Matte coating agent and laminate using the same

Abstract

To provide a mat coating agent having special effects in blocking resistance, heat resistance, reverse gloss properties, friction resistance and matting properties.SOLUTION: The problem is solved by a matte coating agent containing a binder resin, a matting agent, and an organic solvent, in which the binder resin contains a urethane resin, the urethane resin contains a constituent unit derived from a dibasic acid, and the matting agent contains silica and an extender pigment (A) other than the silica.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a matte coating agent, and more particularly to a matte coating agent that provides excellent blocking resistance, heat resistance, reverse gloss resistance, abrasion resistance, and matte properties for protecting the surface of a substrate and improving the design of packaging materials. [Background technology]

[0002] Conventionally, various matte coating layers have been applied to various substrates for surface protection and design enhancement. Matte coating layers impart a matte finish and a cloudy appearance. They are typically formed as the outermost layer of a laminate by printing or applying a matte coating agent. By covering the substrate, they aim to protect the surface of the substrate, or to adjust gloss and matte finish, transparency and cloudiness as needed to provide the desired design. Furthermore, matte coating layers are sometimes applied to impart tactile sensation or slipperiness. Applications span a wide range of fields, including food packaging, pharmaceutical packaging, household goods materials, electronic packaging, reflective materials, electrical appliances, and automobiles.

[0003] The matte coating layer is disposed as the outermost layer of the laminate, and therefore requires abrasion resistance and substrate adhesion. To improve substrate adhesion, for example, Patent Document 1 discloses the use of a compound containing an isocyanate group as a curing component of a binder resin containing a urethane resin to form a crosslinked structure. Furthermore, the addition of a wax component, polypropylene resin particles, or glass beads is also known. The addition of polytetrafluoroethylene wax particles has also been proposed to improve abrasion resistance.

[0004] Furthermore, Patent Document 2 proposes a matte coating agent in which the binder resin contains a urethane resin, the matting agent contains barium sulfate and resin fine particles, and the mass ratio of the binder resin to the matting agent (binder resin / matting agent) is 1:1 to 1:3.

[0005] However, it has been difficult for any of the above matte coating agents to satisfy all of the requirements for sufficient blocking resistance, heat resistance, reverse gloss resistance, abrasion resistance, and matte properties, which has been a problem. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 2018-070847 [Patent Document 2] Patent No. 6994615 Summary of the Invention [Problem to be solved by the invention]

[0007] An object of the present invention is to provide a matte coating agent having blocking resistance, heat resistance, negative gloss resistance, abrasion resistance, and matte properties. [Means for solving the problem]

[0008] In view of the above problems, the present inventors have conducted extensive research and have found that the problems can be solved by using the matte coating agent described below, thereby completing the present invention.

[0009] That is, the present invention provides a matte coating agent containing a binder resin, a matting agent, and an organic solvent, The matte coating agent relates to a matte coating agent in which the binder resin contains a urethane resin, the urethane resin contains a structural unit derived from a dibasic acid, and the matting agent contains silica and an extender pigment (A) (excluding the case where the extender pigment (A) is silica).

[0010] That is, the present invention relates to the matte coating agent, wherein the extender pigment (A) comprises at least one selected from the group consisting of calcium carbonate, barium sulfate, and kaolin.

[0011] That is, the present invention relates to the matte coating agent, wherein the binder resin further contains a vinyl chloride copolymer resin and / or a cellulose resin.

[0012] That is, the present invention relates to the matte coating agent, wherein the content of the matting agent in the total solid content of the matte coating agent is 20 to 60 mass %.

[0013] That is, the present invention relates to the matte coating agent, wherein the dibasic acid-derived constitutional units are biomass dibasic acid-derived constitutional units.

[0014] That is, the present invention relates to the matte coating agent, wherein the urethane resin further contains a non-biomass urethane resin.

[0015] That is, the present invention relates to the matte coating agent, wherein the content of the urethane resin in the total solid content of the matte coating agent is 15 to 65 mass %.

[0016] That is, the present invention relates to the matte coating agent, wherein the content of silica in the total solid content of the matting agent is 0.1 to 50 mass %.

[0017] That is, the present invention relates to the matte coating agent, which further contains a wax.

[0018] That is, the present invention relates to a printed matter having a matte coating layer formed from the above matte coating agent.

[0019] That is, the present invention relates to a laminate having a matte coating layer formed from the matte coating agent, a substrate 1, a printing ink layer, and a substrate 2 in this order. [Effects of the Invention]

[0020] The present invention makes it possible to provide a matte coating agent having blocking resistance, heat resistance, negative gloss resistance, abrasion resistance, and matte properties. DETAILED DESCRIPTION OF THE INVENTION

[0021] The following describes in detail the embodiments of the present invention. However, the description of the constituent elements described below is an example (representative example) of an embodiment of the present invention, and the present invention is not limited to these contents as long as it does not exceed the gist of the present invention.

[0022] Hereinafter, the matte coating agent may be abbreviated simply as "coating agent," but this has the same meaning. Furthermore, the "matte coating layer" formed by the matte coating agent may be abbreviated as "coating layer," but this has the same meaning. In this specification, the "solid content" refers to the total mass of nonvolatile components in the total mass of the coating agent.

[0023] (Matte coating agent) The present invention is characterized by a matte coating agent containing a urethane resin containing a structural unit derived from a dibasic acid, silica, an extender pigment (A) other than silica, and an organic solvent. In the present invention, the combination of a urethane resin containing a dibasic acid-derived structural unit, silica, and an extender pigment (A) other than silica improves blocking resistance. This is believed to be due to the fact that the combination of silica and an extender pigment (A) other than silica creates irregularities on the surface of the matte coating layer, and the use of a urethane resin containing a dibasic acid-derived structural unit adsorbs the silica and the extender pigment (A) to form a tough coating film, further improving blocking resistance. The solids content of the matte coating agent is preferably 10% to 60% by mass, more preferably 12% to 50% by mass, and even more preferably 15% to 40% by mass. Furthermore, when a biomass dibasic acid such as sebacic acid or dimer acid is used as the dibasic acid, the flexible resin properties improve the coating agent stability, heat resistance, and blocking resistance. Note that this discussion is based solely on speculation and does not limit the invention in any way.

[0024] (binder resin) The binder resin used in the present invention includes a urethane resin. The binder resin refers to the binding resin in the matte coating agent of the present invention, and is preferably a thermoplastic resin soluble in an organic solvent. The content of the binder resin in the total solid content of the matte coating agent is preferably 20 to 80 mass %, more preferably 25 to 75 mass %, and even more preferably 30 to 70 mass %.

[0025] (urethane resin) The urethane resin used in the present invention contains a dibasic acid-derived structural unit. The phrase "containing a dibasic acid-derived structural unit" refers to a state in which the polyol constituting the urethane resin is obtained by dehydration condensation of a dibasic acid and a diol. The content of the dibasic acid-derived structural unit is preferably 8% by mass or more, more preferably 10% by mass or more, and even more preferably 13% by mass or more, based on the total mass of the urethane resin. The content of the dibasic acid-derived structural unit is preferably 30% by mass or more, more preferably 35% by mass or more, and even more preferably 40% by mass or more, based on the total mass of the polyol constituting the urethane resin. The urethane resin is preferably a urethane resin obtained by the condensation reaction of a polyol and a polyisocyanate, or a urethane resin (urethane urea resin) obtained by the reaction (called chain extension) of a urethane prepolymer having an isocyanate group at its terminal, which is the condensation reaction product of a polyol and a polyisocyanate, with a polyamine. It is particularly preferable that the polyol contains a high molecular weight polyol. The use of a urethane resin has significant effects on substrate adhesion, abrasion resistance, heat resistance, and blocking resistance. In the present invention, multiple types of urethane resins may be used in combination. The content of the urethane resin in the total solid content of the matte coating agent is preferably 15 to 65% by mass, more preferably 20 to 60% by mass, and even more preferably 25 to 55% by mass. Furthermore, the content of the urethane resin in the total solid content of the binder resin is preferably 20 to 100% by mass, more preferably 30 to 95% by mass, and even more preferably 50 to 85% by mass. Being within the above ranges improves ink stability and blocking resistance. The weight-average molecular weight (Mw) of the urethane resin is preferably 10,000 to 200,000, more preferably 11,000 to 180,000, and even more preferably 12,000 to 150,000. The amine value of the urethane resin is preferably 1 to 20 mgKOH / g, more preferably 1.5 to 15 mgKOH / g, and even more preferably 1.7 to 10 mgKOH / g.

[0026] (Polyol) The polyol preferably includes a polyester polyol containing a dibasic acid-derived structural unit, and the weight-average molecular weight of the polyester polyol is preferably 400 to 10,000. The polyester polyol preferably accounts for 50% by mass or more, more preferably 70% by mass or more, of the total mass of the polyol. Furthermore, a polyol other than the polyester polyol may be used in combination. Examples of such polyols include polyether polyols, polycarbonate polyols, and polyolefin polyols. The polyol other than the polyester polyol is preferably used in an amount of 50% by mass or less of the total mass of the polyol. The polyol used in combination with the polyester polyol is preferably a polyether polyol, and among the polyether polyols, polytrimethylene glycol, polytetramethylene glycol, polypropylene glycol, polyethylene glycol, and copolymers thereof are more preferred.

[0027] (polyester polyol) The polyester polyol is preferably a condensation reaction product of a dibasic acid and a diol. By using a polyester polyol, which is a condensation reaction product of a dibasic acid and a diol, as the polyol, the urethane resin contains structural units derived from the dibasic acid.

[0028] (Dibasic acid) Specific examples of dibasic acids include adipic acid (also referred to as AdA), sebacic acid (also referred to as SeA), phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, oxalic acid, succinic acid, malonic acid, glutaric acid, dimer acid, pimelic acid, suberic acid, azelaic acid, trimellitic acid, pyromellitic acid, etc. The dibasic acid preferably includes a biomass dibasic acid.

[0029] (Biomass dibasic acid) In the present invention, the term "biomass dibasic acid" refers to a dibasic acid derived from biomass. Specific examples include succinic acid, sebacic acid, and dimer acid. It is preferable to use at least one of these biomass dibasic acids, with sebacic acid being particularly preferred.

[0030] (Biomass urethane resin) In the present invention, a urethane resin produced using a biomass-derived structural unit is referred to as a biomass urethane resin. The biomass-derived structural unit is preferably a urethane resin produced using a polyester polyol composed of the condensate of the biomass dibasic acid and a diol. The biomass dibasic acid is preferably contained in an amount of 40% by mass or more, more preferably 50% by mass or more, and even more preferably 55% by mass or more, based on the total mass of the dibasic acid used as the raw material for the polyester polyol constituting the biomass urethane resin. The above ranges result in good blocking resistance. Furthermore, the urethane resin contains structural units derived from a polyester polyol composed of the biomass dibasic acid and a diol containing a branched diol and a linear diol, imparting appropriate hardness and flexibility as a binder resin and significantly improving coating film properties such as blocking resistance.

[0031] (Non-biomass urethane resin) Non-biomass urethane resin refers to a urethane resin that does not contain biomass-derived structural units. For example, a polyester polyol composed solely of a dibasic acid that is not a biomass dibasic acid and a diol that is not biomass-derived is preferably used. The use of a non-biomass urethane resin is expected to result in the formation of a tough resin coating film. Furthermore, the combined use of a non-biomass urethane resin and a biomass urethane resin, particularly a biomass urethane resin derived from a biomass dibasic acid and a non-biomass urethane resin derived from a dibasic acid that is not a biomass dibasic acid, improves the storage stability of the coating agent, resulting in a coating film with a good balance of flexibility and toughness, and imparting substrate conformability and blocking resistance.

[0032] The biomass urethane resin preferably accounts for 40 to 99% by mass, more preferably 45 to 95% by mass, and even more preferably 50 to 90% by mass of the total urethane resin. The mass ratio of biomass urethane resin to non-biomass urethane resin is preferably 99:1 to 50:50, even more preferably 95:5 to 55:45, and even more preferably 90:10 to 60:40. This is because blocking resistance and heat resistance are improved.

[0033] (diol) The diol constituting the polyester polyol preferably contains both a branched diol and a linear diol. This allows the urethane resin to form a tough coating film, resulting in better blocking resistance and heat resistance in the laminate. Here, the linear diol refers to a diol that does not have a substituent such as a branched alkyl group, and suitable examples include alkylene glycol, dialkylene glycol, and trialkylene glycol. Furthermore, the branched diol refers to a diol in which at least one hydrogen atom in the hydrocarbon group of an alkylene glycol is substituted with a group other than a hydrogen atom. Since the linear diol imparts crystallinity and the branched diol imparts flexibility, urethane resins using branched and linear diols have excellent coating film properties, such as blocking resistance, as binder resins.

[0034] Suitable examples of the branched diol include 2-butyl-2-ethyl-1,3-propanediol (hereinafter also referred to as BEPG), 2-methyl-1,3-propanediol (hereinafter also referred to as MPO), 3-methyl-1,5-pentanediol (hereinafter also referred to as MPD), neopentyl glycol (hereinafter also referred to as NPG), 1,2-propylene glycol (hereinafter also referred to as PG), 2,4-diethyl-1,5-pentanediol, 1,3-butanediol, and dipropylene glycol. In the present invention, it is preferable to use at least one branched diol selected from MPO, MPD, BEPG, NPG, PG, and 2,4-diethyl-1,5-pentanediol, it is more preferable to use NPG and / or BEPG, and it is even more preferable to use NPG.

[0035] The linear diol is preferably an alkylene glycol, and suitable examples of such compounds include ethylene glycol (EG), diethylene glycol, 1,3-propanediol (1,3-PD), 1,4-butanediol (1,4-BD), 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,4-butynediol, 1,4-butylenediol, diethylene glycol, and triethylene glycol. Among these, linear diols having 8 or fewer carbon atoms, preferably 6 or fewer carbon atoms, are preferred, such as EG, 1,3-PD, 1,4-BD, 1,5-pentanediol, 1,6-hexanediol, and 1,8-octanediol. Furthermore, from the viewpoints of blocking resistance and substrate adhesion, EG, 1,3-PD, and 1,4-BD are more preferred.

[0036] (Polyisocyanate) The polyisocyanate preferably contains a diisocyanate, such as an aliphatic diisocyanate, such as tetramethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, or 2,4,4-trimethylhexamethylene diisocyanate; Alicyclic diisocyanates such as cyclohexane-1,4-diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, lysine diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, methylcyclohexane diisocyanate, m-tetramethylxylylene diisocyanate, and dimer diisocyanate in which the carboxyl groups of dimer acid are converted to isocyanate groups; Examples of the diisocyanate include α,α,α',α'-tetramethylxylylene diisocyanate, 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl isocyanate, dimethyldiphenylmethane diisocyanate, tetramethyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, o-xylylene diisocyanate, and aromatic diisocyanates such as 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate. Among these, alicyclic or araliphatic diisocyanates are preferred, and isophorone diisocyanate and α,α,α',α'-tetramethylxylylene diisocyanate are particularly preferred, from the viewpoints of easy reaction control and well-balanced performance of the resulting urethane resin. At least one diisocyanate may be used, or two or more may be used in combination.

[0037] (Polyamine) The polyamine is preferably a diamine, and suitable examples of such diamines include ethylenediamine, propylenediamine, hexamethylenediamine, isophoronediamine, and dicyclohexylmethane-4,4'-diamine. Also suitable are amines having a hydroxyl group in the molecule, such as 2-hydroxyethylethylenediamine, 2-hydroxyethylpropyldiamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine, and di-2-hydroxypropylethylenediamine. These diamines can be used alone or in combination, with isophoronediamine being preferred. Furthermore, it is also preferable to use a polyamine having three or more amino groups, such as diethylenetriamine, iminobispropylamine (IBPA, 3,3'-diaminodipropylamine), N-(3-aminopropyl)butane-1,4-diamine (spermidine), 6,6-iminodihexylamine, 3,7-diazanonane-1,9-diamine, or N,N'-bis(3-aminopropyl)ethylenediamine, in combination with the above diamines.

[0038] (Other resins) In the present invention, it is also preferable to use a urethane resin and other resins in combination as the binder resin. This is because the use of other resins in combination can control the flexibility and toughness of the coating film and can impart significant effects in terms of blocking resistance, heat resistance, abrasion resistance, and substrate adhesion. Examples of such resins include, but are not limited to, cellulose-based resins, polyamide resins, vinyl chloride copolymer resins, rosin-based resins, ethylene-vinyl acetate copolymer resins, vinyl acetate resins, acrylic resins, styrene resins, dammar resins, styrene-maleic acid copolymer resins, polyester resins, alkyd resins, terpene resins, phenol-modified terpene resins, ketone resins, cyclized rubber, chlorinated rubber, butyral, polyacetal resins, petroleum resins, and modified resins thereof. Among these, vinyl chloride copolymer resins and cellulose-based resins are preferred. Among vinyl chloride copolymer resins, vinyl chloride-vinyl acetate copolymer resins and vinyl chloride-acrylic copolymer resins are preferred. These resins can be used alone or in combination.

[0039] In the binder resin, the mass ratio of urethane resin to other resins is preferably 99:1 to 15:85, more preferably 95:5 to 20:80, and even more preferably 85:15 to 30:70. This is because blocking resistance, heat resistance, and abrasion resistance are improved. Of the total solid mass of the coating agent, the total content of urethane resin and other resins is preferably 30 to 80 mass%, more preferably 35 to 70 mass%, and even more preferably 40 to 60 mass%.

[0040] (Vinyl chloride-vinyl acetate copolymer resin) The vinyl chloride-vinyl acetate copolymer resin contains vinyl chloride units and vinyl acetate units. It is also preferable for it to further contain vinyl alcohol units. The mass ratio of vinyl chloride units to vinyl acetate units (vinyl chloride units:vinyl acetate units) is preferably 98:2 to 70:30, more preferably 95:5 to 80:20, from the viewpoints of improving the hot water resistance and blocking resistance of the matte coating agent and suppressing a decrease in adhesion to the support (substrate) film. The weight-average molecular weight is preferably 5,000 to 50,000, more preferably 10,000 to 35,000.

[0041] (Vinyl chloride-acrylic copolymer resin) Vinyl chloride-acrylic copolymer resins are primarily composed of copolymer resins of vinyl chloride monomers and acrylic monomers. The acrylic monomer preferably contains a (meth)acrylic acid hydroxyalkyl ester, which improves adhesion to substrates and solubility in organic solvents. The acrylic monomer may be incorporated into the main chain of polyvinyl chloride in a block or random manner, or may be graft-polymerized onto the side chain of polyvinyl chloride. The vinyl chloride-acrylic copolymer resin preferably has a weight-average molecular weight of 10,000 to 100,000, more preferably 30,000 to 70,000. The hydroxyl value is preferably 20 to 200 mgKOH / g, and the glass transition temperature is preferably 50 to 90°C.

[0042] In the following description, (meth)acrylic and (meth)acrylate refer to methacrylic and acrylic, methacrylate and acrylate, respectively.

[0043] The acrylic monomer preferably contains one having a hydroxyl group. Examples 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 hydroxyethyl acrylamide. Among these, 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 2-hydroxypropyl acrylate are more preferred because they improve the solubility in solvents and the storage stability of the coating agent. These monomers can be used alone or in combination. Acrylic monomers other than those listed above may also be added as needed.

[0044] (cellulose resin) Examples of cellulose-based resins include acyl-substituted celluloses such as nitrocellulose, cellulose acetate, cellulose acetate propionate, and cellulose acetate butyrate; alkyl-substituted celluloses such as methylcellulose and ethylcellulose; and hydroxyl-containing celluloses such as benzyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, and hydroxymethylpropyl cellulose. Nitrocellulose is preferred as the cellulose-based resin from the viewpoint of improving the heat resistance of the matte coating agent, and acyl-substituted celluloses and / or alkyl-substituted celluloses are preferred from the viewpoint of improving the adhesion of the matte coating agent to the substrate. The degree of hydroxyl group substitution of the cellulose-based resin is preferably about 30 to 85%. At least one type of cellulose-based resin may be used, or two or more types may be used in combination.

[0045] The weight-average molecular weight of the cellulose-based resin is preferably 10,000 to 500,000. As the molecular weight increases, it becomes more difficult to dissolve the resin in an organic solvent, and the matte coating agent tends to become highly viscous, limiting the amount that can be contained. Therefore, the weight-average molecular weight is more preferably 10,000 to 300,000, and even more preferably 10,000 to 100,000.

[0046] (Matte agent) The matting agent is a component added to impart matte properties. It is believed that the matting agent imparts matte properties by forming fine irregularities on the surface of the matte coating layer, thereby causing diffuse reflection of light. In the present invention, the matting agent contains silica and an extender pigment (A) in fine particle form (excluding cases where the extender pigment (A) is silica). The content of the matting agent in the total solids content of the matte coating agent is preferably 20 to 60 mass%, more preferably 25 to 55 mass%, and even more preferably 30 to 50 mass%. Furthermore, the total mass of the matting agent preferably contains 50 to 100 mass%, more preferably 55 to 100 mass%, and even more preferably 60 to 100 mass% of silica and extender pigment (A). Furthermore, the mass ratio of silica to extender pigment (A) is preferably 1:99 to 60:40, more preferably 2:98 to 50:50, and even more preferably 3:97 to 25:75. This is because the matte finish, reverse gloss, blocking resistance and coating surface suitability are improved. Furthermore, the solid content of silica in the matting agent is preferably 0.1 to 50 mass%, more preferably 1 to 25 mass%, and even more preferably 2 to 15 mass%. The matting agent is effective in achieving matte properties, reverse gloss properties, blocking resistance, and coating film surface suitability, and the average particle size, type, etc. of the matting agent to be added will be described later.

[0047] (silica) In a preferred embodiment of the silica that can be used in the present invention, from the viewpoint of matte finish and blocking resistance, the average particle size of the silica is preferably 0.1 to 7 μm, more preferably 1 to 5 μm. In the present invention, the average particle size refers to that measured by a laser diffraction / scattering method, and can be measured using, for example, an MT3300EXII manufactured by MicrotracMRB. The apparent specific gravity is 0.05 to 1 g / cm. 3 Preferably, the density is 0.1 to 0.6 g / cm 3 is more preferable from the viewpoint of the stability, abrasion resistance, and blocking resistance of the coating agent. Although there is no particular limitation on the method for producing silica, a wet method is preferred from the viewpoint of dispersibility, and among these, a gel method (gel silica) is more preferred. Furthermore, silica whose surface has been treated with wax or the like is preferred from the viewpoint of storage stability and blocking resistance of the coating agent.

[0048] (Extender pigment (A)) Suitable examples of the extender pigment (A) other than silica include solid particles of calcium carbonate, calcium silicate, magnesium silicate, barium sulfate, kaolin, zinc oxide, titanium oxide, clay, and alumina. Of these, calcium carbonate, barium sulfate, and kaolin are preferred from the viewpoints of negative gloss, blocking resistance, and matte properties. Calcium carbonate is particularly preferred.

[0049] (Calcium carbonate) In a preferred embodiment of the calcium carbonate that can be used in the present invention, from the viewpoint of reverse gloss and blocking resistance, the average particle size is preferably 0.1 to 5 μm, and more preferably 1 to 5 μm. The oil absorption is preferably 1 to 80 mL / 100 g, and more preferably 1 to 60 mL / 100 g. The bulk density is preferably 0.1 to 10 g / ml, more preferably 0.1 to 1 g / ml, and even more preferably 0.1 to 0.5 g / ml. The bulk density can be measured according to JIS K5115-1965, etc. Furthermore, the pH of the calcium carbonate is preferably 5 to 10, which improves dispersibility.

[0050] (barium sulfate) In a preferred embodiment of the barium sulfate usable in the present invention, from the viewpoint of negative gloss and blocking resistance, the average particle size is preferably 0.1 to 3 μm, more preferably 0.1 to 1 μm, and even more preferably 0.1 to 0.6 μm. The oil absorption is preferably 1 to 40 mL / 100 g, more preferably 5 to 25 mL / 100 g. The bulk density is preferably 50 to 600 mL / 100 g, more preferably 100 to 500 mL / 100 g, and even more preferably 200 to 400 mL / 100 g. The bulk density can be measured according to JIS K5115-1965 or the like. Furthermore, the pH of the barium sulfate is preferably 5 to 9, which improves dispersibility.

[0051] (Kaolin) Kaolin is primarily composed of kaolinite (Al2O3·2SiO2·H2O) or halloysite (Al2O3·2SiO2·2H2O), and may be a natural or synthetic product. Depending on the production method, kaolin can be dry kaolin, wet kaolin, calcined kaolin, or the like, but is not limited to any of these. In terms of reverse gloss and blocking resistance, a preferred embodiment of kaolin that can be used in the present invention has an average particle size of preferably 0.1 to 6 μm, more preferably 0.1 to 4 μm, and even more preferably 0.1 to 3 μm. Furthermore, the oil absorption is preferably 1 to 70 mL / 100 g, more preferably 1 to 50 mL / 100 g.

[0052] (Other matting agents) In the present invention, the matting agent is not limited to silica and non-silica extender pigment (A), and other matting agents can also be used.Other matting agents include, for example, urethane resin microparticles, silicone resin microparticles, melamine resin microparticles, melamine-benzoguanamine resin microparticles, acrylic resin microparticles (for example, polymethyl methacrylate resin microparticles), acrylic-styrene copolymer resin microparticles, polycarbonate resin microparticles, polyethylene resin microparticles, polystyrene resin microparticles, benzoguanamine resin microparticles, and other resin microparticles.

[0053] (organic solvent) The matte coating agent preferably contains an organic solvent as the main component of the liquid medium (at least 50% by mass of the total medium) to improve printing performance. The organic solvent used is preferably a mixed solvent consisting of two or more organic solvents. Known organic solvents such as aromatic organic solvents, ketone organic solvents, ester organic solvents, alcohol organic solvents, and glycol ether organic solvents can be used. Examples of aromatic organic solvents include toluene and xylene. Examples of ketone organic solvents include methyl ethyl ketone and methyl isobutyl ketone. Examples of ester organic solvents include ethyl acetate, n-propyl acetate, isopropyl acetate, and isobutyl acetate. Examples of alcohol organic solvents include methanol, ethanol, n-propanol, isopropyl alcohol, and n-butanol. Examples of glycol ether solvents include ethylene glycol monopropyl ether and propylene glycol monomethyl ether. Among these, organic solvents that do not contain aromatic organic solvents (non-toluene organic solvents) are more preferred. Even more preferred are organic solvents that do not contain aromatic organic solvents and / or ketone organic solvents. Furthermore, a mixed solvent of an ester-based organic solvent and an alcohol-based organic solvent is preferred to improve printability. A preferred mass ratio of the ester-based organic solvent to the alcohol-based organic solvent (ester-based organic solvent / alcohol-based organic solvent) is 40 / 60 to 90 / 10.

[0054] (Other additives) The matte coating agent of the present invention may further contain, as optional components, additives such as plasticizers such as wax, sulfonamide, polyester, phosphate ester, citrate ester, and epoxidized vegetable oil, leveling agents such as acrylic resin and modified silicone, surfactants, silane coupling agents, curing agents, dispersants, and defoamers. Of these, wax is significantly effective in improving coating surface properties such as blocking resistance.

[0055] (wax) Examples of waxes include solid or liquid polyolefin waxes and amide waxes, with amide wax being preferred. Amide waxes are fatty acid amides, preferably those having a fatty acid residue and an amide group. It is believed that the fatty acid amides orient on the surface of the surface protective layer after printing, exhibiting slip properties and improving blocking resistance and abrasion resistance. This explanation is based on technical considerations and does not limit the invention in any way. Suitable examples of fatty acid amides include monoamides, substituted amides, bisamides, methylolamides, and esteramides, with at least one selected from the group consisting of monoamides, substituted amides, and bisamides being preferred. The melting point of the fatty acid amide is preferably 50°C to 150°C.

[0056] <Matte coating agent manufacturing> As a method for producing the matte coating agent of the present invention, since simple mixing tends to result in sedimentation, it is preferable to produce it by kneading using a commonly used dispersing machine such as a sand mill, attritor, pebble mill, ball mill, roller mill, etc. More specifically, the matting agent, urethane resin solution, and organic solvent are added and stirred with a stirrer for 10 to 30 minutes, and then dispersed in a sand mill for 10 to 30 minutes. Thereafter, the urethane resin solution, additives such as hydrocarbon wax, and organic solvent are further blended with the dispersion and stirred thoroughly again to produce the matte coating agent of the present invention.

[0057] <Printed matter with a matte coating layer> A printed matter having a matte coating layer is formed by printing or applying the matte coating agent of the present invention onto a substrate and then "evaporating the organic solvent with hot air and drying." The printing process also includes a step of volatilizing the organic solvent using an oven or the like. The printed matter preferably has a printing ink layer on the side of the substrate opposite the side having the matte coating layer.

[0058] Suitable methods for printing or applying the matte coating agent include printing methods such as gravure printing, flexographic printing, and screen printing. In addition, coating methods such as roll coating, gravure coating, gravure reverse coating, microgravure coating, curtain coating, spray coating, and die coating can also be used.

[0059] The drying temperature during printing of the matte coating agent is usually preferably 40°C or higher and 100°C or lower, and more preferably 50°C or higher and 70°C or lower, but the processing temperature and processing time may be adjusted appropriately depending on the heat resistance and thermal deformation properties of the substrate used.

[0060] The thickness of the matte coating layer is usually preferably 0.5 to 10 μm, more preferably 1 to 8 μm, and even more preferably 1 to 5 μm. The coating amount in a dry state is 1 to 5 g / m 2 The degree is preferable.

[0061] A preferred embodiment of a printed matter including a matte coat layer is shown below. Matte coating layer / substrate 1 Matte coating layer / substrate 1 / printing ink layer

[0062] (Base material 1) The substrate applicable to the present invention can be any plastic film, including, for example, polyamide resins such as nylon (Ny) 6, nylon 66, and nylon 46; polyester resins such as polyethylene phthalate (PET), polyethylene naphthalate, polytrimethylene terephthalate, polytrimethylene naphthalate, polybutylene terephthalate, and polybutylene naphthalate; biodegradable resins such as polyhydroxycarboxylic acids such as polylactic acid, aliphatic polyester resins such as polyethylene succinate and polybutylene succinate; cellulose resins such as diacetyl cellulose and triacetyl cellulose; polyolefin resins such as polypropylene (PP) and polyethylene; polyimide resins; polyarylate resins; and thermoplastic resins such as mixtures thereof, as well as laminates thereof. Among these, films made of polyester, polyamide, and polypropylene are particularly preferred. These films may be unstretched or stretched, and their manufacturing method is not limited. The thickness of the substrate film is also not particularly limited, but is typically within the range of 1 to 500 μm.

[0063] The substrate may be surface-treated by corona treatment, plasma treatment, or the like in order to improve the printability (wettability and adhesion) of the matte coating agent, and may be laminated with a vapor-deposited layer of a transparent inorganic oxide, or the like, in order to improve the gas barrier properties.

[0064] (printing ink layer) The printed matter of the present invention may have a printing ink layer on the surface opposite to the surface on the substrate 1 having the matte coat layer. The printing ink layer in the present invention refers to a substrate on which printing ink is printed. There are no particular restrictions on the ink used to form the printing ink layer, but laminating ink is preferred. The printing ink can be obtained by a known method, for example, the method disclosed in JP-A-2011-122064, JP-A-2020-147720, etc. Furthermore, there are no particular restrictions on the printing method, but gravure printing is preferred.

[0065] (Laminate having a matte coat layer, a substrate 1, a printing ink layer, and a substrate 2 in this order) The laminate of the present invention has a laminated structure of matte coating layer / substrate 1 / printed ink layer / adhesive layer / substrate 2, and is obtained by providing an adhesive layer on the printed ink layer formed on the surface of substrate 1 different from the matte coating layer, and then bonding (laminating) it to substrate 2. Here, substrate 2 may be the same as or different from substrate 1. Typical examples of lamination include extrusion lamination, dry lamination, and non-solvent lamination. Extrusion lamination is a method in which an anchor coating agent is applied to the printed ink layer of a printed material, and then molten polyethylene resin, molten polypropylene resin, etc. is extruded onto it, simultaneously laminating it with the substrate. Dry lamination and non-solvent lamination are methods in which an adhesive is applied to the printed ink layer of a printed material, dried, and then laminated with a sealant by thermocompression. The difference between dry lamination and non-solvent lamination is whether or not an organic solvent or other volatile medium is used.

[0066] (adhesive layer) Suitable adhesive layers include layers formed from molten polyethylene resin, molten polypropylene resin, urethane adhesive, acrylic adhesive, and anchor coat layers. Among these, an adhesive layer made from molten polyethylene resin is preferred. Suitable urethane adhesives include two-component adhesives made from a mixture of polyol and an isocyanate curing agent, and examples of polyols include polyester and polyether adhesives. Specific examples include TM-250HV / CAT-RT86L-60, TM-550 / CAT-RT37, and TM-314 / CAT-14B manufactured by Toyo-Morton Co., Ltd.

[0067] (Base material 2) The substrate 2 may be the same as or different from the substrate 1. A thermoplastic substrate (sometimes called a sealant) is preferred, and unstretched polyethylene substrates, unstretched polypropylene substrates, unstretched polyester substrates, etc. are preferred. [Example]

[0068] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples as long as the gist of the present invention is not exceeded. In the present invention, parts and % represent parts by mass and % by mass unless otherwise noted.

[0069] (Measuring methods for various measurement parameters)

[0070] (amine value) The amine value was determined in accordance with JIS K0070 using the equivalent amount of potassium hydroxide (mg) required to neutralize the amino groups in 1 g of resin. 0.5 to 2 g of sample was precisely weighed out (sample solids: 5 g). 50 mL of a 60 / 40 (mass ratio) methanol / methyl ethyl ketone mixture was added to dissolve the sample. Bromophenol blue was added as an indicator to the resulting solution, which was then titrated with 0.2 mol / L ethanolic hydrochloric acid solution (titer: 5). The point at which the solution changed color from green to yellow was defined as the endpoint, and the titer (A mL) at this point was used to calculate the amine value according to the following formula (1). (Equation 1) Amine value = (A × f × 0.2 × 56.108) / S [mgKOH / g]

[0071] (Weight average molecular weight Mw) The weight average molecular weight Mw was determined by measuring the molecular weight distribution using a GPC (gel permeation chromatography) device (HLC-8220 manufactured by Tosoh Corporation) and calculating the molecular weight converted using polystyrene as a standard substance. The measurement conditions are shown below. Columns: The following columns were used in series. Tosoh Corporation TSKgel Super AW2500 Tosoh Corporation TSKgel Super AW3000 Tosoh Corporation TSKgel Super AW4000 Tosoh Corporation's TSK gelguard column Super AWH Detector: RI (differential refractometer) Measurement conditions: Column temperature 40°C Eluent: tetrahydrofuran Flow rate: 1.0mL / min

[0072] (Synthesis Example 1) (Synthesis of Biomass Urethane Resin A1 Solution) A four-neck flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen gas inlet tube was charged with 30.4 parts by mass of polyester polyol A (a condensate of 1,3-PD:NPG:AdA:SeA = 1:1:1:3 (mass ratio) dissolved in ethyl acetate with a solids content of 73.5%), 0.1 parts by mass of 1,3-propanediol, 3.7 parts by mass of isophorone diisocyanate (hereinafter also abbreviated as IPDI), and 0.01 parts by mass of catalyst (stannous 2-ethylhexylate), and the mixture was reacted at 90°C for 3 hours under a nitrogen stream. Mixed solvent A (1.1 parts by mass of ethyl acetate and 6.5 parts by mass of n-propyl acetate) was added, and the mixture was cooled to obtain a solution of a terminal isocyanate prepolymer. Next, the obtained solution of isocyanate-terminated prepolymer was gradually added to 1.6 parts by mass of isophoronediamine (hereinafter also abbreviated as IPDA), 0.2 parts by mass of dibutylamine (hereinafter also abbreviated as DBA), and mixed solvent B (21.2 parts of ethyl acetate, 6.5 parts of n-propyl acetate, 28.7 parts of isopropyl alcohol) at room temperature, and then the mixture was allowed to react at 40°C for 1 hour to obtain biomass urethane resin solution A1 (solid content 28% by mass, weight average molecular weight Mw 60,000).

[0073] (Synthesis Examples 2 and 3) (Synthesis of Non-Biomass Urethane Resin A2 Solution and Biomass Urethane Resin A3 Solution) A non-biomass urethane resin A2 solution and a biomass urethane resin A3 solution were obtained in the same manner as in Synthesis Example 1, except that the raw materials and charging ratios were changed to those shown in Table 1. The properties of the resins are shown in the same table. The abbreviations in the table represent the following: Polyester polyol B (NPG:1,3-PD:SeA = 1:1:3 (mass ratio)) dissolved in ethyl acetate with 73.5% solids) Polyester polyol C (NPG:1,3-PD:AdA = 1:1:4 (mass ratio)) dissolved in ethyl acetate with a solid content of 73.5%)

[0074] (Comparative Synthesis Example 1) (Synthesis of non-biomass urethane resin A4 solution) A non-biomass urethane resin A4 solution was obtained in the same manner as in Synthesis Example 1, except that the raw materials and charging ratios were changed as shown in Table 1. The abbreviations in the table represent the following. PPG: Polypropylene glycol

[0075] [Table 1]

[0076] [Example 1] (Production of Matte Coating Agent S1) 23 parts by mass of biomass urethane resin A1 solution, 13 parts by mass of vinyl chloride-acrylic copolymer resin C1 solution (manufactured by Wacker Chemical Co., Ltd., product name Binnol E15 / 40A, solid content 24 mass%), and silica (manufactured by Mizusawa Industrial Chemical Co., Ltd., product name C-444, gel silica, average particle size 4 μm, apparent specific gravity 0.16 g / cm 3 ), 10 parts by weight of calcium carbonate (Shiraishi Kogyo Co., Ltd., product name PC, average particle size 3.2 μm, oil absorption 40 mL / 100 g, bulk density 0.22 g / mL), and 13 parts by weight of mixed solvent C were stirred and mixed and dispersed using a bead mill (sand mill). Then, 13 parts by weight of non-biomass urethane resin A2 solution, 8 parts by weight of hydrocarbon wax (Kao Corporation, product name Amide P), and 19 parts by weight of mixed solvent C were further added and stirred and mixed to prepare matte coating agent S1. Mixed solvent C was a mixture of n-propyl acetate, ethyl acetate, isopropyl alcohol, and methyl propylene glycol (mixture ratio of n-propyl:ethyl acetate:isopropyl alcohol:methyl propylene glycol = 3:3:2:2).

[0077] [Examples 2 to 21] (Production of matte coating agents S2 to S21) Matte coating agents S2 to S21 were obtained in the same manner as in Matte Coating Agent Example 1, except that the raw materials and charging ratios were changed as shown in Table 2.

[0078] [Comparative Examples 1 to 4] (Production of Matte Coating Agents T1 to T4) Matte coating agents T1 to T4 were obtained in the same manner as in Matte Coating Agent Example 1, except that the raw materials and charging ratios were changed as shown in Table 3. The abbreviations in the table represent the following. Barium sulfate: Sakai Chemical Industry Co., Ltd. Product name: Variace B-30 Kaolin: Takehara Chemical Industry Co., Ltd. Product name: ST Kaolin Clay Cellulose resin solution C2: Nitrocellulose manufactured by ICI Novel Enterprises, product name DLX5-8, solid content 24% by mass

[0079] (Matte coating agent S1 printing) Using a gravure proofing machine equipped with a gravure printing solid plate with 175 lines of helio, the matte coating agent S1 obtained in Example 1 above was applied to a PET (polyethylene terephthalate) film (manufactured by Toyobo Co., Ltd., product name: E-5102, film thickness: 12 μm) at a coating speed of 40 m / min so that the dry film thickness was approximately 2 μm, and the film was dried with hot air at 60°C (air volume 80%) to obtain a printed matter.

[0080] (Matte coating S2 to S21, T1 to T4 printing) Each print was obtained in the same manner as in the printing of the matte coating agent S1, except that the matte coating agent S1 was changed to matte coating agents S2 to S21 and T1 to T4.

[0081] (Preparation of Laminate Containing Matte Coating Agent S1) The matte coating agent S1 print was then applied to the substrate on the side opposite the matte coating agent using a gravure proofing machine equipped with a 25 μm deep gravure plate (drying temperature: 60°C, printing speed: 40 m / min). A 1% by weight methanol solution of a butadiene anchor coating agent (Toyo Morton EL451) was then applied to the ink layer. A 15 μm thick layer of molten polyethylene (Sumitomo Chemical Sumikathen L417) was then extruded at 320°C using an extrusion laminator (Musashino Kikai Co., Ltd.) at a line speed of 100 m / min. A 20 μm thick CPP (Futamura Chemical FCMN) was then laminated to the surface, resulting in a laminate containing the matte coating agent S1.

[0082] (Preparation of Laminates Containing Matte Coating Agents S2 to S21 and T1 to T4) Each laminate was obtained in the same manner as for the laminate containing the matte coating agent S1, except that the matte coating agent S1 was changed to matte coating agents S2 to S21 and T1 to T4.

[0083] (Measurement and Evaluation) The printed matter and laminates obtained in the above Examples and Comparative Examples were evaluated as follows. The evaluation results are shown in Tables 2 and 3. In the following explanation, "reverse gloss" refers to the occurrence of gloss in the rubbed areas of the coating layer.

[0084] (reverse gloss) The matte coating surface of the printed matter was evaluated for its negative gloss using a multi-rub tester (reciprocating rotary abrasion tester). A 7cm x 7cm piece of printed matter was attached to the head, and K-liner paper was attached to the stage. The friction test was carried out so that the K-liner paper rubbed against the surface of the matte coating layer, and the negative gloss was evaluated visually. (Judgment criteria) 5 (Excellent): No reverse gloss occurs on the surface of the printed material. 4 (Good): Reverse gloss can be seen only when the surface of the printed matter is viewed from a different angle. 3 (Acceptable): When the printed surface is visually inspected from the front, the occurrence of reverse gloss can be confirmed. The occurrence of reverse gloss is less than 10% of the worn area. 2 (Not acceptable): When the surface of the printed material is visually inspected from the front, the occurrence of reverse gloss can be easily confirmed, and the occurrence of reverse gloss is 10% or more but less than 30% of the worn area. 1 (Poor): When the printed surface is visually inspected from the front, the occurrence of reverse gloss can be easily confirmed, and the occurrence of reverse gloss is 30% or more of the worn area. Incidentally, 3 to 5 is a range that does not pose any practical problems.

[0085] (Abrasion resistance) The matte coating surface of the printed matter was subjected to an abrasion test using a Gakushin-type abrasion resistance tester (manufactured by Daiei Kagaku Co., Ltd.) with a dry cotton cloth and K-liner paper, with a load of 500 g applied 30 times. The condition of the coating film in the abraded area was visually evaluated according to the following criteria. 5 (Excellent): No scratches on the coating, transfer to the K-liner paper, or reverse gloss were observed. 4 (Good): No transfer to K-liner paper, but negative gloss was observed. 3 (Fair): Less than 10% of the coating layer was transferred to the K-liner paper. 2 (Unacceptable): 10% or more but less than 30% of the coating layer was transferred to the K-liner paper. 1 (poor): 30% or more of the coating layer was transferred to the K-liner paper. Incidentally, 3 to 5 is a range that does not pose any practical problems.

[0086] (Heat resistance) Using a heat seal tester equipped with a hot plate with a thermal gradient of 80 to 200°C, the matte coat layer surface of the printed material was pressed against aluminum foil at 2.0 kg / cm. 2 The aluminum foil was peeled off and the degree to which the matte coating layer was removed was visually evaluated. 5 (Excellent): No cracking was observed even at temperatures above 180°C. 4 (Good): Cracks were observed at 160°C or higher and below 180°C. 3 (Acceptable): Removal was observed at temperatures above 120°C and below 160°C. 2 (Not acceptable): Failure was observed at temperatures above 100°C and below 120°C. 1 (poor): Debris was observed even at temperatures below 100°C. Incidentally, 3 to 5 is a range that does not pose any practical problems.

[0087] (blocking resistance) The corona discharge treated surface of a PET (polyethylene terephthalate) film (manufactured by Toyobo Co., Ltd., product name: E-5102, film thickness: 12 μm) and the matte coated surface of the printed material were heated at 40°C and 5 kg / cm 2 The printed surface was then pressed under these conditions for 24 hours, and the behavior of the printed surface when peeled off was evaluated. [Evaluation criteria] 5 (Excellent): No peeling on the printed surface and no resistance felt 4 (Good): There is no peeling on the printed surface, but resistance is felt. 3 (Acceptable): Slight peeling of less than 20% on the printed surface 2 (Fail): Thin and / or thick peeling of 20% to less than 50% of the printed surface 1 (poor): More than 50% of the printed surface is peeled off Incidentally, 3 to 5 is a range that does not pose any practical problems.

[0088] (Matte) The gloss of the matte coating layer surface of the printed matter was measured at an incident angle of 60° and a reflection angle of 60° using a Micro Trigloss glossmeter manufactured by BYKCHEMIE, and evaluated according to the following criteria. 5 (Excellent): Gloss value less than 5 4 (Good): Gloss value is 5 or more but less than 10 3 (Acceptable): Gloss value is 10 or more and less than 25 2 (unacceptable): Gloss value is 25 or more and less than 40 1 (poor): Gloss value is 40 or more Incidentally, 3 to 5 is a range that does not pose any practical problems.

[0089] (Laminate strength) The laminate was cut into a length of 150 mm and a width of 15 mm, and the ink / PET film interface was peeled off at one end in a width that could be clamped with the jig of a tensile tester. The laminate strength was measured in the 90° direction using the tensile tester at a peel rate of 300 mm / min. 5 (Excellent): Laminate strength is 1.5N / 15mm or more 4 (Good): Laminate strength is 1.0N / 15mm or more and less than 1.5N / 15mm 3 (Acceptable): Laminate strength is 0.8N / 15mm or more and less than 1.0N / 15mm 2 (Not acceptable): Laminate strength is 0.5N / 15mm or more but less than 0.8N / 15mm 1 (poor): Laminate strength is less than 0.5N / 15mm Incidentally, 3 to 5 is a range that does not pose any practical problems.

[0090] [Table 2-1]

[0091] [Table 2-2]

[0092] [Table 3]

[0093] Comparative Examples 3 and 4, which did not contain either silica or a non-silica extender pigment (A), or Comparative Examples 1 and 2, which did not contain a urethane resin containing a dibasic acid-derived structural unit, failed to achieve any of the properties of blocking resistance, heat resistance, reverse gloss, abrasion resistance, and matte finish. In contrast, Examples 1 to 21, in which the matting agent contained silica and a non-silica extender pigment (A) and the binder resin contained a urethane resin containing a dibasic acid-derived structural unit, exhibited performance in all of blocking resistance, heat resistance, reverse gloss, abrasion resistance, and matte finish at levels at which practical problems were not encountered. This demonstrates that the present invention can provide a matte coating agent that solves all of the above problems.

Claims

1. A matte coating agent containing a binder resin, a matting agent, and an organic solvent, The matte coating agent includes a binder resin containing a urethane resin, the urethane resin containing a structural unit derived from a dibasic acid, and the matting agent containing silica and an extender pigment (A) (excluding the case where the extender pigment (A) is silica).

2. 2. The matte coating agent according to claim 1, wherein the extender pigment (A) comprises at least one selected from the group consisting of calcium carbonate, barium sulfate, and kaolin.

3. 3. The matte coating agent according to claim 1, wherein the binder resin further comprises a vinyl chloride copolymer resin and / or a cellulose resin.

4. 3. The matte coating agent according to claim 1, wherein the content of the matting agent in the total solid content of the matte coating agent is 20 to 60 mass %.

5. The matte coating agent according to claim 1 or 2, wherein the dibasic acid-derived structural unit is a biomass dibasic acid-derived structural unit.

6. The matte coating agent according to claim 5 , wherein the urethane resin further comprises a non-biomass urethane resin.

7. 3. The matte coating agent according to claim 1, wherein the content of the urethane resin in the total solid content of the matte coating agent is 15 to 65 mass %.

8. 3. The matte coating agent according to claim 1, wherein the content of silica in the total solid content of the matting agent is 0.1 to 50 mass %.

9. The matte coating agent according to claim 1 or 2, further comprising a wax.

10. A printed matter having a matte coating layer formed from the matte coating agent according to claim 1 or 2 on a substrate 1.

11. A laminate comprising a matte coating layer formed from the matte coating agent according to claim 1 or 2, a substrate 1, a printing ink layer, and a substrate 2 in this order.

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