polyethyleneimine compound are each independently 1,000 to 200,000. 5. The laminate according to any one of 1 to 4, wherein the polyethyleneimine compound and the siloxane-modified polyethyleneimine compound each independently have a mass average molecular weight of 4,000 to 800,000. 6. A laminate using the detachment primer composition according to any one of 1 to 5, wherein the polybutadiene compound is a hydroxyl group-containing polybutadiene compound and / or a carboxyl group-containing polybutadiene compound. 7. A laminate using the removal primer composition according to any one of 1 to 6, wherein the sealant layer is formed from a non-stretched plastic film or a molten resin. Effect of the Invention

[0008] According to the present invention, the printed layer can be more easily separated and detached from the resin substrate or the sealant layer by using a release liquid, and the laminate suitability is excellent. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] The present invention relates to a laminate in which a resin substrate, a detachable primer layer, a printed layer, a detachable primer layer, and a sealant layer are formed in this order, and the detachable primer composition forming the detachable primer layer is a detachable primer composition containing a polyethyleneimine-based compound having an amine value of 5.0 to 25.0 mmol / g and / or a polybutadiene-based compound. In addition, in a printed matter in which a resin substrate, a removable primer layer, a printed layer, an adhesive layer, and a removable primer layer are formed in this order, any known layer may be further formed between any of these layers.

[0010] [Resin substrate] As the resin substrate, those conventionally used in printing inks for lamination can be used. Specifically, biaxially oriented polypropylene, polyester, oriented nylon, transparent vapor deposition film, etc., which have water resistance, heat resistance, and impact resistance, and are also excellent in moisture resistance and gas barrier properties, are preferable.

[0011] [Removable primer layer] The detachable primer layer in the present invention is provided between the surface of the resin substrate and the printed layer, and between the printed layer and the sealant layer, and is a detachable primer layer for separating the resin substrate from the printed layer formed thereon and separating the sealant layer from the printed layer when the printed matter is to be reused after use, thereby detaching the printed layer from the substrate and the sealant layer. The detachable primer composition for forming the detachable primer layer will be described. The present invention relates to a laminate having a specific detachable primer layer. For example, the detachable primer layer provided between the surface of a resin substrate and a printed layer differs in its application and required properties from an anchor coating agent used when forming an anchor coating layer on the printed surface formed on the substrate and laminating a resin film or the like thereon. The detachable primer composition is a composition for forming a detachable primer layer in advance before printing on a resin substrate with a printing ink composition. Furthermore, the removable primer composition may also be used to form a removable primer layer on the sealant layer in advance before dry laminating the print layer and the sealant layer. Furthermore, the removable primer composition may also be used to form a removable primer layer in advance between the printed layer and the sealant layer before the printed layer and the sealant layer are extrusion laminated. The detachment primer composition for forming the detachment primer layer disposed so as to be located between the resin substrate and the printed layer, and the detachment primer composition for forming the detachment primer layer disposed so as to be located between the printed layer and the sealant layer may be the same or different. The detachment primer composition contains a polyethyleneimine-based compound having an amine value of 5.0 to 25.0 mmol / g and / or a polybutadiene-based compound.

[0012] The detachment primer composition containing a polyethyleneimine-based compound having an amine value of 5.0 to 25.0 mmol / g and / or a polybutadiene-based compound contains at least one type selected from a. to d. a. Polybutadiene compounds b. Polyethyleneimine compounds c. A mixture containing a polyethyleneimine compound and a glycidyl group-containing silane coupling agent and / or an isocyanate group-containing silane coupling agent d. Siloxane-modified polyethyleneimine compound

[0013] (a. Polybutadiene Compounds) The polybutadiene compound is preferably an aqueous composition. In order to make it aqueous and improve adhesion, a hydroxyl group-containing polybutadiene compound or a carboxyl group-containing polybutadiene compound in which a hydroxyl group or a carboxyl group is introduced into the polybutadiene compound is preferred. In order to exert releasability, it is preferable that the polybutadiene compound is not crosslinked. Specific examples include EL-451 (Toyo-Morton Co., Ltd.) and T-180E (Nippon Soda Co., Ltd.).

[0014] (b. Polyethyleneimine Compounds) The polyethyleneimine compound has an amine value of 15.0 to 25.0 mmol / g, preferably 16.0 mmol / g or more and 20.0 mmol / g or less. In addition, among the amino groups in the molecule, a polyethyleneimine-based compound having all of the primary amino groups to the tertiary amino groups is preferred, and among them, as a content based on the number of each amino group, it is preferred that the secondary amino groups are contained more than the primary and tertiary amino groups, and further, it is more preferred that the content of the secondary amino groups in the total amino groups from primary to tertiary is 40% or more by number of groups. The more within these ranges, the easier the elimination can be performed. It should be noted that b. polyethyleneimine compound does not include d. siloxane-modified polyethyleneimine compound, and d. siloxane-modified polyethyleneimine compound is a compound different from b. polyethyleneimine compound.

[0015] (c. A mixture containing a polyethyleneimine compound and one or more selected from a glycidyl group-containing silane coupling agent and an isocyanate group-containing silane coupling agent) In order to improve lamination suitability, it is preferable to further include a silane coupling agent containing a glycidyl group and / or an isocyanate group in the above polyethyleneimine compound. As the polyethyleneimine compound, the same polyethyleneimine compounds as those described in (b) above can be used, and this polyethyleneimine compound does not include d. siloxane-modified polyethyleneimine compounds. Examples of silane coupling agents containing a glycidyl group include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethoxydimethoxysilane, 3-glycidyloxypropylmethoxydiethoxysilane, 3-glycidyloxypropyltriethoxysilane, etc. Examples of silane coupling agents containing an isocyanate group include 3-isocyanatepropyltriethoxysilane, 3-isocyanatepropyltrimethoxysilane, 2-isocyanateethyltriethoxysilane, 2-isocyanateethyltrimethoxysilane, etc. From the viewpoint of lamination suitability after retort, it is preferable to mix the silane coupling agent containing a glycidyl group and the silane coupling agent containing an isocyanate group so that the ratio of (the number of glycidyl groups of the silane coupling agent + the number of isocyanate groups) to (the number of amino groups of the polyethyleneimine compound) ((the number of glycidyl groups of the silane coupling agent + the number of isocyanate groups of the silane coupling agent) / the total number of primary amino groups and secondary amino groups of the polyethyleneimine compound) is 0.20 to 2.50. It is more preferable that it is 0.30 or more, even more preferable that it is 0.50 or more, more preferable that it is 2.20 or less, and even more preferable that it is 1.90 or less. The number of amino groups is the sum of the number of primary amino groups and the number of secondary amino groups. This ratio of (the number of glycidyl groups in the silane coupling agent + the number of isocyanate groups) to (the number of amino groups in the polyethyleneimine compound) (the number of glycidyl groups in the silane coupling agent + the number of isocyanate groups / the total number of primary amino groups and secondary amino groups in the polyethyleneimine compound) can be calculated by the following formula: [(Amount of glycidyl-containing silane coupling agent applied (g / m 2 ) × average number of glycidyl groups in one molecule) / average molecular weight of glycidyl group-containing silane coupling agent (g / mmol)] + [(coating amount of isocyanate group-containing silane coupling agent (g / m 2) × average number of isocyanate groups in one molecule) / average molecular weight of isocyanate group-containing silane coupling agent (g / mmol)], [(coating amount of polyethyleneimine compound (g / m 2 ) × amine value (mmol / g) × (average (number of primary amino groups + number of secondary amino groups) per molecule) / (average (number of primary amino groups + number of secondary amino groups + number of tertiary amino groups) per molecule). In addition, when the detachment primer composition of the present invention selectively contains b. a polyethyleneimine compound, and c. a mixture containing a polyethyleneimine compound and a glycidyl group-containing silane coupling agent and / or an isocyanate group-containing silane coupling agent, these overlap in that they contain a polyethyleneimine compound, so that essentially a mixture containing c. a polyethyleneimine compound and a glycidyl group-containing silane coupling agent and / or an isocyanate group-containing silane coupling agent has been selected.

[0016] (d. Siloxane-modified polyethyleneimine compounds) To improve lamination suitability, a siloxane-modified polyethyleneimine compound can be used. The amine value of the siloxane-modified polyethyleneimine compound is preferably 5.0 mmol / g or more and 15.0 mmol / g or less. The siloxane-modified polyethyleneimine compound may be a polyethyleneimine compound having the formula: RZ-SiY 3 and a silane coupling agent-modified polyethyleneimine compound obtained by reacting at least one amine-reactive hydrolyzable organosilane represented by the formula: [wherein R represents an amine-reactive group selected from the group consisting of an isocyanate group, an oxiranyl group, a glycidoxy group, an acryloxy group, a carbethoxy group, a carbomethoxy group, a vinylsulfonyl group, and an acrylamide group, Z represents a divalent organic group containing a carbon atom, and each Y independently represents a hydrolyzable group], and a component comprising the following compound can be used. This siloxane-modified polyethyleneimine compound has a structure in which the group R of the silane coupling agent reacts with the amino group of polyethyleneimine to bond the silane coupling agent to the polyethyleneimine. However, as described above, it is preferable that the siloxane-modified polyethyleneimine compound has a predetermined amine value. In the present invention, the molecular weights of the polyethyleneimine compounds in (b) and (c) and the siloxane-modified polyethyleneimine compound in (d) that may be contained in the primer composition are preferably each independently a number average molecular weight of 1,000 to 200,000 in terms of suitability for lamination, and each independently a mass average molecular weight of 4,000 to 800,000. It should be noted that d. siloxane-modified polyethyleneimine compound is not included in the above b. polyethyleneimine compound and c. polyethyleneimine compound, and is a compound different from the polyethyleneimine compound.

[0017] (Removal primer composition) The detachment primer composition preferably contains the above-mentioned components and is based on a solvent obtained by mixing water and at least one of methanol, ethanol, and isopropyl alcohol as an alcohol. (Removable primer layer) The layer of the composition for the detachable primer provided between the resin substrate and the printed layer, and between the printed layer and the sealant layer, is 0.010 g / m2 as the coating amount (solid content) of the composition for the detachable primer. 2 More than 0.015 g / m is preferable. 2 More preferably, 0.400 g / m or more is also preferable. 2 Less than 0.300 g / m is preferred. 2 Less than 0.200 g / m is more preferable. 2 The following is even more preferred:

[0018] [Print layer] The printing layer is formed from a printing ink composition for lamination. As the printing ink composition for laminate, a printing ink composition for laminate that has been conventionally used can be used. <Laminate printing ink composition used for laminate printing> The printing ink composition for laminate contains a pigment, a binder resin, various additives and a solvent, and is not limited to the following composition.

[0019] (Pigments) As the pigment used in the printing ink composition for laminate, one or more kinds of known inorganic and organic pigments that have been conventionally used in printing ink compositions for laminate can be used. Examples of inorganic pigments include color pigments such as titanium oxide, red iron oxide, antimony red, cadmium yellow, cobalt blue, Prussian blue, ultramarine blue, carbon black, and graphite, and examples of extender pigments include silica particles, calcium carbonate, kaolin, clay, barium sulfate, aluminum hydroxide, and talc. Of these, it is preferable to use titanium oxide as a white pigment. Examples of the organic pigment include oil-soluble azo pigments, insoluble azo pigments, azo lake pigments, condensed azo pigments, copper phthalocyanine pigments, and condensed polycyclic pigments. The content of these pigments in the printing ink composition is usually about 1 to 50 mass %.

[0020] (binder resin) The binder resin includes a polyurethane resin, preferably a polyurethane resin having an amine value from the viewpoints of the stability, adhesiveness and lamination suitability of the printing ink composition. (Polyurethane resin) The polyurethane resin may contain a polyurethane resin that is not modified with an acid and / or a polyurethane resin that is modified with an acid. The polyurethane resin that is not modified with an acid is a polyurethane resin that does not have acidic groups such as carboxylic acid groups, sulfonic acid groups, and phosphoric acid groups at the molecular terminals and / or other positions in the molecule. The polyurethane resin that is modified with an acid is a polyurethane resin that has acidic groups such as carboxylic acid groups, sulfonic acid groups, and phosphoric acid groups at the molecular terminals and / or other positions in the molecule. The printed layer can be smoothly detached from the resin substrate even if it is formed from an ink composition that uses an acid-modified polyurethane resin as a vehicle, or even if it is formed from an ink composition that uses a resin that is inherently difficult to detach, such as a non-acid-modified polyurethane resin, as a vehicle.

[0021] As such a polyurethane resin, a polyurethane resin that is generally used in printing ink compositions can be used. Among them, from the viewpoints of the stability over time, adhesion, and lamination suitability of the printing ink composition, polyurethane resins having amino groups (having an amine value) are preferred. Among polyurethane resins having amino groups, polyurethane resins having at least one selected from a primary amino group, a secondary amino group, and a tertiary amino group at the molecular end, particularly at least one selected from a primary amino group and a secondary amino group at the molecular end, are more preferred. More preferred is a polyurethane resin having a hydroxyl group and at least one type of amino group selected from a primary amino group, a secondary amino group and a tertiary amino group at the molecular terminal. The polyurethane resin has a specific functional group such as the amino group, and thus has excellent printability and adhesiveness when used as a printing ink composition for laminate. The amine value of the polyurethane resin is preferably from 1.0 to 15.0 mgKOH / g, and more preferably from 2.0 to 8.0 mgKOH / g. If the amine value is less than 1.0 mgKOH / g, the adhesion of the film printing ink composition of the present invention to the film may decrease, and further, the lamination suitability may decrease. If the amine value is more than 15.0 mgKOH / g, the blocking resistance may decrease. In the present invention, the amine value means the amine value per 1 g of solid content, and refers to a value converted into the equivalent amount of potassium hydroxide after measuring by potentiometric titration (e.g., COMTITE (AUTO TITRATOR COM-900, BURET B-900, TITSTATION K-900), Hiranuma Sangyo Co., Ltd.) using a 0.1 N aqueous hydrochloric acid solution. In addition, the polyurethane resin preferably has hydroxyl groups within the molecule and at the molecular terminals from the viewpoint of resolubility.

[0022] (non-acid-modified polyurethane resin) As the polyurethane resin that is not acid-modified, a polyurethane polyurea resin and / or a polyurethane polyurea resin obtained by using a compound in which the amino group of a polyamine compound is ketiminated with a ketone compound is preferable. The polyurethane polyurea resin is prepared by chain extension and / or terminal termination of a urethane prepolymer obtained from an organic diisocyanate component and a polymer diol component. The polyurethane polyurea resin obtained by using a ketiminated compound as a chain extender and / or reaction terminator is: a. a polyurethane polyurea resin obtained by reacting a compound in which the amino group of a polyamine compound has been ketiminated with a ketone compound in an organic solvent with a urethane prepolymer; or b. a polyurethane polyurea resin obtained by adding a compound in which the amino group of a polyamine compound has been ketiminated with a ketone compound in an organic solvent to a urethane prepolymer, mixing them by stirring, adding water, and then carrying out chain extension and reaction termination. By using a and / or b as a chain extender and / or reaction terminator, the amine odor of the reverse printing ink composition obtained is reduced and the stability over time is excellent. In consideration of the environmental aspect, the polyurethane polyurea resin may contain a biomass polyurethane polyurea resin.

[0023] (non-acid-modified polyurethane polyurea resin) The non-acid-modified polyurethane polyurea resin has at least one type selected from a primary amino group and a secondary amino group at the molecular terminal. More preferred is a non-acid-modified polyurethane polyurea resin which has a hydroxyl group and at least one type selected from a primary amino group and a secondary amino group at the molecular terminal. As these polyurethane polyurea resins, polyurethane resins obtained by synthesizing a urethane prepolymer by reacting an organic diisocyanate compound with a polymeric diol compound and reacting this with a chain extender and a reaction terminator described below can be suitably used.

[0024] (Synthesis of urethane prepolymer) Each of the above urethane prepolymers is obtained by reacting the following organic diisocyanate compound with a polymeric diol compound.

[0025] (Organic diisocyanate compounds) Examples of the organic diisocyanate compound include aromatic diisocyanate compounds such as tolylene diisocyanate, alicyclic diisocyanate compounds such as 1,4-cyclohexane diisocyanate, isophorone diisocyanate, and dicyclohexylmethane-4,4-diisocyanate (hydrogenated MDI), aliphatic diisocyanate compounds such as hexamethylene diisocyanate, and aromatic aliphatic diisocyanate compounds such as α,α,α',α'-tetramethylxylylene diisocyanate. These organic diisocyanate compounds can be used alone or in combination of two or more. Among them, alicyclic diisocyanate compounds, aliphatic diisocyanate compounds, and aromatic aliphatic diisocyanate compounds are more preferred.

[0026] In addition, as other organic diisocyanate compounds, aromatic diisocyanate compounds such as 1,3- and / or 1,4-phenylene diisocyanate, 4,4-diisocyanatobiphenyl, 3,3-dimethyl-4,4-diisocyanatobiphenyl, etc.; alicyclic diisocyanate compounds such as cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), etc.; aliphatic diisocyanate compounds such as ethylene diisocyanate, tetramethylene diisocyanate, dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, etc.; and aromatic aliphatic diisocyanate compounds such as m- and / or p-xylylene diisocyanate (XDI), etc. can also be used. When other organic diisocyanate compounds are used in combination, the number of isocyanate groups of the other organic diisocyanate compounds can be 50% or less, more preferably 30% or less, and even more preferably 10% or less, of the total number of isocyanate groups of all the organic diisocyanate compounds. Alternatively, the amount of other organic diisocyanate compounds is 50 parts by mass or less, more preferably 30 parts by mass or less, and further preferably 10 parts by mass or less, based on 100 parts by mass of all organic diisocyanate compounds.

[0027] (Polymer diol compound) Examples of the polymer diol compound include polyalkylene glycols such as polyethylene glycol and polypropylene glycol, polyether diol compounds such as alkylene oxide adducts of bisphenol A with ethylene oxide and propylene oxide, polyester diols obtained by condensation reaction of one or more dibasic acids such as adipic acid, sebacic acid, and phthalic anhydride with one or more glycols such as ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, and 3-methyl-1,5-pentanediol, polyester diol compounds such as polycaprolactone diols, etc. These polymer diol compounds can be used alone or in combination of two or more. In addition to the above-mentioned polymeric diol compounds, one or more of alkanediols such as 1,4-pentanediol, 2,5-hexanediol, and 3-methyl-1,5-pentanediol, and low molecular weight diol compounds such as ethylene glycol, propylene glycol, 1,4-butanediol, and 1,3-butanediol can be used in combination. The polymer diol compound preferably has a number average molecular weight of 1,000 to 8,000, more preferably 1,000 to 5,500, and even more preferably 1,000 to 4,000. Moreover, as the polymer diol compound, one containing 3-methyl-1,5-pentylene adipate diol can be selected. In this case, the following polymer diol compounds can be used in combination. Examples of polymeric diol compounds other than 3-methyl-1,5-pentylene adipate diol include polyester diols obtained by condensation reaction of one or more dibasic acids such as adipic acid, sebacic acid, phthalic anhydride, etc. with one or more glycols such as ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, etc., polyester diol compounds such as polycaprolactone diols, and further, polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polyether diol compounds such as alkylene oxide adducts of bisphenol A with ethylene oxide, propylene oxide, etc. These polymeric diol compounds can be used alone or in combination of two or more.

[0028] Among the above, 3-methyl-1,5-pentylene adipate diol having a number average molecular weight of 1,000 to 8,000 obtained by a condensation reaction of adipic acid and 3-methyl-1,5-pentanediol is preferred, and 3-methyl-1,5-pentylene adipate diol having a number average molecular weight of 1,000 to 4,000 is more preferred. When other polymer diol compounds are used in combination, the number of hydroxyl groups of the other polymer diol compounds can be 70% or less, more preferably 55% or less, and even more preferably 40% or less, of the total number of hydroxyl groups of all the polymer diol compounds. Alternatively, the amount of the other polymer diol compounds is 50 parts by mass or less, more preferably 35 parts by mass or less, and further preferably 20 parts by mass or less, based on 100 parts by mass of the total polymer diol compounds. When the organic solvent of the printing ink composition for laminate is a mixed solvent system of an ester-based solvent and an alcohol-based solvent (hereinafter sometimes referred to as a "mixed liquid") described below, using a polyether diol compound, preferably polypropylene glycol, as the polymer diol compound tends to increase the solubility of the resulting polyurethane resin and also tends to improve printing suitability such as gradation reproduction and anti-fogging properties, which is preferable in that it enables the design of a wide range of printing ink compositions in accordance with the required performance.

[0029] (Non-acid-modified biomass polyurethane polyurea resin) The polyurethane resin may contain a biomass polyurethane polyurea resin that is not modified with an acid, taking into consideration the environmental aspect. The biomass polyurethane polyurea resin that is not modified with an acid will be described below. In the description of the biomass polyurethane polyurea resin that is not modified with an acid, the description common to the above-mentioned polyurethane polyurea resin that is not modified with an acid will be omitted as appropriate. The non-acid-modified biomass polyurethane polyurea resin is a polyurethane resin containing a biomass-derived (plant-derived) component. The non-acid-modified biomass polyurethane resin can contribute to preventing global warming and reducing the environmental load compared to the case of using other exhaustible resources. The non-acid-modified biomass polyurethane polyurea resin is preferably obtained by synthesizing a biomass urethane prepolymer by reacting a biopolyester polyol compound with an organic diisocyanate compound, and reacting this with a chain extender and a reaction terminator as necessary, and more preferably the isocyanate compound is a plant-derived bioisocyanate.

[0030] (Isocyanate compounds) In addition to the organic diisocyanate described in the above non-acid-modified polyurethane polyurea resin, a diisocyanate derived from vegetable oil can be used. The organic diisocyanate compound derived from vegetable oil can be obtained by converting a divalent carboxylic acid derived from a plant into a terminal amino group by acid amidation and reduction, and then reacting with phosgene to convert the amino group into an isocyanate group. Examples of bio-polyisocyanates derived from plants include dimer acid diisocyanate (DDI), octamethylene diisocyanate, and decamethylene diisocyanate. In addition, a plant-derived isocyanate compound can be obtained by using a plant-derived amino acid as a raw material and converting its amino group into an isocyanate group. For example, lysine diisocyanate (LDI) can be obtained by methyl esterifying the carboxyl group of lysine, and then converting the amino group into an isocyanate group. In addition, 1,5-pentamethylene diisocyanate can be obtained by decarbonating the carboxyl group of lysine, and then converting the amino group into an isocyanate group.

[0031] (Biopolyester polyol compound) The biopolyester polyol compound (biomass polyester polyol) will be described below. In consideration of the environmental aspect, among the biopolyester polyol compounds, a biopolyester polyol compound obtained by synthesis from a material containing a plant-derived component may be used in combination as the other polymer diol compound. In addition, a non-acid-modified polyurethane polyurea resin obtained by reacting a polyester polyol compound including a biopolyester polyol compound with the above-mentioned specific isocyanate compound can be mixed with the non-acid-modified polyurethane polyurea resin of the present invention and used. For this reason, the biopolyester polyol compound may be a biopolyester polyol obtained by reacting a short-chain diol compound having 2 to 4 carbon atoms with a carboxylic acid compound. It is more preferable that at least one of the short-chain diol compound and the carboxylic acid compound of the biopolyol component is derived from a plant, and it is even more preferable that both are derived from a plant. The plant-derived short-chain diol compound having 2 to 4 carbon atoms is not particularly limited. For example, the short-chain diol compound may be 1,3-propanediol, 1,4-butanediol, ethylene glycol, etc., which are obtained from plant raw materials by the following method. These may be used in combination. 1,3-propanediol can be produced from glycerol via 3-hydroxypropylaldehyde (HPA) by a fermentation method in which glucose is obtained by decomposing plant resources (such as corn, etc.). The 1,3-propanediol component produced by a biomethod such as the fermentation method is safer than the 1,3-propanediol component of the EO production method, and useful by-products such as lactic acid can be obtained, and the production cost can be kept low. 1,4-butanediol can be produced by producing glycol from plant resources, fermenting it to obtain succinic acid, and hydrogenating it. Ethylene glycol can also be produced from bioethanol obtained by a conventional method via ethylene.

[0032] The carboxylic acid compound derived from a plant is not particularly limited. For example, the carboxylic acid compound is sebacic acid, succinic acid, lactic acid, glutaric acid, dimer acid, etc. These may be used in combination. Among these, the carboxylic acid compound preferably contains at least one selected from the group consisting of sebacic acid, succinic acid, and dimer acid. In addition, 0.05 to 0.5 parts by mass of malic acid may be contained per 100 parts by mass of sebacic acid. The biopolyester polyol compound is produced as a 100% plant-derived biopolyester polyol by appropriately condensing a plant-derived short-chain diol compound and a plant-derived carboxylic acid. Specifically, polytrimethylene sebacate polyol is obtained by directly dehydrating and condensing plant-derived sebacic acid and plant-derived 1,3-propanediol. Also, polybutylene succinate polyol is obtained by directly dehydrating and condensing plant-derived succinic acid and plant-derived 1,4-butanediol. One or more of these biopolyester polyol compounds may be used. The urethane prepolymer obtained by using these plant-derived components may be contained in an amount of 10% by mass or more, or 40% by mass or more, calculated as solid content, of the total urethane prepolymer.

[0033] (Chain extenders and reaction terminators) Next, the chain extender and reaction terminator used in the non-acid-modified polyurethane polyurea resin and the non-acid-modified biomass polyurethane polyurea resin will be described. The chain extender may be any of the known chain extenders used in polyurethane polyurea resins as binders for printing ink compositions. Examples of the chain extender include, among polyamine compounds, aliphatic diamines such as ethylenediamine, propylenediamine, tetramethylenediamine, and hexamethylenediamine; alicyclic diamines such as isophoronediamine and 4,4'-dicyclohexylmethanediamine; aromatic diamines such as toluylenediamine; aromatic aliphatic diamines such as xylylenediamine; diamines having a hydroxyl group such as N-(2-hydroxyethyl)ethylenediamine (aminoethylethanolamine), N-(2-hydroxyethyl)propylenediamine, and N,N'-di(2-hydroxyethyl)ethylenediamine; and diol compounds such as ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, diethylene glycol, and triethylene glycol. Furthermore, polyamine compounds such as diethylenetriamine and triethylenetetramine can be used in combination within the range in which the polyurethane polyurea resin does not gel. Examples of reaction terminators that introduce primary and secondary amino groups to the ends of polyurethane polyurea resins include polyamine compounds such as aliphatic diamines such as ethylenediamine, propylenediamine, tetramethylenediamine, and hexamethylenediamine, alicyclic diamines such as isophoronediamine and 4,4'-dicyclohexylmethanediamine, polyamines such as diethylenetriamine and triethylenetetratriamine, aromatic diamines such as toluylenediamine, aromatic aliphatic diamines such as xylenediamine, and diamines having hydroxyl groups such as N-(2-hydroxyethyl)ethylenediamine (aminoethylethanolamine) and N-(2-hydroxyethyl)propylenediamine. Among these, polyamines having primary amino groups such as diethylenetriamine and triethylenetetratriamine are preferred. Examples of reaction terminators that introduce hydroxyl groups into polyurethane polyurea resins include alkanolamines such as monoethanolamine and diethanolamine, and diamines having hydroxyl groups such as N-(2-hydroxyethyl)ethylenediamine and N-(2-hydroxyethyl)propylenediamine. Known reaction terminators such as monoamine compounds and monoalcohol compounds can also be used, and specific examples include monoalkylamines such as n-propylamine and n-butylamine, dialkylamines such as di-n-butylamine, and monoalcohols such as ethanol.

[0034] As a method for producing the above-mentioned non-acid-modified polyurethane polyurea resin and non-acid-modified biomass polyurethane polyurea resin, a known method for producing a polyurethane resin can be used as is using the above-mentioned materials. In addition, since the hardness of the obtained polyurethane resin varies depending on the mass average molecular weight, chemical structure, and equivalent ratio of each component, it is possible to adjust the printability and lamination suitability by appropriately combining these components. The mass average molecular weight of the non-acid-modified polyurethane polyurea resin and the non-acid-modified biomass polyurethane polyurea resin is preferably 10,000 to 70,000, and more preferably 20,000 to 60,000. Furthermore, in order to provide appropriate flexibility and increase laminate strength, a polyurethane resin having no urea bond and a mass average molecular weight of 1,000 to 70,000 can be blended as the polyurethane resin.

[0035] (Reaction of organic diisocyanate compound with polymeric diol compound) In addition, the ratio of the organic diisocyanate compound and the polymer diol compound used when reacting them is usually in the range of 1.2:1.0 to 3.0:1.0, more preferably 1.3:1.0 to 2.0:1.0, in terms of the equivalent ratio (isocyanate index) of isocyanate group:hydroxyl group. If the isocyanate index is smaller than 1.2, the resulting polyurethane polyurea resin is likely to be soft and not acid-modified, or the polyurethane polyurea resin is not acid-modified, and there is a possibility that the blocking resistance is low when the printing ink composition is printed. In this case, it may be necessary to use the resin in combination with another hard resin.

[0036] A catalyst can be used in the reaction of an organic diisocyanate compound with a polymer diol compound to obtain the non-acid-modified polyurethane polyurea resin and the non-acid-modified biomass polyurethane polyurea resin used in the present invention. Among these, it is preferable to use an organometallic compound. Examples of such an organometallic compound include titanium compounds such as dibutyltitanium dichloride, tetrabutyltitanium, and butoxytitanium trichloride, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate, dibutyltin diacetate, dioctyltin dilaurate, tributyltin dilaurate, and the like. Examples of suitable compounds include tin compounds such as tin acetate, tributyltin chloride, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin trichloroacetate, and tin 2-ethylhexanoate, lead compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate, and lead naphthenate, and further compounds such as iron 2-ethylhexanoate, iron acetylacetonate, cobalt benzoate, cobalt 2-ethylhexanoate, zinc naphthenate, zinc 2-ethylhexanoate, and zirconium naphthenate. Among these, titanium compounds such as tetrabutyl titanate are preferred. Also, tertiary amine compounds can be used, such as triethylamine, triethylenediamine, 1,4-diazabicyclo(2,2,2)octane, and 1,8-diazabicyclo(5,4,0)-undecene-7 (DBU).

[0037] (Polyurethane polyurea resin not modified with acid obtained by using a compound in which the amino group of a polyamine compound is ketiminated with a ketone compound, and biomass polyurethane polyurea resin not modified with acid obtained by using a compound in which the amino group of a polyamine compound is ketiminated with a ketone compound) The non-acid-modified polyurethane polyurea resin obtained by using a compound in which the amino group of a polyamine compound has been ketiminated with a ketone compound, and the non-acid-modified biomass polyurethane polyurea resin obtained by using a compound in which the amino group of a polyamine compound has been ketiminated with a ketone compound can be produced by using a ketimine compound obtained by previously ketiminizing a polyamine compound with an excess amount of a ketone compound among the above chain extenders and / or reaction terminators, c. employing a compound in which the amino group of a polyamine compound has been ketiminized with a ketone compound in an organic solvent and reacting it with a urethane prepolymer and / or a biomass urethane prepolymer, or d. employing a compound in which the amino group of a polyamine compound has been ketiminized with a ketone compound in an organic solvent and adding it to the urethane prepolymer and / or biomass urethane prepolymer and stirring and mixing, further adding water, and then performing chain extension and reaction termination, thereby producing a non-acid-modified polyurethane polyurea resin and a non-acid-modified biomass polyurethane polyurea resin. In particular, it is preferable to employ one or more selected from the above chain extenders and reaction terminators: isophoronediamine, N-(2-hydroxyethyl)ethylenediamine, and ethylenediamine. The polyamine compound ketiminated with a ketone compound has a structure in which the oxygen atom of the ketone compound is substituted with the nitrogen atom of the amino group of the polyamine compound. The ketone compound to be used is preferably acetone, diethyl ketone, methyl ethyl ketone, diacetone alcohol, or methyl isobutyl ketone. In this ketiminization reaction, it is preferable not to use any solvent other than the ketone compound. However, as a solvent other than the ketone compound, an alcohol compound can be used, and among them, isopropyl alcohol can be used. The absence of a solvent other than the ketone compound is defined as ketiminization under solvent-free conditions. Note that a polar organic solvent may be added instead of solvent-free conditions, as long as it does not inhibit the subsequent chain extension reaction or the fact that the non-acid-modified polyurethane polyurea resin and the non-acid-modified biomass polyurethane polyurea resin have no odor. The present invention may be a printing ink composition containing a non-acid-modified polyurethane polyurea resin and / or a non-acid-modified biomass polyurethane polyurea resin obtained by a process of chain extension or reaction termination using a ketiminated chain extender and / or a reaction terminator according to the above method c or d, and the printing ink composition and printed matter do not emit a ketimine odor.In addition, the peel strength can be increased when the printed surface is laminated by means of dry lamination, extrusion lamination, or the like. The ketiminated amines and the like may be used as a chain extender, a reaction terminator, or both a chain extender and a reaction terminator.

[0038] (Synthesis of non-acid-modified polyurethane polyurea resin obtained by using a compound in which the amino group of a polyamine compound is ketiminated with a ketone compound, and non-acid-modified biomass polyurethane polyurea resin obtained by using a compound in which the amino group of a polyamine compound is ketiminated with a ketone compound) A ketimine compound obtained by previously ketiminizing a polyamine compound with an excess amount of a ketone compound is used for a urethane prepolymer and / or a biomass urethane prepolymer obtained by reacting an organic diisocyanate compound with a polymer diol compound, e. a compound in which the amino group of a polyamine compound has been ketiminized with a ketone compound in an organic solvent is used and reacted with the urethane prepolymer and / or the biomass urethane prepolymer, f. a compound in which the amino group of a polyamine compound has been ketiminized with a ketone compound in an organic solvent is used and added to the urethane prepolymer and / or the biomass urethane prepolymer, stirred and mixed, and further water is added, followed by chain extension and reaction termination, thereby obtaining a non-acid-modified polyurethane polyurea resin and a non-acid-modified biomass polyurethane polyurea resin obtained by using a compound in which the amino group of a polyamine compound has been ketiminized with a ketone compound, and a non-acid-modified biomass polyurethane polyurea resin obtained by using a compound in which the amino group of a polyamine compound has been ketiminized with a ketone compound. When a solvent is used during the reaction, an ester-based solvent and / or an alcohol-based solvent is preferred, a mixture of an ester-based solvent and an alcohol-based solvent is more preferred, propyl acetate and isopropyl alcohol are further preferred, and a mass ratio of propyl acetate:isopropyl alcohol in the range of 1:1 to 5:1 is most preferred.

[0039] (Acid-modified polyurethane resin, acid-modified biomass polyurethane resin) As the polyurethane resin for forming the printing layer in the present invention, an acid-modified polyurethane resin and / or an acid-modified biomass polyurethane resin can also be used. It may be used together with the above-mentioned non-acid-modified polyurethane resin and / or non-acid-modified biomass polyurethane resin, or only the acid-modified polyurethane resin and / or the acid-modified biomass polyurethane resin, or only the non-acid-modified polyurethane resin and / or non-acid-modified biomass polyurethane resin may be used. The acid-modified polyurethane resin and the acid-modified biomass polyurethane resin can be obtained by reacting the polymer diol component with a tetrabasic acid anhydride such as pyromellitic anhydride as the polymer diol compound constituting the polyurethane resin, or by using a polymer diol compound having a free carboxyl group obtained by ring-opening polymerization of lactones using dimethylolpropionic acid, dimethylolbutanoic acid, or the like as an initiator, or by using a hydroxycarboxylic acid such as dimethylolpropionic acid or dimethylolbutanoic acid together with the polymer diol compound constituting the polyurethane resin. The acid value of the acid-modified polyurethane resin and the acid-modified biomass polyurethane resin is preferably 70 mgKOH / g or less.

[0040] Other binder resins that can be used in combination with the polyurethane resin for forming the print layer in the present invention will be described below. (Vinyl chloride / vinyl acetate copolymer) The vinyl chloride-vinyl acetate copolymer that may be incorporated in the printing ink composition for laminate may be one produced by a known method using the vinyl chloride monomer and vinyl acetate monomer conventionally used in gravure printing ink compositions as essential components, and, if necessary, fatty acid vinyl monomers such as vinyl propionate, vinyl monochloroacetate, vinyl versatate, vinyl laurate, vinyl stearate, vinyl benzoate, and monomers having functional groups such as hydroxyl groups as copolymerization components. Vinyl chloride-vinyl acetate copolymers having hydroxyl groups can be obtained by partially saponifying the acetate moieties and by introducing (meth)acrylic monomers having hydroxyl groups. In the case of vinyl chloride-vinyl acetate copolymers having hydroxyl groups obtained by partially saponifying the acetate ester moieties, the film properties and dissolution behavior of the resin are determined by the ratio of the structural units based on the reactive sites of vinyl chloride (formula 1 below), the structural units based on the reactive sites of vinyl acetate (formula 2 below), and the structural units based on the saponification of the reactive sites of vinyl acetate (formula 3 below) in the molecule. That is, the structural units based on the reactive sites of vinyl chloride impart strength and hardness to the resin film, the structural units based on the reactive sites of vinyl acetate impart adhesion and flexibility, and the structural units based on the saponification of the reactive sites of vinyl acetate impart good solubility in the organic solvent system of the environmentally friendly printing ink composition. Formula 1 -CH 2 -CHCl- Formula 2 -CH 2 -CH(OCOCH 3 )- Formula 3 -CH 2 -CH(OH)-

[0041] From the viewpoint of solubility in organic solvents described below and printability used in the printing ink composition for laminate, the vinyl chloride-vinyl acetate copolymer may have various functional groups in the molecule. When an environmentally friendly solvent is used as the organic solvent, the vinyl chloride-vinyl acetate copolymer preferably has a hydroxyl group concentration of 50 to 200 mg KOH / g. Commercially available products of such vinyl chloride-vinyl acetate copolymers include, for example, Solbin A, AL, TA5R, TA2, TA3, TAO, and TAOL.

[0042] (Vinyl chloride-acrylic copolymer) The vinyl chloride-acrylic copolymer that can be incorporated in the printing ink composition for laminate is a copolymer of vinyl chloride and an acrylic monomer as the main component, and the form of the copolymer is not particularly limited. For example, the acrylic monomer may be incorporated in the main chain of polyvinyl chloride in a block or random manner, or may be graft-copolymerized in the side chain of polyvinyl chloride.

[0043] The acrylic monomer may be a (meth)acrylic acid ester, an acrylic monomer having a hydroxyl group, etc. Examples of the (meth)acrylic acid ester include a (meth)acrylic acid alkyl ester, and the alkyl group may be linear, branched, or cyclic, but is preferably a linear alkyl group. For example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, tetradecyl (meth)acrylate, hexadecyl (meth)acrylate, octadecyl (meth)acrylate, and the like.

[0044] Examples of acrylic monomers having a hydroxyl group include (meth)acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, and 8-hydroxyoctyl (meth)acrylate; glycol mono(meth)acrylates such as polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and 1,4-cyclohexanedimethanol mono(meth)acrylate; caprolactone-modified (meth)acrylate; and hydroxyethylacrylamide. The acrylic monomer may also have a functional group other than a hydroxyl group, such as a carboxyl group, an amide bond, an amino group, or an alkylene oxide group. The vinyl chloride-acrylic copolymer preferably has a mass average molecular weight of 10,000 to 70,000. From the standpoint of solubility in environmentally friendly organic solvents and adhesion to substrates, it is preferable that the vinyl chloride-acrylic copolymer has hydroxyl groups in an amount of 50 to 200 mg KOH / g.

[0045] The printing ink composition for laminate may contain a polyurethane resin and (vinyl chloride-vinyl acetate copolymer and / or vinyl chloride-acrylic copolymer) in a mass ratio of polyurethane resin / (vinyl chloride-vinyl acetate copolymer and / or vinyl chloride-acrylic copolymer)=95 / 5 to 45 / 55, and preferably 92 / 8 to 70 / 30. In addition, the ratio of polyurethane resin / (vinyl chloride-vinyl acetate copolymer) may be in the range of 90 / 10 to 75 / 25, and the ratio of polyurethane resin / (vinyl chloride-acrylic copolymer) may be in the range of 95 / 5 to 85 / 15. By containing the polyurethane resin and the vinyl chloride-vinyl acetate copolymer and / or the vinyl chloride-acrylic copolymer in a ratio of 95 / 5 to 45 / 55, the printing ink composition for laminate has better printability and adhesion to the film, and further has better lamination suitability when lamination processing is performed. If the ratio of the polyurethane resin to (vinyl chloride-vinyl acetate copolymer and / or vinyl chloride-acrylic copolymer) exceeds 95 / 5, the proportion of (vinyl chloride-vinyl acetate copolymer and / or vinyl chloride-acrylic copolymer) may become small, and adhesion to the film may become insufficient. On the other hand, if the polyurethane resin / (vinyl chloride-vinyl acetate copolymer and / or vinyl chloride-acrylic copolymer) ratio is less than 45 / 55, the proportion of (vinyl chloride-vinyl acetate copolymer and / or vinyl chloride-acrylic copolymer) will be high, and the printed matter formed using the printing ink composition will become hard, which may also result in insufficient adhesion to the film.

[0046] The combined content of the polyurethane resin and the vinyl chloride-vinyl acetate copolymer and / or vinyl chloride-acrylic copolymer in the printing ink composition for laminate is preferably 5 to 30 mass %. The printing ink composition for laminate may contain one or more selected from an adhesion improver and an antiblocking agent within a range that does not impair the intended performance of the present invention, and it is preferable to use an adhesion improver and an antiblocking agent in combination.

[0047] (Adhesion improver) Examples of adhesion improvers that can be incorporated in the printing ink composition for laminate include rosin and its derivatives, chlorinated polypropylene, dammar resin, etc., and it is desirable to contain at least one type, more preferably two or more types, selected from rosin and its derivatives.

[0048] (Rosin and its derivatives) Examples of rosin include gum rosin, tall oil rosin, wood rosin, etc. Generally, rosin is an amber-colored, amorphous resin obtained from pine trees, and since it is obtained naturally, it is a mixture, but it may be used after being isolated into its constituent components, namely abietic acid, neoabietic acid, palustric acid, pimaric acid, isopimaric acid, sandaracopimaric acid, and dehydroabietic acid, and these are also defined as rosin in the present invention. The rosin derivatives are compounds obtained by modifying the above-mentioned rosins, and specific examples thereof are listed below. (1) Hydrogenated rosin: A rosin whose weather resistance has been improved by adding hydrogen to the conjugated double bonds (hydrogenation). (2) Disproportionated rosin: Disproportionation is a process in which two molecules of rosin react with each other, and two molecules of abietic acid with conjugated double bonds are modified, one to an aromatic compound and the other to a molecule with a single double bond. In general, disproportionated rosin is less weather resistant than hydrogenated rosin, but its weather resistance is better than that of untreated rosin. (3) Rosin-modified phenolic resin: Rosin-modified phenolic resin is sometimes used as the main binder. Rosin-modified phenolic resin can be obtained by a known manufacturing method. (4) Rosin ester: An ester resin derived from rosin, which has long been used as a tackifier in adhesives and adhesives. (5) Rosin-modified maleic acid resin: This is obtained by adding maleic anhydride to rosin, and may also include those in which a hydroxyl-containing compound such as glycerin is esterified with the anhydride group and grafted, if necessary. (6) Polymerized rosin: A derivative containing dimerized resin acid derived from the natural resin rosin. In addition, known rosins and rosin derivatives can also be used, and these can be used alone or in combination. Furthermore, the acid value of the rosin and its rosin derivatives is preferably 120 mgKOH / g or more. When the acid value is 120 mgKOH / g or more, the laminate strength is improved. More preferably, the acid value is 160 mgKOH / g or more. Furthermore, the total amount of rosin and its derivatives used when blending is preferably 0.1 to 3.0 mass% in terms of solid mass% of the printing ink composition for laminate.

[0049] (chlorinated polypropylene) The chlorinated polypropylene may have a chlorination degree of 20 to 50. A chlorinated polypropylene having a chlorination degree of less than 20 tends to have a low compatibility with organic solvents. On the other hand, when the chlorination degree exceeds 50, the chlorinated polypropylene tends to have a low adhesiveness to films. In the present invention, the chlorination degree is defined as the mass% of chlorine atoms in the chlorinated polypropylene resin. The chlorinated polypropylene is preferably a modified or unmodified chlorinated polypropylene having a mass average molecular weight of 5,000 to 200,000. When the mass average molecular weight is less than 5,000, the chlorinated polypropylene tends to have a low adhesiveness. On the other hand, when the mass average molecular weight exceeds 200,000, the chlorinated polypropylene tends to have a low solubility in organic solvents. The amount of the chlorinated polypropylene to be used when blending is preferably 0.1 to 3.0 mass% in terms of solid mass% of the printing ink composition for lamination.

[0050] (Dammar resin) Dammar resin, also written as damar or dammar, is a type of natural resin derived from plants. More specifically, it is a type of natural resin obtained from Dipterocarpaceae or Burseraceae plants that grow in Southeast Asia, such as Malaysia and Indonesia. When used, it is dissolved in an appropriate organic solvent to make a varnish. Since dammar resin does not contain chlorine, it is possible to eliminate or reduce chlorine compared to the use of chlorinated polypropylene in the printing ink composition. In addition, the amount of dammar resin used when blending is preferably 3.0 mass% or less in terms of solid mass% of the printing ink composition for laminate.

[0051] (Anti-blocking agent) Examples of anti-blocking agents include silica particles, polyethylene wax, fatty acid amides, cellulose acetate butyrate resin, cellulose acetate propionate resin, soluble nitrocellulose, etc. It is preferable to contain one or more, preferably two or more, of silica particles, polyethylene wax, and fatty acid amides, and depending on the type of pigment, it is preferable to further contain cellulose acetate butyrate resin, cellulose acetate propionate resin, and soluble nitrocellulose.

[0052] (Silica particles) Examples of silica particles include natural products, synthetic products, crystalline, non-crystalline, hydrophobic, and hydrophilic particles. The silica particles preferably have an average particle size of 1.0 to 5.0 μm (the average particle size of silica particles means the particle size at 50% cumulative value (D50) in particle size distribution, and can be determined by the Coulter counter method). The silica particles may be hydrophilic silica having a hydrophilic functional group on the surface, or may be hydrophobic silica in which the hydrophilic functional group is modified with alkylsilane or the like to be hydrophobic, but hydrophilic particles are preferred, and a printing ink composition containing hydrophilic silica particles has the effect of promoting the wetting and spreading of the printing ink composition during overprinting, and improving the overprinting effect (hereinafter sometimes referred to as "trapping property"). The amount of silica particles used in the printing ink composition for lamination is preferably 3.0 mass% or less, more preferably 0.1 to 1.0 mass%.

[0053] (Polyethylene wax) It is preferable to use a polyethylene wax having an average particle size in the range of 1.0 to 3.0 μm (the average particle size means the particle size measured by Honeywell Microtrac UPA). If the particle size of the polyethylene wax is smaller than 1.0 μm, the slipping property and blocking property may decrease, and if the particle size is larger than 3.0 μm, the trapping property may decrease. The content of the polyethylene wax in the printing ink composition for lamination is preferably in the range of 0.1 to 1.5% by mass. If the content is less than 0.1% by mass, the desired effect cannot be obtained, and if the content is more than 1.5% by mass, the gloss may decrease.

[0054] (nitrocellulose) As the soluble nitrocellulose, soluble nitrocellulose that has been used in gravure printing ink compositions can be used. The soluble nitrocellulose is obtained by reacting natural cellulose with nitric acid to replace three hydroxyl groups in a six-membered ring of anhydrous glucopyranose group in natural cellulose with nitric acid groups to obtain a nitric acid ester. As the soluble nitrocellulose used in the present invention, one having a nitrogen content of 10 to 13% and an average degree of polymerization of 35 to 90 is preferably used. Specific examples include SS1 / 2, SS1 / 4, SS1 / 8, TR1 / 16, NCRS-2, (KOREA CNC LTD), etc. The amount of soluble nitrocellulose used in the printing ink composition for laminate is preferably in the range of 0.1 to 2.0% by mass depending on the type of pigment.

[0055] (Cellulose acetate propionate resin) As the cellulose acetate propionate resin, resins that have been conventionally used in gravure printing ink compositions can be used. The cellulose acetate propionate resin is obtained by triesterifying cellulose with acetic acid and propionic acid, followed by hydrolysis. Generally, resins with 0.6 to 2.5% by mass of acetylation, 42 to 46% by mass of propionylation, and 1.8 to 5% by mass of hydroxyl groups are commercially available. The cellulose acetate propionate resin is preferably used in the range of 0.1 to 3.0% by mass in the printing ink composition for laminate, depending on the type of pigment.

[0056] (Cellulose acetate butyrate resin) As the cellulose acetate butyrate resin, resins that have been conventionally used in gravure printing ink compositions can be used. Cellulose acetate butyrate resin is obtained by triesterifying cellulose with acetic acid and butyric acid, followed by hydrolysis. Generally, resins with 2 to 30% by mass of acetylation, 17 to 53% by mass of butyrylation, and 1 to 5% by mass of hydroxyl groups are commercially available. The amount of cellulose acetate butyrate resin used in the printing ink composition for laminate is preferably within the range of 0.1 to 3.0% by mass, depending on the type of pigment.

[0057] (Fatty acid amide) The fatty acid amide is not particularly limited as long as it has a residue obtained by removing an acid group from a fatty acid and an amide group. Examples of the fatty acid amide include monoamide, substituted amide, bisamide, methylol amide, and ester amide, and at least one selected from the group consisting of monoamide, substituted amide, and bisamide is preferable because it improves blocking resistance. The amount of the fatty acid amide used is preferably in the range of 0.01 to 1.0 mass% in the printing ink composition for laminate.

[0058] Monoamides: Monoamides are represented by the following general formula (1): General formula (1) R 1 -CONH 2 (In the formula, R 1 represents the residue obtained by removing COOH from a fatty acid.) Specific examples of monoamides include lauric acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, hydroxystearic acid amide, oleic acid amide, and erucic acid amide.

[0059] Substituted amide: The substituted amide is represented by the following general formula (2). General formula (2) R 2 -CONH-R 3 (In the formula, R 2 and R 3 represents the residue obtained by removing COOH from a fatty acid, and may be the same or different.) Specific examples of the substituted amide include N-oleyl palmitic acid amide, N-stearyl stearic acid amide, N-stearyl oleic acid amide, N-oleyl stearic acid amide, and N-stearyl erucic acid amide.

[0060] Bisamides: Bisamides are represented by the following general formula (3) or (4). General formula (3) R 4 -CONH-R 5 -HNCO-R 6 General formula (4) R 7 -NHCO-R 8 -CONH-R 9 (In the formula, R 4 , R 6 , R 7 , and R 9 represents the residue obtained by removing COOH from a fatty acid, and may be the same or different. R 5 and R 8 represents an alkylene group or an arylene group having 1 to 10 carbon atoms. Specific examples of bisamides include methylene bisstearic acid amide, ethylene biscapric acid amide, ethylene bislauric acid amide, ethylene bisstearic acid amide, ethylene bishydroxystearic acid amide, ethylene bisbehenic acid amide, hexamethylene bisstearic acid amide, hexamethylene bisbehenic acid amide, hexamethylene hydroxystearic acid amide, ethylene bisoleic acid amide, ethylene biserucic acid amide, hexamethylene bisoleic acid amide, N,N'-distearyl adipamide, N,N'-distearyl sebacic acid amide, N,N'-dioleyl adipamide, and N,N'-dioleyl sebacic acid amide.

[0061] Methylolamide: Methylolamide is represented by the following general formula (5). General formula (5) R 10 -CONHCH 2 OH (In the formula, R 10 represents the residue obtained by removing COOH from a fatty acid.) Specific examples of methylol amides include methylol palmitic acid amide, methylol stearic acid amide, methylol behenic acid amide, methylol hydroxystearic acid amide, methylol oleic acid amide, and methylol erucic acid amide. Esteramide: Esteramide is represented by the following general formula (6): General formula (6) R 11 -CONH-R 12 -OCO-R 13 (In the formula, R 11 and R 13 represents the residue obtained by removing COOH from a fatty acid, and may be the same or different. R 12 represents an alkylene group or an arylene group having 1 to 10 carbon atoms. Specific examples of ester amides include stearylamide ethyl stearate, oleylamide ethyl stearate, and the like. The melting point of the fatty acid amide is preferably 50 to 150°C. Moreover, the fatty acid constituting the fatty acid amide is preferably a saturated fatty acid having 12 to 22 carbon atoms and / or an unsaturated fatty acid having 16 to 25 carbon atoms, and more preferably a saturated fatty acid having 16 to 18 carbon atoms and / or an unsaturated fatty acid having 18 to 22 carbon atoms. Particularly preferred saturated fatty acids are lauric acid, palmitic acid, stearic acid, behenic acid, and hydroxystearic acid, and particularly preferred unsaturated fatty acids are oleic acid and erucic acid.

[0062] (Organic solvent) The printing ink composition for lamination that forms the printing layer is oil-based. The organic solvents used are the same as those used in the ink compositions for surface printing and shrink printing, and include, for example, alcohol-based solvents such as methanol, ethanol, isopropanol, normal propanol, butanol, isobutanol, and tert-butanol, aromatic hydrocarbon-based solvents such as toluene and xylene, aliphatic hydrocarbon-based solvents such as hexane, cyclohexane, methylcyclohexane, and ethylcyclohexane, ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, ester-based solvents such as ethyl acetate, n-propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, and tert-butyl acetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol dimethyl Examples of the esters include glycol solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether, and esters thereof, and as the esters, acetates are mainly selected, such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. These can be used alone or in combination of two or more. From the standpoint of environmental issues, it is preferable to use a mixed solvent of an ester-based organic solvent, an alcohol-based organic solvent and a ketone-based organic solvent, or a mixed solvent of an ester-based organic solvent and an alcohol-based organic solvent which is more environmentally friendly. Furthermore, the printing ink composition for laminate may contain 0.1 to 20 mass% of a glycol ether-based organic solvent in 100 mass% of the organic solvent in order to improve wetting and spreading properties. Specific examples of glycol ether-based organic solvents include ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, ethylene glycol mono n-propyl ether, ethylene glycol monoisopropyl ether, diethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol mono n-propyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and the like.

[0063] It is preferable that the printing ink composition for laminate contains water in order to reduce printing defects caused by static electricity, prevent plate fogging, and improve cell reproducibility. The amount of water used is preferably 10% by mass or less in the printing ink composition for laminate, and more preferably in the range of 0.1 to 5.0% by mass.

[0064] (Other materials) The printing ink composition for laminate may further contain various additives such as a pigment dispersant, an antistatic agent, and a plasticizer.

[0065] (Method for producing laminate printing ink composition) The method for producing a printing ink composition for laminate using the above-mentioned constituent materials includes first stirring and mixing the pigment, binder resin, organic solvent, and, if necessary, pigment dispersant, surfactant, etc., and then grinding the mixture using various grinding machines, such as a bead mill, ball mill, sand mill, attritor, roll mill, pearl mill, etc., and further adding and mixing the various predetermined additives and the remaining materials. Furthermore, a metal tetraalkoxide and / or a hydroxy acid may or may not be contained.

[0066] (Printing method using printing ink composition for laminate, and laminate obtained thereby) Next, a method for obtaining a laminate by using the printing ink composition for laminate will be described. The laminated body in the present invention is a body in which a resin substrate, a detachable primer layer, a printed layer, and a sealant layer are formed in this order, but any layer known to be used in laminated bodies, such as an anchor coating agent layer or an adhesive layer, may or may not be provided between the layers. In addition, the resin substrate, the detachable primer layer, the printed layer, and the sealant layer may each be formed from a plurality of layers. Furthermore, for example, the resin substrate, the detachable primer layer, the printed layer, the detachable primer layer, the printed layer, and the sealant layer may be formed in this order. The method for obtaining the laminated body includes at least the following printing method. For example, the detachment primer composition of the present invention is applied to a resin film that is a known substrate for lamination as a resin substrate, and the resulting layer of the detachment primer composition is printed one or more times in-line or off-line with a printing ink composition for lamination by any printing method such as gravure printing, and then dried by a dryer. The printing speed and drying temperature of the printing ink composition for laminate can be appropriately selected from known speeds and temperatures.

[0067] [Sealant layer] The sealant layer is formed from a resin film used when a lamination means using dry lamination processing is employed, or from a molten resin used when a lamination means using extrusion lamination is employed. Examples of the resin film include unstretched plastic films (e.g., unstretched polyolefin resin films such as unstretched polyethylene film and unstretched polypropylene film), and examples of the molten resin include polyolefin resins such as low-density polyethylene and polypropylene, and ethylene-vinyl acetate copolymers. The properties of the laminated interface of the formed sealant layer differ slightly depending on whether it is derived from a resin film or is formed by laminating molten resin.

[0068] [Method for producing a laminate having a removable primer layer] Next, a method for obtaining a laminate having a removable primer layer will be described. The method for obtaining a laminate having a removable primer layer includes at least the following method (1) or (2). (1) The above-mentioned detachment primer composition is applied to one surface of the above-mentioned resin substrate to form a detachment primer layer, and then the above-mentioned printing ink composition for lamination is printed on the surface of the detachment primer layer at least once by any printing method such as gravure printing, and dried to form a printed layer. Separately from these steps, a removable primer composition is applied to one side of the above-mentioned film for a sealant layer, and then dried to prepare a film for a sealant layer having a removable primer layer. After applying an adhesive to the surface of the above-mentioned printed layer to form an adhesive layer, a laminate having a removable primer layer of the present invention can be produced by a dry lamination method in which the surface of the sealant layer having a removable primer layer is bonded to the surface of the adhesive layer so that the surface of the removable primer layer faces the surface of the adhesive layer. The dry lamination method is a method in which an adhesive layer is formed by applying an adhesive such as a urethane adhesive or an isocyanate adhesive to the surface of a printed layer made of a laminate printing ink composition, and then a sealant layer having a removable primer layer is laminated using a known dry laminating machine. A laminate having a removable primer layer can also be obtained by a known method other than the dry lamination method. (2) The above-mentioned detachment primer composition is applied to one surface of the above-mentioned resin substrate to form a detachment primer layer, and then the above-mentioned printing ink composition for lamination is printed on the surface of the detachment primer layer at least once by any printing method such as gravure printing, and then dried to form a printing layer. Next, a detachable primer composition is applied onto the printed layer, and after drying, an anchor coating agent is applied onto the formed detachable primer layer. After drying, a laminate having a detachable primer composition layer of the present invention can be produced by an extrusion lamination method in which a molten resin such as polyethylene is laminated and solidified on the anchor coating agent layer. The extrusion lamination method is a method in which an anchor coating agent such as a urethane-based, isocyanate-based, or polyethyleneimine-based agent is applied to the surface of the detachable primer layer, and then molten polyethylene is laminated using a known extrusion laminator. When the detachment primer layer uses a polyethyleneimine compound, the polyethyleneimine compound also functions as an anchor coat layer, so that the anchor coat agent may or may not be used. EXAMPLES

[0069] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "%" means "% by mass" and "parts" means "parts by mass". The figures for the amounts of each material in the tables are also "parts by mass". The desorption primer composition used in the examples and comparative examples is a mixture in which the solvent has a mass composition of 8 parts ethanol and 2 parts water. However, the present invention is not limited to this mixture.

[0070] <Examples and Comparative Examples> First, the laminate structure will be described. The laminate structure is (Dry Lamination) Laminated structure 1 OPP / Various detachable primer compositions / Various reverse printing ink compositions / Adhesives / Various detachable primer compositions / Sealant layer Laminated Structure 2 ·PET / Various detachable primer compositions / Various reverse printing ink compositions / Adhesive / Various detachable primer compositions / Sealant layer Laminated structure 3 ·NY / Various detachable primer compositions / Various reverse printing ink compositions / Adhesives / Various detachable primer compositions / Sealant layer Laminated structure 4 ·Transparent deposition film / Various detachable primer compositions / Various reverse printing ink compositions / Adhesives / Various detachable primer compositions / Sealant layer (Extrusion Lamination) Laminated Structure 5 ·PET, NY, transparent deposition film / Various detachable primer compositions / Various reverse printing ink compositions / Various detachable primer compositions / Anchor coating agents / Sealant layers Laminated Structure 6 OPP / Various detachable primer compositions / Various reverse printing ink compositions / Various detachable primer compositions Adhesives (anchor coating agents) / Sealant layers

[0071] <Production example of polyurethane resin varnish 1 (biomass polyurethane)> In a four-neck flask equipped with a stirrer, a cooling tube, and a nitrogen gas inlet tube, 200 parts by mass of polyester diol having a mass average molecular weight of 2000 obtained from sebacic acid (derived from castor oil) / succinic acid (derived from plant) = 30 / 70 (mass ratio) and 1,3-propanediol (derived from plant), 17.6 parts by mass of isophorone diisocyanate, and 21.0 parts by mass of hydrogenated MDI were charged, and reacted for 6 hours at 100 to 105 ° C. while introducing nitrogen gas. After cooling to near room temperature, 400 parts by mass of ethyl acetate and 171 parts by mass of isopropyl alcohol were added, and then 8.2 parts by mass of isophorone diamine were added to extend the chain, and 0.35 parts by mass of monoethanolamine were added to react, and then 1.3 parts by mass of isophorone diamine and 0.6 parts by mass of diethylene triamine were added to stop the reaction, and polyurethane resin varnish 1 (solid content 30 mass%, amine value 6.4 mg KOH / g) was obtained.

[0072] <Production example of polyurethane resin varnish 2 (not biomass polyurethane)> A four-neck flask equipped with a stirrer, a cooling tube and a nitrogen gas inlet tube was charged with 100 parts by mass of 3-methyl-1,5-pentylene adipate diol having a number average molecular weight of 2000, 100 parts by mass of polypropylene glycol having a mass average molecular weight of 2000, 17.6 parts by mass of isophorone diisocyanate, and 21.0 parts by mass of hydrogenated MDI, and reacted for 6 hours at 100 to 105 ° C. while introducing nitrogen gas. After cooling to near room temperature, 400 parts by mass of ethyl acetate and 171 parts by mass of isopropyl alcohol were added, and then 8.2 parts by mass of isophorone diamine were added to extend the chain, and 0.35 parts by mass of monoethanolamine were added to react, and then 1.3 parts by mass of isophorone diamine and 0.6 parts by mass of diethylene triamine were added to stop the reaction, and polyurethane resin varnish 2 (solid content 30% by mass, amine value 6.4 mg KOH / g) was obtained.

[0073] <Production Example of Polyurethane Resin Varnish 3 Obtained by Using a Compound in Which the Amino Group of a Polyamine Compound is Ketiminated with a Ketone Compound> (Method of producing ketimine solution) 51 parts of isophoronediamine, 31.2 parts of N-(2-hydroxyethyl)ethylenediamine, and 174 parts of acetone were mixed and stirred at room temperature for 1 hour to obtain a ketimine solution. (Method of manufacturing polyurethane resin) A four-neck flask equipped with a stirrer, a cooling tube, and a nitrogen gas inlet tube was charged with 400 parts of 3-methyl-1,5-pentylene adipate diol having a number average molecular weight of 4000, 33.3 parts of isophorone diisocyanate, and 0.04 parts of tetrabutyl titanate, and the mixture was reacted at 90 to 100°C for 6 hours while introducing nitrogen gas. Next, 812 parts of propyl acetate and 203 parts of isopropyl alcohol were added, and the mixture was cooled to near room temperature. 32.29 parts of the above ketimine solution was added and stirred for 20 minutes, and then 3 parts of water was added and stirred for 15 minutes to obtain a polyurethane resin varnish 3 (solid content 30%) having a mass average molecular weight of 35,000 and an amine value of 6.5 mgKOH / g.

[0074] <Vinyl chloride / vinyl acetate copolymer> Solvine TA-3, Nissin Chemical Industry Co., Ltd. <Rosin and its derivatives> Polymerized rosin: Acid value 160mgKOH / g <Chlorinated polypropylene varnish> 40 parts by mass of chlorinated polypropylene (solid content 50%) having a chlorination degree of 40% and a mass average molecular weight of 100,000 and 60 parts by mass of methylcyclohexane were mixed and stirred to obtain a chlorinated polypropylene varnish having a solid content of 20%.

[0075] <Production of printing ink composition for laminate> 10 parts by mass of pigment (CIPB15:4), 30 parts by mass of polyurethane resin 1, and 3 parts by mass of vinyl chloride-vinyl acetate copolymer (Solvine TA-3) were kneaded using Red Devil's paint conditioner, and 2 parts by mass of the above chlorinated polypropylene varnish (solid content 20%), 0.5 parts by mass of polymerized rosin, 0.5 parts by mass of silica particles with an average particle size of 4.5 μm, 0.2 parts by mass of polyethylene wax with an average particle size of 2.11 μm, 0.2 parts by mass of ethylene bisstearic acid amide, 51 parts by mass of solvent, and 2 parts by mass of water were added to obtain printing ink composition 1 for laminate. Furthermore, printing ink compositions for laminate 2 and 3 were also obtained in which polyurethane resins 2 and 3 were used instead of the polyurethane resin 1 described above.

[0076] (Resin substrate) Corona-discharged biaxially oriented polypropylene film: P-2161#25 (Toyobo Co., Ltd.) Polyester film: E-5102#12 (Toyobo) Nylon film: ON-15#12 (Unitika) Transparent vapor-deposited polyester film: GL-ARH-F (Toppan Printing) Transparent vapor-deposited nylon film: GL-AEY-W (Toppan Printing)

[0077] (Removal primer compositions 1 to 7) Desorption primer composition 1: Polyethyleneimine compound (product name Epomin P-1000 (Nippon Shokubai Co., Ltd.)) number average molecular weight (Mn) 70,000, mass average molecular weight (Mw) 350,000, amine value 18 mmol / g, amine ratio (molar ratio (%) of primary, secondary and tertiary amino groups) primary / secondary / tertiary = 25 / 50 / 25 (Table 1 below) (the number average molecular weight (Mn) was measured by a viscosity method, the mass average molecular weight was measured by GPC, the amine value was measured by acid titration using a non-aqueous system, and the amine ratio was measured by NMR (13C) (same below)) Desorption primer composition 2: Polyethyleneimine compound (product name Epomin P-3000 (Nippon Shokubai Co., Ltd.)) number average molecular weight (Mn) 100,000, mass average molecular weight (Mw) 450,000, amine value 18 mmol / g, amine ratio (molar ratio (%) of primary, secondary and tertiary amino groups) primary / secondary / tertiary = 30 / 40 / 30 (Table 1 below) (the number average molecular weight (Mn) was measured by a viscosity method, the amine value was measured by acid titration using a non-aqueous system, and the amine ratio was measured by NMR (13C).) Desorption primer composition 3: polyethyleneimine-based compound (trade name Lupasol P (manufactured by BASF), mass average molecular weight (Mw) 750,000, amine value 18 mmol / g, amine ratio (molar ratio (%) of primary, secondary and tertiary amino groups) primary / secondary / tertiary = 37 / 37 / 26 (Table 1 below) (the number average molecular weight (Mn) was measured by a viscosity method, the amine value was measured by acid titration using a non-aqueous system, and the amine ratio was measured by NMR (13C)). Detachment primer composition 4: Polybutadiene compound (product name: Titabond T-180E, (NV10%), Nippon Soda Co., Ltd.) Desorption primer composition 5: A composition (solid content 3.0% by mass) in which a polyethyleneimine compound (trade name Epomin P-1000 (Nippon Shokubai Co., Ltd.)) contains 3-glycidyloxypropyltrimethoxysilane (Table 1 below): the polyethyleneimine compound (trade name Epomin P-1000 (Nippon Shokubai Co., Ltd.)) / 3-glycidyloxypropyltrimethoxysilane (mass ratio)=1 / 2. The ratio of the number of glycidyl groups of the silane coupling agent to the amino groups of the polyethyleneimine compound in Table 2 is determined based on the above-mentioned concept, and is the number of the glycidyl groups in the applied desorption primer composition divided by the total number of the primary amino groups and the secondary amino groups. Desorption primer composition 6: A composition (solid content 3.0% by mass) in which a polyethyleneimine compound (trade name Epomin P-1000 (Nippon Shokubai Co., Ltd.)) is mixed with triethoxy(3-isocyanatepropyl)silane (Table 1 below): the polyethyleneimine compound (trade name Epomin P-1000 (Nippon Shokubai Co., Ltd.)) / triethoxy(3-isocyanatepropyl)silane (mass ratio)=1 / 2. The ratio of the number of isocyanate groups of the silane coupling agent to the amino groups of the polyethyleneimine compound in Table 2 is determined based on the above-mentioned concept, and is the number of isocyanate groups in the applied desorption primer composition divided by the total number of the primary amino groups and the secondary amino groups. Desorption primer composition 7: Trimethoxysilylpropyl-modified (polyethyleneimine) (siloxane-modified polyethyleneimine) (product name: SSP-060, Gelest), molecular weight 1,500 to 1,800, amine value 10 mmol / g, amine value measured by acid titration using a non-aqueous system, amine ratio measured by NMR (13C).

[0078] [Table 1]

[0079] [Table 2]

[0080] (glue) Takelac A-969V / Takelac A-5 Two-component polyurethane adhesive (Mitsui Chemicals) Takelac A-515 / Takelac A-50 Two-component polyurethane adhesive (Mitsui Chemicals) (Anchor coating agent) Takelac A-3210 / Takenate A-3072 (Mitsui Chemicals) Polyethylenimine P-1000 (Nippon Paper Industries), which also acts as a desorption primer composition (Lamination film) P-1128#25 Non-oriented polypropylene film (Toyobo) RXC-22 Non-oriented polypropylene film (Mitsui Chemicals Tocello) (Melted Polyethylene) Sumikasen L705 (Sumitomo Chemical Co., Ltd.)

[0081] (Laminate printing, laminates, test results) (For dry lamination) Each of the detachable primer compositions shown in Table 2 above was diluted and applied to one side of a resin substrate and dried under the following conditions using a gravure printer to obtain a detachable primer layer so as to obtain a laminate having the following laminate structure. The coating amount in Table 2 is the solid content amount of the detachment primer composition layer, which was adjusted according to the concentration of the solid content in the detachment primer composition. Laminate printing ink composition 1 was further diluted with a mixed solvent of normal propyl acetate / isopropyl alcohol = 80 / 20 to 16 seconds using a Rigosha Zahn Cup No. 3 to obtain diluted laminate printing ink composition 1. The diluted laminate printing ink composition 1 was printed on the surface of each of the detachment primer layers using a gravure printing machine under the following conditions, and then dried to obtain a printed layer. When the resin substrate was a corona-discharged biaxially oriented polypropylene film, an adhesive (Takelac A-969V / Takelac A-5) was applied; when the resin substrate was a polyester film, nylon film, transparent vapor-deposited polyester film, or transparent vapor-deposited nylon film, an adhesive (Takelac A-515 / Takelac A-50, 30% solids) was applied. Next, the removable primer layer side of the sealant layer having the removable primer layer applied on one side thereof was adhered to the printed layer by a dry laminator to prepare a laminate.

[0082] (In the case of extrusion lamination) Each detachment primer composition shown in Table 2 above was diluted and applied to one side of a resin substrate and dried under the following conditions using a gravure printer to obtain a detachment primer layer so as to obtain a laminate having the following laminate structure. The application amount in Table 2 is the solid content of the detachment primer composition layer. The coating amount was adjusted according to the concentration of the solid content in the release primer composition. Laminate printing ink composition 1 was further diluted with a mixed solvent of n-propyl acetate / isopropyl alcohol = 80 / 20 to 16 seconds using a Rigosha Zahn Cup No. 3 to obtain diluted laminate printing ink composition 1. The diluted laminate printing ink composition 1 was printed on the surface of each release primer layer using a gravure printer under the following conditions and dried to obtain a printed layer. When the resin substrate was a corona-discharged biaxially oriented polypropylene film, an anchor coating agent (P-1000) was applied thereon; when the resin substrate was a polyester film, a nylon film, a transparent vapor-deposited polyester film, or a transparent vapor-deposited nylon film, each release primer composition was applied thereon, dried, and then an anchor coating agent (Takelac A-3210 / Takelac A-3072, 7% solids) was applied thereon. Next, when an anchor coating agent (Takelac A-3210 / Takelac A-3072, solid content 7%) was applied, molten polyethylene was attached to the undercoat agent surface by an extrusion laminator to adhere to the anchor coating agent layer, creating a laminate. However, when P-1000 was used as the undercoat agent, molten polyethylene was attached to the undercoat agent layer by an extrusion laminator to create a laminate.

[0083] (Application conditions for each primer composition for detachment) Coating machine: Gravure printing machine Coating speed: 100m / min Plate: Helio 175 line / inch (130°) solid plate Drying temperature: 70℃ (Printing conditions for laminate printing ink composition 1) Coating machine: Gravure printing machine Coating speed: 100m / min Plate: Helio 175 line / inch (130°) solid plate Drying temperature: 55℃

[0084] [Table 3]

[0085] <Evaluation of Release (Ink Release)> 1.5 g of each of the above laminates was cut into small pieces of about 15 mm MD×25 mm TD to obtain samples for ink release property testing. (Preparation of the release solution consisting of an alkaline aqueous solution) 2.0 parts by mass of sodium hydroxide was added to 98.0 parts by mass of water, and the mixture was stirred and dissolved to obtain a release liquid consisting of an alkaline aqueous solution. 100 g of the alkaline aqueous solution was placed in a 200 cc HDPE (high density polyethylene) container and heated in a hot water bath until the liquid temperature reached 70°C. (Detachment) The corresponding ink release test samples were added to each of the heated release liquids and stirred for 30 minutes using a stainless steel stirring blade with a blade diameter of 25 mm. After stirring, the HDPE (high density polyethylene) container was removed from the hot water bath and allowed to stand at room temperature for 5 minutes. The release liquid and the various film pieces were separated using a stainless steel mesh with a mesh opening of approximately 2 mm. (rinse) After removal, each film was transferred to a 200cc HDPE container and 100g of water was added. The mixture was stirred for 5 minutes using a stainless steel stirring blade with a blade diameter of 25mm. After leaving the mixture to stand for 5 minutes, the film pieces were separated from the water using a stainless steel mesh. After drying the film pieces, the releasability of the ink from the films was visually evaluated. (Evaluation Criteria) ○: The ink film was completely peeled off from the resin base film and the sealant film as film pieces. △: The ink film is completely detached from the resin substrate film as film pieces, but is not detached from the sealant film. ×: Neither the resin base film nor the sealant film peeled off.

[0086] (Adhesion immediately after printing (adhesion immediately after printing and drying the printing ink composition for lamination 1)) Each release primer composition was diluted to the prescribed coating amount as shown in Table 3 above using a gravure printer on various resin substrate films and then dried under the following conditions using the gravure printer: Each laminate printing ink composition 1, which was diluted by adding a normal propyl acetate / isopropyl alcohol = 80 / 20 mixed solvent to each laminate printing ink composition and diluting it to 16 seconds using a Rigosha Zahn Cup No. 3, was printed on the surface of each release primer composition layer using the gravure printer under the above conditions and dried to obtain each print. A cellophane tape was applied to the printed surface of each of the obtained prints, and the tape was quickly peeled off. Based on the degree to which the printed film peeled off, the adhesion was evaluated according to the following evaluation criteria. (Evaluation Criteria) ◯: The area ratio of the printed coating that peeled off from the resin substrate film was less than 5%. △: 5% or more and less than 30% of the area of ​​the printed coating peeled off from the resin substrate film. ×: 30% or more of the area of ​​the printed coating was peeled off from the resin substrate film.

[0087] (Laminate strength) After each laminate print was obtained, it was cut to a width of 15 mm, and the T-peel strength was measured using a Yasuda Seiki Seisakusho peel tester. -Takelac A-969V / Takelac A-5 two-component polyurethane adhesive (Mitsui Chemicals) was used as the adhesive. (Evaluation Criteria) ○: Peel strength is 1.2N / 15mm or more △: Peel strength is 0.7N / 15mm or more and less than 1.2N / 15mm ×: Peel strength is less than 0.7N / 15mm -Takelac A-515 / Takelac A-50 Two-component polyurethane adhesive (Mitsui Chemicals) (Evaluation Criteria) ○: Peel strength is 5N / 15mm or more △: Peel strength is 3N / 15mm or more and less than 5N / 15mm ×: Peel strength is less than 3N / 15mm

[0088] (Blocking resistance) Using a gravure printer, each of the release primer compositions diluted as shown in Table 3 above was applied to various resin substrate films and dried under the following conditions. Each of the lamination printing ink compositions, which had been diluted by adding a mixed solvent of normal propyl acetate / isopropyl alcohol = 80 / 20 and using a Rigosha Zahn Cup No. 3 to give a dilution of 16 seconds, was printed on the surface of each release primer composition layer using a gravure printer under the following conditions, and dried. The printed surface of each print and the untreated surface of each resin substrate film were combined, and 400 g / cm 2 After leaving the sample at 40° C. for 12 hours under a load of 1000 μm, the blocking resistance was evaluated based on the state of each resin substrate film when it was peeled off. (Evaluation Criteria) ○: Peels off without resistance and there is no transfer of the ink film △: There is resistance, but the ink film does not transfer at all ×: Transfer of the ink film was observed. The following evaluations were the same when using not only the above laminate printing ink composition 1 but also the above laminate printing ink compositions 2 and 3. Therefore, the results for the above laminate printing ink composition 1 are shown below.

[0089] (Dry Lamination) Laminated structure 1 ·OPP / Various removable primer compositions / Various reverse printing ink compositions / Adhesive / Various removable primer compositions / Sealant layer (P-1128#25) <Examples and Comparative Examples shown in Table 4 below> In each example shown in Table 4, P-2161#25 was used as the resin substrate, and layers were formed thereon using various types of primer compositions for detachment, a printing ink composition for lamination, an adhesive (Takelac A-969V / Takelac A-5 solid content 30%), various types of primer compositions for detachment, and P-1128#25. As a result, all evaluation results were excellent. In addition, Examples 1 to 7 are examples in which a detachment primer composition containing a polyethyleneimine compound is used, Example 8 is an example in which a polybutadiene-based compound is used, Example 9 is an example in which a polyethyleneimine compound containing a silane coupling agent containing a glycidyl group is used, Example 10 is an example in which a polyethyleneimine compound containing a silane coupling agent containing an isocyanate group is used, and Example 11 is an example in which a siloxane-modified polyethyleneimine compound is used. In the laminate structure 1, "double-sided application" means that the detachment primer composition is applied to the resin substrate, and is applied between the adhesive layer and the laminate layer to form a detachment primer layer. Furthermore, Comparative Example 1 shown in Table 4 is an example in which, unlike the above-mentioned Examples, neither of the layers made of the detachment primer composition was formed, and as a result, detachment was insufficient.

[0090] [Table 4]

[0091] Dry Lamination Laminated Structure 2 ·PET / Various detachable primer compositions / Various reverse printing ink compositions / Adhesive / Various detachable primer compositions / Sealant layer (RXC-22) <Examples and Comparative Examples shown in Table 5 below> In each example shown in Table 5, E-5102#12 was used as the resin substrate, and layers were formed thereon using various types of primer compositions for detachment, a printing ink composition for lamination, an adhesive (Takelac A-515 / Takelac A-50, solid content 30%), various types of primer compositions for detachment, and RXC-22. As a result, all evaluation results were excellent. In addition, Examples 12 to 18 are examples of using a detachment primer composition containing a polyethyleneimine compound, Example 19 is an example of using a polybutadiene compound, Example 20 is an example of using a polyethyleneimine containing a silane coupling agent containing a glycidyl group, Example 21 is an example of using a polyethyleneimine compound containing a silane coupling agent containing an isocyanate group, and Example 22 is an example of using a siloxane-modified polyethyleneimine compound. In the laminate structure 2, "double-sided application" means that the detachment primer composition is applied to the resin substrate, and is applied between the adhesive layer and the laminate layer to form a detachment primer layer. Furthermore, Comparative Example 2 shown in Table 5 is an example in which, unlike the above-mentioned Examples, neither of the layers made of the detachment primer composition was formed, resulting in insufficient detachment.

[0092] [Table 5]

[0093] Dry Lamination Laminated structure 3 ·NY / Various detachable primer compositions / Various reverse printing ink compositions / Adhesive / Various detachable primer compositions / Sealant layer (RXC-22) <Examples and Comparative Examples shown in Table 6 below> In each example shown in Table 6, ON#15 was used as the resin substrate, and layers were formed thereon using various types of primer compositions for detachment, a printing ink composition for lamination, an adhesive (Takelac A-515 / Takelac A-50 solid content 30%), various types of primer compositions for detachment, and RXC-22. As a result, all evaluation results were excellent. In addition, Examples 23 to 29 are examples in which a polyethyleneimine compound is used as the detachment primer composition, Example 30 is an example in which a polybutadiene compound is used, Example 31 is an example in which a silane coupling agent containing a glycidyl group is used in polyethyleneimine, Example 32 is an example in which a silane coupling agent containing an isocyanate group is used in polyethyleneimine, and Example 33 is an example in which a siloxane-modified polyethyleneimine compound is used. In the laminate structure 3, "both-side application" means that the detachment primer composition is applied to the resin substrate, and the detachment primer layer is formed by applying between the adhesive layer and the laminate layer. do. Furthermore, Comparative Example 3 shown in Table 6 is an example in which, unlike the above-mentioned Examples, neither of the layers made of the detachment primer composition was formed, resulting in insufficient detachment.

[0094] [Table 6]

[0095] Dry Lamination Laminated structure 4 ·Transparent deposition film / Various detachable primer compositions / Various reverse printing ink compositions / Adhesives / Various detachable primer compositions / Sealant layer (RXC-22) In each of the examples shown in Table 7, GL-ARH-F and GL-AEY-W were used as the resin substrate, and layers were formed thereon using various types of primer compositions for detachment, a printing ink composition for lamination, an adhesive (Takelac A-515 / Takelac A-50, solid content 30%), various types of primer compositions for detachment, and RXC-22, in that order. As a result, all evaluation results were excellent. In addition, Examples 34 to 40 are examples in which a polyethyleneimine-based compound was used as the detachment primer composition, Example 41 is an example in which a polybutadiene-based compound was used, Example 42 is an example in which a silane coupling agent containing a glycidyl group was used in polyethyleneimine, Example 43 is an example in which a silane coupling agent containing an isocyanate group was used in polyethyleneimine compound, and Example 44 is an example in which a siloxane-modified polyethyleneimine compound was used. In the laminate structure 4, "both-side application" means that the detachment primer composition is applied to the resin substrate, and is applied between the adhesive layer and the laminate layer to form a detachment primer layer. The evaluation is the same regardless of whether the transparent vapor deposition film GL-ARH-F or GL-AEY-W is used, and Table 7 shows the evaluation results of both GL-ARH-F and GL-AEY-W. do. Furthermore, Comparative Example 4 shown in Table 7 is an example in which, unlike the above-mentioned Examples, neither of the layers made of the detachment primer composition was formed, resulting in insufficient detachment.

[0096] [Table 7]

[0097] (Extrusion Lamination) Laminated Structure 5 ·PET, NY, transparent deposition film / Various detachable primer compositions / Various reverse printing ink compositions / Various detachable primer compositions / Undercoat agents / Sealant layer (Sumikathene L705) In each example shown in Table 8, E-5102#12, ON#15, GL-ARH-F, and GL-AEY-W were used as the resin substrate, and layers were formed thereon in order of various primer compositions for detachment, printing ink composition for lamination, various primer compositions for detachment, anchor coating agent (Takelac A-3210 / Takenate A-3072 solid content 7%), and Sumikathene L705 by extrusion lamination. As a result, all evaluation results were excellent. In addition, Examples 45 to 50 are examples in which a polyethyleneimine compound is used as the detachment primer composition, Example 51 is an example in which a polybutadiene compound is used, Example 52 is an example in which a silane coupling agent containing a glycidyl group is used in polyethyleneimine, Example 53 is an example in which a silane coupling agent containing a glycidyl group is used in polyethyleneimine, Example 54 is an example in which a silane coupling agent containing an isocyanate group is used in polyethyleneimine compound, and Example 55 is an example in which a siloxane-modified polyethyleneimine compound is used. In the laminate structure 5, "both-side application" means that the detachment primer composition is applied to the resin substrate, and the detachment primer layer is formed by application between the anchor coat layer and the extrusion laminate layer. The evaluation was the same regardless of whether E-5102#12, ON#15, or GL-ARH-F was used, and Table 8 shows all the evaluation results for E-5102#12, ON#15, and GL-ARH-F. do. Furthermore, Comparative Example 5 shown in Table 8 is an example in which, unlike the above-mentioned Examples, neither of the layers made of the detachment primer composition was formed, and as a result, detachment was insufficient.

[0098] [Table 8]

[0099] (Extrusion Lamination) Laminated Structure 6 ·OPP / Various detachable primer compositions / Various reverse printing ink compositions / Various detachable primer compositions (anchor coating agents) / Sealant layer (Sumikathene L705) In each example shown in Table 9, P-2161#25 was used as the resin substrate, and layers were formed thereon in order using various detachment primer compositions, printing ink compositions for lamination, various detachment primer compositions (which also act as anchor coating agents), and Sumikathene L705 by extrusion lamination. As a result, all evaluation results were excellent. In addition, Examples 56 to 61 are examples in which a polyethyleneimine compound is used as the detachment primer composition, Example 62 is an example in which a polybutadiene compound is used, Example 63 is an example in which a silane coupling agent containing a glycidyl group is used in polyethyleneimine, Example 64 is an example in which a silane coupling agent containing a glycidyl group is used in polyethyleneimine, Example 65 is an example in which a silane coupling agent containing an isocyanate group is used in polyethyleneimine compound, and Example 66 is an example in which a siloxane-modified polyethyleneimine compound is used. In the laminate structure 5, "both-side application" means that the detachment primer composition is applied to the resin substrate, and the detachment primer layer is formed by application between the printing layer and the extrusion laminate layer. Furthermore, Comparative Example 6 shown in Table 9 is an example in which, unlike the above-mentioned Examples, neither of the layers made of the detachment primer composition was formed, resulting in insufficient detachment.

[0100] [Table 9]

[0101] Desorption primer composition 8 A detachment primer composition 8 (number of glycidyl groups in the silane coupling agent) / (total number of primary amino groups and secondary amino groups in the polyethyleneimine compound)=1.55) was obtained in the same manner as in detachment primer composition 5, except that the mass ratio of polyethyleneimine compound (trade name Epomin P-1000 (Nippon Shokubai)) / 3-glycidyloxypropyltrimethoxysilane in detachment primer composition 5 was changed from 1 / 2 to 1 / 5. For the laminate structures 1 to 6 in which the detachment primer composition 8 was used, the detachment, adhesiveness immediately after printing, laminate strength, and blocking resistance were all rated as ◯.

Claims

1. The laminate is formed by laminating a resin substrate, a detachable primer layer, a printed layer, a detachable primer layer, and a sealant layer in this order, and the detachable primer composition for forming the detachable primer layer is a detachable primer composition containing a polyethyleneimine-based compound having an amine value of 5.0 to 25.0 mmol / g and / or a polybutadiene-based compound.

2. The laminate according to claim 1, wherein the detachment primer composition containing a polyethyleneimine-based compound having an amine value of 5.0 to 25.0 mmol / g and / or a polybutadiene-based compound contains one or more compounds selected from the following a. to d.: a. Polybutadiene compounds b. Polyethyleneimine compounds c. A mixture containing a polyethyleneimine compound and a glycidyl group-containing silane coupling agent and / or an isocyanate group-containing silane coupling agent. d. Siloxane-modified polyethyleneimine compound

3. The laminate according to claim 1 or 2, which is any one of the following (1) to (3). (1) A laminate having, in order, a resin substrate, a removable primer layer, a printed layer, an adhesive layer, a removable primer layer, and a sealant layer formed by dry lamination. (2) In the case of extrusion lamination: a laminate having, in order, a resin substrate, a removable primer layer, a printed layer, a removable primer layer, an anchor coating agent, and a sealant layer formed by extrusion lamination. (3) In the case of extrusion lamination: a laminate having, in order, a resin substrate, a removable primer layer, a printed layer, a removable primer layer, and a sealant layer formed by extrusion lamination.

4. 3. The laminate according to claim 1, wherein the number average molecular weight of the polyethyleneimine compound and the number average molecular weight of the siloxane-modified polyethyleneimine compound are each independently from 1,000 to 200,000.

5. 3. The laminate according to claim 1, wherein the polyethyleneimine compound and the siloxane-modified polyethyleneimine compound each independently have a mass average molecular weight of 4,000 to 800,000.

6. 3. A laminate using the detachment primer composition according to claim 1 or 2, wherein the polybutadiene compound is a hydroxyl group-containing polybutadiene compound and / or a carboxyl group-containing polybutadiene compound.

7. 3. A laminate using the release primer composition according to claim 1 or 2, wherein the sealant layer is formed from a non-oriented plastic film or a molten resin.

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