WO2023054472A1

WO2023054472A1 - Non-aqueous adhesive composition, recording method, method for producing recorded matter, set of compositions, and recorded matter

Info

Publication number: WO2023054472A1
Application number: PCT/JP2022/036177
Authority: WO
Inventors: 由佳折笠; 悟志井手之上; 圭士郎吉森; 保真齋藤; 公淳宇高; 充功田村
Original assignee: 株式会社Ｄｎｐファインケミカル
Priority date: 2021-09-30
Filing date: 2022-09-28
Publication date: 2023-04-06
Also published as: JPWO2023054472A1

Abstract

Provided is a novel adhesive composition that can be discharged from a nozzle onto a base material and can fix a solid such as a powder or foil to the base material.　A non-aqueous adhesive composition discharged from a nozzle, wherein the non-aqueous adhesive composition includes an organic solvent and a resin, the resin contains a resin A including the following monomer (a) as a constituent, and the proportion of the monomer (a) constituting the resin A is 50 mass% or more of the total monomer weight constituting resin A. (In formula (1), Ry is a hydrogen group or an optionally branched C1-12 hydrocarbon group. When Ry is a hydrogen group, Rx is a C1-18 hydrocarbon group that may be branched and may be monocyclic. When Ry is an optionally branched C1-12 hydrocarbon group, Rx is an optionally branched C2 -18 hydrocarbon group.)

Description

Non-aqueous adhesive composition, recording method, method for producing recorded matter, set of composition, and recorded matter

The present invention relates to a non-aqueous adhesive composition, a recording method, a method for producing a recorded matter, a composition set, and a recorded matter.

As ink compositions, non-aqueous ink compositions in which various coloring materials and resins are dissolved or dispersed in a mixed liquid with an organic solvent are widely used. Characters and images can be obtained by ejecting the ink composition from a nozzle of an inkjet method or the like onto a substrate such as paper directly or via another layer, and drying the non-aqueous ink composition.

For example, Patent Document 1 discloses an ink jet recording method in which an acrylic resin solution-polymerized in a glycol ether dialkyl ether solvent using a radical polymerization initiator is contained in an oil-based ink composition having a glycol ether dialkyl ether as a main solvent. Disclosed is an oil-based ink composition for Patent Document 1 discloses that this composition can obtain good print drying property, scratch resistance and re-solubility by using solubilized acrylic resin, which has been difficult to dissolve in the past. It is stated that it is possible.

In addition, an image having a metallic tone is sometimes expressed on a substrate (recording medium) or a substrate such as a printed matter in which a colored layer is partially or entirely laminated on the surface. Techniques for imparting such metallic luster include applying an ink composition using metal powder made from brass, aluminum fine particles, etc., foil stamping using metal foil, and thermal transfer using metal foil. etc. have been used.

For example, Patent Literature 2 describes a metal thin film decorative sheet and its manufacturing method. Patent Document 2 describes that by adjusting the projected area and thickness of the metal film, it is possible to obtain a sheet-like material decorated with a thin metal film that is excellent in appearance and texture and has high peel strength.

JP 2007-169492 A JP 2016-182675 A

An object of the present invention is to provide a novel adhesive composition that can be discharged onto a substrate from a nozzle and that can fix solids such as powder and foil to the substrate.

As a result of intensive studies aimed at solving the above problems, the present inventors have found that a composition containing an organic solvent and a resin containing a specific monomer in a predetermined ratio can solve the above problems. The present invention has been solved.

(1) A non-aqueous adhesive composition discharged from a nozzle, comprising an organic solvent and a resin, wherein the resin contains a resin A containing the following monomer (a) as a configuration, and the resin A The ratio of the monomer (a) constituting the non-aqueous adhesive composition is 50% by mass or more in the total amount of the monomers constituting the resin A.

(In formula (1), Ry represents a hydrogen group or an optionally branched hydrocarbon group having 1 to 12 carbon atoms. When Ry is a hydrogen group, Rx may be branched monocyclic represents a hydrocarbon group having 1 to 18 carbon atoms which may be branched, and when Ry is a hydrocarbon group having 1 to 12 carbon atoms which may be branched, Rx is an optionally branched hydrocarbon group having 2 to 18 carbon atoms. represents a hydrocarbon group.)

(2) The non-aqueous adhesive composition according to (1), wherein the content of the resin A is 70% by mass or more based on the total amount of the resin contained in the non-aqueous adhesive composition.

(3) The non-aqueous adhesive composition according to (1) or (2), wherein the proportion of the monomer (a) constituting the resin A is 70% by mass or more in the total amount of the monomers constituting the resin A.

(4) The monomer (a) constituting the resin A contains at least one selected from the group consisting of methyl acrylate, cyclohexyl acrylate, n-butyl methacrylate, and 2-ethylhexyl methacrylate (1) to (3) ), the non-aqueous adhesive composition according to any one of

(5) The content of the resin contained in the non-aqueous adhesive composition is 1% by mass or more and 30% by mass or less based on the total amount of the non-aqueous adhesive composition (1) to (4). Non-aqueous adhesive composition.

(6) The non-aqueous adhesive composition according to any one of (1) to (5), wherein the resin A has a weight average molecular weight Mw of 10000 or more and 60000 or less.

(7) The non-aqueous adhesive composition according to any one of (1) to (6), wherein the organic solvent contains a glycol ether solvent represented by the following formula (2).
R _a —(—OR _b ) _n —OR _c (2)
(In formula (2), R _a and R _c are each independently hydrogen or an optionally branched alkyl group having 1 to 8 carbon atoms, and R _b is a branched alkyl group having 1 to 4 carbon atoms. (n represents an integer of 1 or more and 6 or less).

(8) The non-aqueous adhesive composition according to (7), wherein the glycol ether-based solvent contains a glycol ether monoalkyl represented by the following formula (3).
R _d —(—OR _e ) _n —OH (3)
(In Formula (3), R _d is an alkyl group having 1 to 8 carbon atoms and may be branched, and R _e represents an alkylene group having 1 to 4 carbon atoms and may be branched. n represents an integer of 1 or more and 6 or less.)

(9) The non-aqueous adhesive composition according to (7) or (8), wherein the glycol ether-based solvent contains a glycol ether dialkyl represented by the following formula (4).
R _f —(—OR _g ) _n —OR _h (4)
(In Formula (4), R _f and R _h are each independently an optionally branched alkyl group having 1 to 8 carbon atoms, and R _g is an optionally branched alkyl group having 1 to 4 carbon atoms. represents a good alkylene group, and n represents an integer of 1 or more and 6 or less.)

(10) The non-aqueous adhesive composition according to any one of (1) to (9), wherein the organic solvent contains a solvent represented by formula (5).

(In Formula (5), R ₁ is hydrogen or an alkyl group having 1 to 4 carbon atoms, and R ₂ and R ₃ each independently represent hydrogen or an alkyl group having 1 to 4 carbon atoms.

(11) The non-aqueous adhesive composition according to any one of (1) to (10), wherein the organic solvent contains a solvent represented by general formula (6).

(In formula (6), R ₄ is an alkylene group having 3 to 5 carbon atoms, and R ₅ represents hydrogen, an alkyl group having 1 to 4 carbon atoms, or an unsaturated hydrocarbon group.)

(12) The non-aqueous adhesive composition according to any one of (1) to (11), wherein the organic solvent contains a solvent represented by general formula (7).

(In formula (7), _R6 is an alkylene group having 3 to 5 carbon atoms, and _R7 represents hydrogen or an alkyl group having 1 to 4 carbon atoms.)

(13) The non-aqueous adhesive composition according to any one of (1) to (12), wherein the organic solvent contains a solvent represented by general formula (8).

(In formula (8), R ₈ is hydrogen or an alkyl group having 1 to 4 carbon atoms, and R ₉ represents an alkylene group having 1 to 3 carbon atoms.)

(14) The non-aqueous adhesive composition according to any one of (1) to (13), wherein the organic solvent contains a solvent represented by general formula (9).

(In formula (9), R ₁₀ , R ₁₁ and R ₁₂ are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms, and R ₁₃ represents an alkylene group having 1 to 4 carbon atoms. .)

(15) The non-aqueous adhesive composition according to any one of (1) to (14), which has a viscosity of 1.0 mPa·s or more and 15.0 mPa·s or less at 25°C.

(16) The non-aqueous adhesive composition according to any one of (1) to (15), which has a surface tension of 20 mN/m or more and 40 mN/m or less at 25°C.

(17) The non-aqueous adhesive composition according to any one of (1) to (16), which is ejected onto a substrate from a nozzle and attaches the solid matter thereon to fix the solid matter on the substrate. .

(18) The non-aqueous adhesive composition according to (17), wherein the solid material is a metal foil, and the metal foil is fixed to the substrate.

(19) Ejected by an inkjet method using an inkjet recording device,
The non-aqueous adhesive composition according to any one of (1) to (18) to be installed in the inkjet recording device.

(20) A recording method comprising ejecting the non-aqueous adhesive composition according to any one of (1) to (19) onto a substrate.

(21) A method for producing a recorded matter, comprising the step of ejecting the non-aqueous adhesive composition according to any one of (1) to (19) onto a substrate.

(22) The method for producing a recorded matter according to (21), further comprising the step of fixing a solid substance to the surface of the non-aqueous adhesive composition discharged onto the substrate.

(23) The method for producing a recorded matter according to (22), wherein, in the step of fixing the solid matter, the solid matter is fixed to the surface of the non-aqueous adhesive composition while heating.

(24) A set of compositions containing the non-aqueous adhesive composition according to any one of (1) to (19) as a first composition and an ink composition as a second composition.

(25) The ink composition, which is the second composition, contains an organic solvent and a resin, and the resin may contain a resin A containing the following monomer (a). The set of compositions according to (24), including a composition in which the ratio of the monomer (a) constituting A is 50% by mass or less in the total amount of the monomers constituting the resin A.

(26) A device for discharging the non-aqueous adhesive composition according to any one of (1) to (19) onto a substrate.

(27) A base material and an adhesive layer formed on the base material, the adhesive layer containing a resin, the resin containing a resin A containing the following monomer (a) as a configuration, A recorded matter, wherein the content of the resin A is 50% by mass or more in the total amount of the resin contained in the adhesive layer.

(28) The recorded matter according to (27), further comprising a solid object on the adhesive layer.

The present invention can provide an adhesive composition that can be discharged onto a substrate from a nozzle and that can fix solids such as powder and foil to the substrate.

Hereinafter, specific embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments at all, and can be implemented with appropriate modifications within the scope of the purpose of the present invention. can do. In addition, in this specification, the notation "to" means "more than" and "less than".

≪1. Non-aqueous adhesive composition>>
The non-aqueous adhesive composition according to the present embodiment is a non-aqueous adhesive composition that is discharged from a nozzle and contains an organic solvent and a resin. As used herein, the term "ejected from a nozzle" means ejecting a predetermined amount of a composition (liquid) through a nozzle onto a substrate such as a substrate. means a discharge format such as

Here, the non-aqueous adhesive composition is a composition containing an organic solvent as a liquid medium without intentionally containing water, and having adhesiveness at a predetermined temperature by volatilizing the solvent. It means a composition that has the function of fixing solid substances such as powders and foils to a substrate due to its stickiness.

Since the non-aqueous adhesive composition according to the present embodiment is a composition containing an organic solvent as a liquid medium without intentionally containing water, it can be suitably used particularly for a resin substrate. can. Although details will be described later, the substrate that can be used for the non-aqueous adhesive composition according to the present embodiment may be a non-absorbent substrate or an absorbent substrate, and various substrates. can be used.

In this specification, the phrase "does not intentionally contain water" means that water that is inevitably contained due to moisture in the atmosphere or additives is not taken into consideration. The water content in the non-aqueous adhesive composition according to the present embodiment is preferably 5.0% by mass or less, more preferably 3.0% by mass, based on the total amount of the non-aqueous adhesive composition. , more preferably 1.0% by mass or less, and even more preferably 0.5% by mass or less. When moisture originating from raw materials or moisture in the atmosphere during the manufacturing process is mixed, the storage stability of the non-aqueous adhesive composition may be deteriorated. By reducing the water content in the non-aqueous adhesive composition so that it contains as little water as possible (intentionally avoiding water), storage stability, etc. can be improved more effectively. It is possible to

Then, the resin contained in this non-aqueous adhesive composition contains a resin A containing the following monomer (a) as a configuration, and the ratio of the monomer (a) constituting the resin A is the total amount of the monomers constituting the resin A It is characterized by being 50% by mass or more.

By including a resin containing such a specific monomer in a predetermined ratio, it becomes adhesive at a predetermined temperature, and the adhesiveness fixes solid objects such as powders and foils to the substrate. It will have a function that allows you to

Moreover, by including such a resin A together with an organic solvent, which is a liquid medium, it becomes possible to eject it from the nozzle. Thereby, the non-aqueous adhesive composition can be stably applied to the subject (substrate). Moreover, with the inkjet method or the dispenser method, by ejecting onto the desired position on the surface of the object (base material), the solid matter such as powder or foil is fixed to the desired position on the surface of the object (base material). For example, it is possible to obtain a patterned recorded matter in which a solid object is fixed at a desired position.

In particular, when the non-aqueous adhesive composition according to the present embodiment is ejected by an inkjet method, the inkjet ejection stability can be increased, and the non-aqueous adhesive composition can form a uniform coating film (adhesive layer ) can be formed. Therefore, it is preferable that the non-aqueous adhesive composition according to the present embodiment is ejected by an inkjet recording apparatus by an inkjet method and mounted on the inkjet recording apparatus.

Each component contained in the non-aqueous adhesive composition according to the present embodiment will be described below.

[resin]
The non-aqueous adhesive composition according to this embodiment contains a resin. The resin has flexibility at a predetermined temperature, thereby imparting the function of fixing solid objects such as powder and foil to the base material.

Then, this resin contains a resin A containing the following monomer (a) as a configuration, and the ratio of the monomer (a) constituting the resin A is 50% by mass or more in the total amount of the monomers constituting the resin A. Characterized by

(In formula (1), Ry represents a hydrogen group or an optionally branched hydrocarbon group having 1 to 12 carbon atoms. When Ry is a hydrogen group, Rx may be branched or monocyclic. represents an optionally branched hydrocarbon group having 1 to 18 carbon atoms, and when Ry is an optionally branched hydrocarbon group having 1 to 12 carbon atoms, Rx is an optionally branched hydrocarbon group having 2 to 18 carbon atoms represents a hydrogen group.)

By containing the resin A containing the monomer (a) as a configuration, the non-aqueous adhesive composition on the substrate becomes flexible at a predetermined temperature, thereby fixing the solid matter to the substrate. becomes possible.

In addition, the resin A containing the monomer (a) as a configuration is a single polymer of the monomer (a) (the ratio of the monomer (a) constituting the resin A is 100% by mass in the total amount of the monomers constituting the resin A). Even if there is, a copolymer with another monomer containing an ethylenic double bond (the ratio of the monomer (a) constituting the resin A is 50% by mass or more and less than 100% by mass of the total amount of the monomers constituting the resin A) may be

The ratio of the monomer (a) constituting the resin A is preferably 70% by mass or more, more preferably 90% by mass or more, of the total amount of the monomers constituting the resin A.

"It may be monocyclic" means that it may be a monocyclic functional group such as a cycloalkyl group, and does not include a polycyclic functional group such as an isobornyl group.

In formula (1), when Ry is a hydrogen group, Rx is preferably a hydrocarbon group of 2 or more and 12 or less, which may be branched or monocyclic, and may be branched or monocyclic. A hydrocarbon group of 4 or more and 12 or less is more preferable, and a hydrocarbon group of 4 or more and 8 or less which may be branched or monocyclic is more preferable.

Further, in formula (1), when Ry is an optionally branched hydrocarbon group having 1 to 12 carbon atoms, Rx is an optionally branched hydrocarbon group having 4 to 12 carbon atoms. More preferably, it is a hydrocarbon group having 4 or more and 8 or less carbon atoms which may be branched.

Examples of monomer (a) include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, n-pentyl acrylate, and 3-pentyl acrylate. , n-hexyl acrylate, n-heptyl acrylate, 2-heptyl acrylate, n-octyl acrylate, n-nonyl acrylate, n-decyl acrylate, undecyl acrylate, isodecyl acrylate, lauryl acrylate, cyclohexyl acrylate, ethyl methacrylate, n- Propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, s-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, n-pentyl methacrylate, neopentyl methacrylate, n-hexyl methacrylate, n-heptyl methacrylate, 2- heptyl methacrylate, n-octyl methacrylate, n-nonyl methacrylate, n-decyl methacrylate, undecyl methacrylate, isodecyl methacrylate, lauryl methacrylate, stearyl methacrylate, dicyclopentanyl acrylate, 4-tert-butylcyclohexyl acrylate, and 3,3 ,5-trimethylcyclohexyl acrylate, preferably containing at least one selected from the group consisting of methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, and 3-pentyl acrylate. Acrylates, 2-heptyl acrylate, lauryl acrylate, cyclohexyl acrylate, n-propyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, n-pentyl methacrylate, neopentyl methacrylate, n-hexyl methacrylate, n-heptyl methacrylate, 2-heptyl methacrylate , n-octyl methacrylate, n-nonyl methacrylate, undecyl methacrylate, isodecyl methacrylate, and stearyl methacrylate. More preferably, it contains at least one selected from the group consisting of pentyl acrylate, lauryl acrylate, cyclohexyl acrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, n-pentyl methacrylate, and n-hexyl methacrylate. Particularly preferred are those containing at least one selected from the group consisting of methyl acrylate, cyclohexyl acrylate, n-butyl methacrylate, and 2-ethylhexyl methacrylate.

The monomer other than the monomer (a) that constitutes the resin A is not particularly limited as long as it is another ethylenically polymerizable monomer that can be copolymerized with the monomer (a). For example, methyl methacrylate, ethoxyethyl methacrylate, benzyl acrylate, benzyl methacrylate, isobornyl acrylate, cyclohexyl methacrylate, 4-acryloylmorpholine, dicyclopentanyl methacrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, cyclic trimethylolpropane formal Acrylates, hydroxycyclohexyl methacrylate, cyclooctyl methacrylate, cycloheptyl methacrylate, cyclopentyl methacrylate, cyclobutyl methacrylate, cyclopropyl methacrylate, tert-butylcyclohexyl methacrylate, trifluoroethyl acrylate, trifluoroethyl methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, phenyl acrylates, phenyl methacrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, caprolactone-modified hydroxy (meth)acrylate, methyl α-(hydroxymethyl) (meth)acrylate, ethyl α-(hydroxymethyl) (meth)acrylate, n-butyl α-(hydroxymethyl) (Meth) acrylates, 1,4-cyclohexanedimethanol mono (meth) acrylate, hydroxyl group-containing monomers containing hydroxyl groups such as 4-hydroxybutyl (meth) acrylate, (meth) acrylamide, N-monomethyl (meth) acrylamide, N - monoethyl (meth)acrylamide, N,N-dimethyl (meth)acrylamide, Nn-propyl (meth)acrylamide, N-isopropyl (meth)acrylamide, methylenebis (meth)acrylamide, N-methylol (meth)acrylamide, N -Acrylamide compounds such as butoxymethyl (meth)acrylamide, dimethylaminoethyl (meth)acrylamide, N,N-dimethylaminopropylacrylamide, diacetoneacrylamide, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, morpholine Nitrogen atom-containing (meth)acrylate compounds such as ethylene oxide addition (meth)acrylates, N-vinylpyrrolidone, N-vinylpyridine, N-vinylimidazole, N-vinylpyrrole, N-vinyloxazolidone, N-vinylsuccinimide, N -vinyl methyl carbamate, N,N-methylvinylacetamide, (meth)acryloyloxyethyltrimethylammonium chloride, 2-isopropenyl-2-oxazoline, 2-vinyl-2-oxazoline, (meth)acrylonitrile and other amino group-containing monomers (Meth) acrylic acid ester monomers different from the monomer (a) such as vinyl acetate, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, N-vinylcarbazole, vinylimidazole, Vinyl monomers such as vinyl ether, vinyl ketone and vinyl pyrrolidone, styrene, α-, o-, m-, p-alkyl, nitro, cyano, amide and ester derivatives of styrene, aromatic vinyl monomers such as vinyl toluene and chlorostyrene, and ethylene , olefin monomers such as propylene and isopropylene; diene monomers such as butadiene and chloroprene; and vinyl cyanide monomers such as acrylonitrile and methacrylonitrile. Diacrylate compounds such as polyethylene glycol diacrylate, triethylene glycol diacrylate and 1,3-butylene glycol diacrylate; and triacrylate compounds such as trimethylolpropane triacrylate, trimethylolethane triacrylate and tetramethylolmethane triacrylate. and dimethacrylate compounds such as ethylene glycol dimethacrylate, diethylene glycol dimethacrylate and triethylene glycol dimethacrylate; trimethacrylate compounds such as trimethylolpropane trimethacrylate and trimethylolethane trimethacrylate; and divinylbenzene. The acrylic resin can be formed using these monomers, but the form of copolymerization of the monomers is not particularly limited, and may be, for example, a block copolymer, a random copolymer, a graft copolymer, or the like. be able to.

The resin A may be synthesized using the above monomers as raw materials, or a commercially available resin may be used.

In addition, the content of resin A is preferably 50% by mass or more, more preferably 70% by mass or more, and 90% by mass or more of the total amount of resin contained in the non-aqueous adhesive composition. More preferred.

The lower limit of the glass transition temperature of the resin A containing the monomer (a) as a configuration is not particularly limited, but is preferably -50°C or higher, more preferably -45°C or higher, and -40°C. It is more preferably at least -35°C, and even more preferably at -35°C or higher. When the resin A has a glass transition temperature of −50° C. or higher, it is possible to improve the abrasion resistance and peeling resistance of the fixed solid matter.

The upper limit of the glass transition temperature of the resin A containing the monomer (a) is not particularly limited, but is preferably 40° C. or lower, more preferably 35° C. or lower, and 30° C. or lower. is more preferable, and 25° C. or less is even more preferable. When the glass transition temperature of the resin A is 40° C. or less, the resin becomes flexible at a predetermined temperature, and the solid material can be more appropriately fixed to the substrate.

In this specification, the "glass transition temperature" of a resin means a calculated value obtained by the following FOX formula.

1/Tg= _W1 / _Tg1 + _W2 / _Tg2 +...+ _Wn / _Tgn
(In the formula, W ₁ to W _n represent the weight fraction of each monomer, and Tg ₁ to Tg _n are the glass transition temperatures of homopolymers obtained by polymerizing each monomer alone (unit is absolute temperature Represents "K").Use the numerical value described in POLYMER HANDBOOK (J. BRANDRUP EH IMMERGUT, Editors), etc., or use the Tg value (glass transition temperature) described in the catalog provided by the monomer manufacturer. do.

Although the weight average molecular weight (relative molecular mass) of Resin A is not particularly limited, it is preferably 10,000 or more, more preferably 15,000 or more. The weight average molecular weight (relative molecular mass) is preferably 60,000 or less, more preferably 50,000 or less. Relative molecular weights of resins can be measured by conventional GPC (gel permeation chromatography).

Also, the resin contained in the non-aqueous adhesive composition according to the present embodiment may contain a resin other than resin A. For example, acrylic resins different from resin A (including copolymers such as styrene-acrylic resins), polystyrene resins, polyester resins, vinyl chloride resins, vinyl acetate resins, vinyl chloride vinyl acetate copolymers Resin, polyethylene resin, polyurethane resin, rosin-modified resin, phenolic resin, terpene resin, polyamide resin, vinyl toluene-α-methylstyrene copolymer, ethylene-vinyl acetate copolymer, cellulose acetate butyrate , cellulose acetate propionate, silicone (silicon)-based resins, acrylamide-based resins, epoxy-based resins, polyether-based resins, polycarbonate-based resins, or copolymer resins or mixtures thereof.

Among these resins, resins other than resin A preferably contain acrylic resins, vinyl chloride-based resins, vinyl chloride-vinyl acetate copolymer resins, cellulose-based resins, polyester-based resins, and polyurethane-based resins.

The acrylic resin different from the resin A may be a homopolymer of one radically polymerizable monomer, or a copolymer of two or more selected radically polymerizable monomers. good. Although such acrylic resins are not particularly limited, for example, a homopolymer of a monomer that does not correspond to the monomer (a) such as methyl methacrylate, or a copolymer of a monomer that does not correspond to the monomer (a) and the monomer (a) It is a coalescence and does not correspond to resin A (the ratio of the monomer (a) constituting the resin is less than 50% by mass). A commercially available (meth)acrylic resin may also be used.

The vinyl chloride resin may be either a homopolymer composed of a vinyl chloride monomer or a copolymer using two or more selected polymerizable monomers. Examples of copolymers of vinyl chloride resins include vinyl chloride-vinyl acetate copolymer resins. A vinyl chloride-vinyl acetate copolymer resin is a polymer of vinyl chloride monomer and vinyl acetate monomer. Vinyl chloride-vinyl acetate copolymer resins include, for example, vinyl chloride-vinyl acetate copolymer, vinyl chloride/vinyl acetate/maleic acid copolymer, vinyl chloride/vinyl acetate/vinyl alcohol copolymer, vinyl chloride/vinyl acetate / hydroxyalkyl acrylate copolymers, etc., and mixtures thereof. Examples of the vinyl chloride-vinyl acetate copolymer resins include "SOLBIN C", "SOLBIN CL", "SOLBIN CNL", "SOLBIN CLL", "SOLBIN CLL2", and "SOLBIN C5R" from Nissin Chemical Industry Co., Ltd. ”, “SOLBIN TA2”, “SOLBIN TA3”, “SOLBIN A”, “SOLBIN AL”, “SOLBIN TA5R”, “SOLBIN M5” and the like.

A vinyl chloride-vinyl acetate copolymer resin can be obtained by polymerizing a vinyl chloride monomer and a vinyl acetate monomer. A conventionally known polymerization method may be used as the polymerization method. The polymerization method is preferably emulsion polymerization or suspension polymerization, more preferably suspension polymerization.

A cellulose-based resin is a resin with a cellulose skeleton that is obtained by biologically or chemically introducing functional groups using cellulose as a raw material. For example, cellulose-based resins include cellulose acetate butyrate resins, cellulose acetate propionate resins, cellulose acetate alkylate resins such as cellulose acetate propionate butyrate resins, cellulose acetate resins, nitrocellulose resins, and mixtures thereof. mentioned. Examples of the cellulose resins include "CAB551-0.01", "CAB551-0.2", "CAB553-0.4", "CAB531-1", "CAB381-0.1" and "CAB381-0.1" available from EASTMAN. 5”, “CAB381-2”, “CAB381-20”, “CAP504”, “CAP482-0.5” and the like.

A polyester resin contains at least a structural unit obtained by polycondensation of an alcohol component and a carboxylic acid component. The polyester-based resin may include a modified polyester-based resin. As the polyester resin, Toyobo's "VYLON226", "VYLON270", "VYLON560", "VYLON600", "VYLON630", "VYLON660", "VYLON885", "VYLONGK250", "VYLONGK810", "VYLONGK890", etc. It can be obtained and used under trade names such as "elitleUE-3200", "elitleUE-3285", "elitleUE-3320", "elitleUE-9800" and "elitleUE-9885" manufactured by Unitika.

A polyurethane resin contains at least a structural unit obtained by copolymerizing an alcohol component and an isocyanate component. Polyurethane-based resins may include polyurethane-based resins modified with polyester, polyether, or caprolactone. Examples of the polyurethane-based resins include "Uriano KL-424", "Uriano KL-564", "Uriano KL-593", and "Uriano 3262" available from Arakawa Chemical Industries, Ltd., and "Pandex 372E" and "Uriano 372E" available from DIC. Pandex 390E”, “Pandex 394E”, “Pandex 304”, “Pandex 305E”, “Pandex P-870”, “Pandex P-910”, “Pandex P-895”, “Pandex 4030", "Pandex 4110", and the like.

These acrylic resins, vinyl chloride resins, cellulose resins, polyester resins, and polyurethane resins may be used alone, or two or more of them may be used in combination.

The content of the resin contained in the non-aqueous adhesive composition is not particularly limited, but it is preferably contained in the range of 1.0% by mass or more in the total amount of the non-aqueous adhesive composition, and 3.0% by mass or more. more preferably in the range of 5.0% by mass or more, and even more preferably in the range of 7.0% by mass or more. As a result, the fixability of the solid substance is improved. For example, when a metal foil is used as the solid substance and the metal foil is transferred (fixed) to the base material, the foil transferability can be improved.

The resin contained in the non-aqueous adhesive composition is preferably contained in the range of 30.0% by mass or less in the total amount of the non-aqueous adhesive composition, and more preferably in the range of 20.0% by mass or less. It is preferably contained in the range of 15.0% by mass or less, and more preferably contained. This improves the ejection stability of the non-aqueous adhesive composition from the nozzle. In particular, when the non-aqueous adhesive composition according to the present embodiment is used as an inkjet non-aqueous adhesive composition for inkjet ejection, it is necessary to effectively improve the ejection stability from the ink head nozzle. becomes possible.

[Organic solvent]
The non-aqueous adhesive composition according to this embodiment contains an organic solvent. The organic solvent is a liquid medium for the non-aqueous adhesive composition, and has the function of dissolving (or dispersing) each component such as the resin.

In addition, by containing an organic solvent, the fluidity of the non-aqueous adhesive composition is improved, and it becomes possible to eject it from a nozzle such as an inkjet or a dispenser.

As the organic solvent, for example, those contained in conventional non-aqueous ink compositions for inkjet (sometimes referred to as non-aqueous or oily) can be used. Examples include those containing a glycol ether solvent represented by the following formula (2).

R _a —(—OR _b ) _n —OR _c (2)
(In formula (2), R _a and R _c are each independently hydrogen or an optionally branched alkyl group having 1 to 8 carbon atoms, and R _b is a branched alkyl group having 1 to 4 carbon atoms. (n represents an integer of 1 or more and 6 or less).

Glycol ether-based solvents include glycol ether monoalkyl represented by the following formula (3) and glycol ether dialkyl represented by the following formula (4).

R _d —(—OR _e ) _n —OH (3)
(In Formula (3), R _d is an alkyl group having 1 to 8 carbon atoms and may be branched, and R _e represents an alkylene group having 1 to 4 carbon atoms and may be branched. n represents an integer of 1 or more and 6 or less.)

R _f —(—OR _g ) _n —OR _h (4)
(In Formula (4), R _f and R _h are each independently an optionally branched alkyl group having 1 to 8 carbon atoms, and R _g is an optionally branched alkyl group having 1 to 4 carbon atoms. represents a good alkylene group, and n represents an integer of 1 or more and 6 or less.)

The resin A containing the monomer (a) as a constituent is easily dissolved in a glycol ether solvent, and by containing a predetermined amount of the glycol ether solvent, the ejection stability of the non-aqueous adhesive composition from the nozzle is improved. . In particular, when the non-aqueous adhesive composition according to the present embodiment is used as an inkjet non-aqueous adhesive composition for inkjet ejection, it is necessary to effectively improve the ejection stability from the ink head nozzle. becomes possible.

Examples of glycol ether monoalkyl include ethylene glycol mono-n-butyl ether, ethylene glycol mono-isobutyl ether, ethylene glycol mono-t-butyl ether, ethylene glycol mono-2-ethylhexyl ether, diethylene glycol monomethyl (or ethyl, propyl, isopropyl , n-butyl, isobutyl, t-butyl, 2-ethylhexyl ether, triethylene glycol monomethyl (or ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, 2-ethylhexyl) ether, tetraethylene glycol monomethyl ether, Propylene glycol mono-n-butyl ether, propylene glycol mono-isobutyl ether, propylene glycol mono-t-butyl ether, propylene glycol mono-2-ethylhexyl ether, dipropylene glycol monomethyl (or ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, 2-ethylhexyl) ether, tripropylene glycol monomethyl ether (or ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl) ether, tetrapropylene glycol monomethyl ether (or ethyl, propyl, isopropyl, n-butyl , isobutyl, t-butyl, 2-ethylhexyl) and the like.

Among these, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, tetraethylene glycol Monomethyl Ether, Tetraethylene Glycol Monoethyl Ether, Tetraethylene Glycol Monopropyl Ether, Tetraethylene Glycol Monobutyl Ether, Propylene Glycol Monomethyl Ether, Propylene Glycol Monoethyl Ether, Propylene Glycol Monopropyl Ether, Propylene Glycol Monobutyl Ether, Dipropylene Glycol Monomethyl Ether , dipropylene glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether and the like are preferred.

Glycol ether dialkyl includes ethylene glycol dibutyl ether, ethylene glycol dipropyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol propyl methyl ether, diethylene glycol dibutyl ether, diethylene glycol butyl methyl ether, diethylene glycol butyl. Ethyl ether, diethylene glycol methyl-2-ethylhexyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol ethyl methyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol ethyl methyl ether, propylene glycol diethyl Ether, propylene glycol ethyl methyl ether, propylene glycol methyl propyl ether, propylene glycol methyl butyl ether, propylene glycol methyl-2-ethylhexyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol ethyl methyl ether, dipropylene glycol methyl Propyl ether, dipropylene glycol dipropyl ether, dipropylene glycol methyl butyl ether, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, tripropylene glycol ethyl methyl ether and the like.

Among these, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dipropyl ether, diethylene glycol propyl methyl ether, diethylene glycol dibutyl ether, diethylene glycol butyl methyl ether, diethylene glycol butyl ethyl ether, diethylene glycol methyl-2-ethylhexyl ether, triethylene glycol Dimethyl ether, triethylene glycol diethyl ether, triethylene glycol ethyl methyl ether, tetraethylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol ethyl methyl ether, propylene glycol methyl propyl ether, propylene glycol methyl butyl ether, propylene glycol methyl-2-ethylhexyl ether , dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol ethyl methyl ether, dipropylene glycol methyl propyl ether, dipropylene glycol dipropyl ether, tripropylene glycol dimethyl ether, tripropylene glycol ethyl methyl ether and the like are preferred. mentioned.

The preferred content of the glycol ether solvent represented by formula (2) is preferably 20% by mass or more, more preferably 50% by mass or more, more preferably 70% by mass in the total amount of the non-aqueous adhesive composition. It is more preferable that it is above.

The preferred content of the glycol ether solvent represented by formula (2) is preferably 95% by mass or less, more preferably 90% by mass or less, and 85% by mass of the total amount of the non-aqueous adhesive composition. More preferably:

The preferred content of the glycol ether monoalkyl represented by formula (3) is preferably 1% by mass or more, more preferably 3% by mass or more, and 5% by mass of the total amount of the non-aqueous adhesive composition. It is more preferable that it is above.

The preferred content of the glycol ether monoalkyl represented by formula (3) is preferably 30% by mass or less, more preferably 20% by mass or less, and 10% by mass of the total amount of the non-aqueous adhesive composition. More preferably:

The preferred content of the glycol ether dialkyl represented by formula (4) is preferably 40% by mass or more, more preferably 50% by mass or more, and 60% by mass or more in the total amount of the non-aqueous adhesive composition. is more preferable.

The preferred content of the glycol ether dialkyl represented by formula (4) is preferably 95% by mass or less, more preferably 90% by mass or less, and 85% by mass or less in the total amount of the non-aqueous adhesive composition. is more preferable.

Further, instead of the glycol ether-based solvent, or together with the glycol ether-based solvent, the solvent represented by the general formula (5), the solvent represented by the general formula (6), and the general formula (7) It is preferable to contain at least one or more selected from the group consisting of the represented solvents.

R ₂ and R ₃ in formula (5) are preferably alkyl groups having 1 to 4 carbon atoms, more preferably alkyl groups having 2 to 4 carbon atoms.

"Unsaturated hydrocarbon group" means a hydrocarbon group containing at least one or more multiple bonds such as a vinyl group.

R ₅ in formula (6) is preferably hydrogen, an alkyl group having 1 to 3 carbon atoms, or an unsaturated hydrocarbon group, and is preferably hydrogen, an alkyl group having 1 to 2 carbon atoms, or an unsaturated hydrocarbon group. A hydrogen group is preferred.

Among these, R ₆ is preferably an alkylene group of 3 or more and 4 or less, more preferably 3. R ₇ is preferably hydrogen or an alkyl group having 1 carbon atom, more preferably hydrogen.

When the non-aqueous adhesive composition according to the present embodiment is used as an inkjet non-aqueous adhesive composition for inkjet ejection, it contains these alkylamide solvents, cyclic amide solvents, and lactone solvents. By doing so, it is possible to effectively eliminate clogging in the nozzles of the ink jet head and effectively improve the ejection stability from the ink head nozzles.

Furthermore, if it is a non-aqueous adhesive composition containing these solvents (solvent represented by formula (5), solvent represented by formula (6), solvent represented by formula (7)), the resin It has high permeability to the base material and dries quickly on the resin base material after ejection. When the non-aqueous adhesive composition according to the present embodiment is discharged onto a resin substrate and the metal foil is transferred (fixed) to the resin substrate by the non-aqueous adhesive composition, drying on the resin substrate Since the transfer speed is fast, it is possible to transfer the metal foil particularly cleanly, and the surface shape of the metal foil on the obtained recorded matter is good, and the fineness is also good. Fine fixing is possible.

Specific examples of the solvent represented by formula (5) include N,N-diethylformamide, N,N-diethylacetamide, N,N-dipropylformamide, N,N-dibutylformamide, N,N- Examples include alkylamide solvents such as diethylpropanamide, N,N-dipropylpropanamide, N-ethylformamide and N-ethylacetamide. Among these, from the viewpoint of particularly exhibiting the effects of the present invention, it is preferable to contain at least one selected from the group consisting of N,N-diethylformamide, N,N-diethylpropanamide and N,N-diethylacetamide. preferable.

Specific examples of solvents represented by formula (6) include 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, N-butyl-2 -pyrrolidone, ε-caprolactam, N-methyl-ε-caprolactam, N-vinylcaprolactam, N-ethyl-ε-caprolactam, N-propyl-ε-caprolactam, N-butyl-ε-caprolactam, N-acetylcaprolactam, etc. A cyclic amide-based solvent can be mentioned. Among these, it is preferable to contain at least one selected from the group consisting of ε-caprolactam, N-methylcaprolactam, and N-vinylcaprolactam.

Specific examples of solvents represented by formula (7) include γ-butyrolactone, γ-valerolactone, γ-hexanolactone, γ-heptanolactone, γ-octanolactone, γ-nonalactone, γ- decalactone, γ-undecalactone, δ-valerolactone, δ-hexanolactone, δ-heptanolactone, δ-octanolactone, δ-nonalactone, δ-decalactone, δ-undecalactone, ε-caprolactone, etc. A lactone solvent can be mentioned. Among these, it is preferable to contain at least one selected from the group consisting of γ-butyrolactone, γ-valerolactone, and ε-caprolactone.

The content of the solvent represented by formula (5) is not particularly limited, but the lower limit of the content of the solvent represented by formula (5) is 1% by mass or more in the total amount of the non-aqueous adhesive composition. is preferred, 5% by mass or more is more preferred, and 8% by mass or more is even more preferred.

The upper limit of the content of the solvent represented by formula (5) is preferably 90% by mass or less, more preferably 80% by mass or less, and 75% by mass or less in the total amount of the non-aqueous adhesive composition. It is even more preferable to have

The content of the solvent represented by formula (6) is not particularly limited, but the lower limit of the content of the solvent represented by formula (6) is 1% by mass or more in the total amount of the non-aqueous adhesive composition. is preferred, 5% by mass or more is more preferred, and 8% by mass or more is even more preferred.

The upper limit of the content of the solvent represented by formula (6) is preferably 90% by mass or less, more preferably 80% by mass or less, and 75% by mass or less in the total amount of the non-aqueous adhesive composition. It is even more preferable to have

The content of the solvent represented by formula (7) is not particularly limited, but the lower limit of the content of the solvent represented by formula (7) is 1% by mass or more in the total amount of the non-aqueous adhesive composition. is preferred, 3% by mass or more is more preferred, and 5% by mass or more is even more preferred.

The upper limit of the content of the solvent represented by formula (7) is preferably 70% by mass or less, more preferably 50% by mass or less, and 30% by mass or less in the total amount of the non-aqueous adhesive composition. It is more preferable that the content is 20% by mass or less, and it is even more preferable that the content is 20% by mass or less.

In addition, instead of the solvent represented by the general formula (5), the solvent represented by the general formula (6), and the solvent represented by the general formula (7), or together with these solvents, the general formula (8) A solvent represented by the general formula (9), a solvent represented by the general formula (9), a solvent represented by the general formula (10), or a solvent represented by the general formula (11) It is preferable to contain at least one or more selected from the group consisting of solvents. As a result, a solvent-based non-aqueous adhesive composition that effectively exhibits the above effects is obtained.

(In formula (10), R ₁₄ represents an optionally branched alkyl group or unsaturated hydrocarbon group having 1 to 4 carbon atoms, and R ₁₅ represents an alkylene group having 1 to 4 carbon atoms.)

(In Formula (11), R ₁₆ and R ₁₇ are each independently an alkyl group having 1 to 4 carbon atoms and may be branched, and R ₁₈ represents an alkylene group having 2 to 4 carbon atoms.

Specific examples of the solvent represented by formula (8) include carbonate esters such as propylene carbonate and ethylene carbonate.

Specific examples of the solvent represented by formula (9) include 3-methoxypropanamide, 3-butoxypropanamide, 3-methoxy-N,N-dimethylpropanamide, 3-methoxy-N,N-dibutyl Propanamide, 3-butoxy-N,N-dibutylpropanamide, 3-butoxy-N,N-dimethylpropanamide, N,N-dimethyl-3-methoxypropanamide, N,N-dibutyl-3-methoxypropanamide , N,N-dibutyl-3-butoxypropanamide and N,N-dimethyl-3-butoxypropanamide.

Specific examples of the solvent represented by formula (10) include oxazolidinone-based solvents such as 3-methyl-2-oxazolidinone, 3-ethyl-2-oxazolidinone, and N-vinylmethyloxazolidinone.

Solvents represented by formula (11) include 1,3-dimethyl-2-imidazolidinone, 1-methyl-3-ethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, and the like. and imidazolidinone-based solvents.

The content of the solvent represented by formula (8) is not particularly limited, but the lower limit of the content of the solvent represented by formula (8) is 1% by mass or more in the total amount of the non-aqueous adhesive composition. is preferred, 3% by mass or more is more preferred, and 5% by mass or more is even more preferred.

The upper limit of the content of the solvent represented by formula (8) is preferably 70% by mass or less, more preferably 50% by mass or less, and 30% by mass or less in the total amount of the non-aqueous adhesive composition. It is more preferable that the content is 20% by mass or less, and it is even more preferable that the content is 20% by mass or less.

The content of the solvent represented by formula (9) is not particularly limited, but the lower limit of the content of the solvent represented by formula (9) is 1% by mass or more in the total amount of the non-aqueous adhesive composition. is preferred, 3% by mass or more is more preferred, and 5% by mass or more is even more preferred.

The upper limit of the content of the solvent represented by formula (9) is preferably 70% by mass or less, more preferably 50% by mass or less, and 30% by mass or less in the total amount of the non-aqueous adhesive composition. It is more preferable that the content is 20% by mass or less, and it is even more preferable that the content is 20% by mass or less.

The content of the solvent represented by formula (10) is not particularly limited, but the lower limit of the content of the solvent represented by formula (10) is 1% by mass or more in the total amount of the non-aqueous adhesive composition. is preferred, 3% by mass or more is more preferred, and 5% by mass or more is even more preferred.

The upper limit of the content of the solvent represented by formula (10) is preferably 70% by mass or less, more preferably 50% by mass or less, and 30% by mass or less in the total amount of the non-aqueous adhesive composition. It is more preferable that the content is 20% by mass or less, and it is even more preferable that the content is 20% by mass or less.

The content of the solvent represented by formula (11) is not particularly limited, but the lower limit of the content of the solvent represented by formula (11) is 1% by mass or more in the total amount of the non-aqueous adhesive composition. is preferred, 3% by mass or more is more preferred, and 5% by mass or more is even more preferred.

The upper limit of the content of the solvent represented by formula (11) is preferably 70% by mass or less, more preferably 50% by mass or less, and 30% by mass or less in the total amount of the non-aqueous adhesive composition. It is more preferable that the content is 20% by mass or less, and it is even more preferable that the content is 20% by mass or less.

A solvent represented by formula (5), a solvent represented by formula (6), a solvent represented by formula (7), a solvent represented by formula (8), a solvent represented by formula (9), Among the solvent represented by the formula (10) and the solvent represented by the formula (11), the solvent represented by the formula (5), the solvent represented by the formula (6), and the solvent represented by the formula (7) a solvent represented by the formula (8), or a solvent represented by the formula (9)" is preferable, and "a solvent represented by the formula (5), a solvent represented by the formula (6) , or a solvent represented by formula (7)” is more preferable. As a result, a non-aqueous adhesive composition that exhibits the above effects more effectively is obtained. In particular, the resin A containing the monomer (a) as a configuration is easily dissolved in the alkylamide solvent represented by the formula (5), and by containing a predetermined amount of the alkylamide solvent, the non-aqueous adhesive composition The ejection stability from the nozzle is improved. In particular, when the non-aqueous adhesive composition according to the present embodiment is used as an inkjet non-aqueous adhesive composition for inkjet ejection, it is necessary to effectively improve the ejection stability from the ink head nozzle. becomes possible. Two or more of these organic solvents may be mixed.

In addition, these solvents (glycol ether solvents, solvents represented by formula (5), solvents represented by formula (6), solvents represented by formula (7), solvents represented by formula (8) , the solvent represented by the formula (9), the solvent represented by the formula (10), and the solvent represented by the formula (11)), it is preferable to combine two or more solvents having different flash points. By containing a solvent with a high flash point (for example, a flash point of 70° C. or higher), a non-aqueous pressure-sensitive adhesive composition having high recovery from cleaning can be obtained. By containing a solvent with a low flash point (for example, a flash point of less than 70° C.), a non-aqueous adhesive composition with high surface drying property on a substrate can be obtained. By containing a solvent with a flash point of 70° C. or higher and a solvent with a flash point of lower than 70° C., it is possible to achieve both high recovery from cleaning and surface drying on the substrate, and the effects of the present invention can be achieved. It becomes a non-aqueous adhesive composition that works particularly effectively.

The non-aqueous adhesive composition according to the present embodiment includes the above glycol ether solvent, the solvent represented by formula (5), the solvent represented by formula (6), and the solvent represented by formula (7). , the solvent represented by the formula (8), the solvent represented by the formula (9), the solvent represented by the formula (10), even if it contains an organic solvent other than the solvent represented by the formula (11) good. Specifically, triethylene glycol butyl ether acetate, ethylene glycol butyl ether acetate, diethylene glycol ethyl ether acetate, diethylene glycol methyl ether acetate, diethylene glycol butyl ether acetate, propylene glycol methyl ether acetate, dipropylene glycol methyl ether acetate, 1-methoxy-2-propyl Acetate-based solvents such as acetate, 3-methoxybutyl acetate, 2-methylbutyl acetate, 3-methoxybutyl ether acetate, cyclohexyl acetate; methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec -Butyl alcohol, tert-butyl alcohol, isobutyl alcohol, alkyl alcohols having 1 to 5 carbon atoms such as n-pentanol; 3-methoxy-3-methyl-1-butanol, 3-methoxy-1-propanol, 1- Monohydric alcohol solvents such as methoxy-2-propanol and 3-methoxy-n-butanol; acetone, diacetone alcohol, methyl ethyl ketone, methyl-n-propyl ketone, methyl isopropyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone , methyl-n-amyl ketone, methylhexyl ketone, methyl isoamyl ketone, diethyl ketone, ethyl-n-propyl ketone, ethyl isopropyl ketone, ethyl-n-butyl ketone, ethyl isobutyl ketone, di-n-propyl ketone, diisobutyl ketone, cyclo ketones or ketoalcohols such as pentanone, cyclohexanone, methylcyclohexanone, isophorone, acetylketone; ethers such as tetrahydrofuran and dioxane; oxyethylene or oxypropylene copolymers such as polyethylene glycol and polypropylene glycol; ethylene glycol, propylene glycol, Diethylene glycol, dipropylene glycol, 1,3-propanediol, isobutylene glycol, triethylene glycol, tripropylene glycol, tetraethylene glycol, 1,3-propanediol, 2-methyl-1,2-propanediol, 2-methyl- 1,2-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,2-hexanediol, 1,5-pentanediol, 1 ,6-hexanediol, 2-methyl-2,4-pentanediol, 3-methyl-1,3-butanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol, etc. diols; glycerin, trimethylolethane, trimethylolpropane, triols such as 1,2,6-hexanetriol: tetrahydric alcohols such as mesoerythritol and pentaerythritol, monoethanolamine, diethanolamine, triethanolamine, N -Alkanolamines such as methylethanolamine, N-ethylethanolamine, N-butylethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-butyldiethanolamine; methyl acetate, ethyl acetate, -n-propyl acetate, acetic acid Acetate esters such as isopropyl, n-butyl acetate, isobutyl acetate, hexyl acetate, and octyl acetate; Saturated hydrocarbons such as hexane, isohexane, n-nonane, isononane, dodecane and isododecane; unsaturated hydrocarbons such as 1-hexene, 1-heptene and 1-octene; cyclohexene, cycloheptene, cyclooctene, 1,1, cyclic unsaturated hydrocarbons such as 3,5,7-cyclooctatetraene and cyclododecene; aromatic hydrocarbons such as benzene, toluene and xylene; N-methylmorpholine, N-ethylmorpholine, N-formylmorpholine and the like; morpholines, terpene solvents; dimethyl oxalate, diethyl oxalate, dimethyl malonate, diethyl malonate, dipropyl malonate, dimethyl succinate, diethyl succinate, dimethyl glutarate, dibasic acid esters such as diethyl glutarate, etc. It is preferable to select a solvent with an appropriate HLB value according to the resin, dispersant, etc. to be combined.

The content of other organic solvents is not particularly limited, but the lower limit of the content of other organic solvents is preferably in the range of 10% by mass or more in the total amount of the non-aqueous adhesive composition, and 20% by mass or more. and more preferably 30% by mass or more. The upper limit of the content of other organic solvents is preferably in the range of 85% by mass or less, more preferably 80% by mass or less, and 75% by mass or less in the total amount of the non-aqueous adhesive composition. is more preferable.

[Surfactant]
In the non-aqueous adhesive composition according to the present embodiment, the purpose is to suppress volatilization and solidification of the non-aqueous adhesive composition in devices such as nozzles and tubes, and to re-dissolve when solidified. Alternatively, a surfactant may be incorporated for the purpose of lowering the surface tension to improve the wettability with the recording medium (substrate) and for the purpose of improving the abrasion resistance of the coating film.

Examples of surfactants include polyoxyalkylene alkyl ethers such as nonionic P-208, P-210, P-213, E-202S, E-205S, E-215, K-204, K-220, S -207, S-215, A-10R, A-13P, NC-203, NC-207 (manufactured by NOF Corporation), Emulgen 106, 108, 707, 709, A-90, A-60 (Kao ( Co., Ltd.), Floren G-70, D-90, TG-740W (manufactured by Kyoeisha Chemical Co., Ltd.), Poem J-0081HV (manufactured by Riken Vitamin Co., Ltd.), and as aliphatic phosphates, Adekatol NP -620, NP-650, NP-660, NP-675, NP-683, NP-686, Adekacol CS-141E, TS-230E (manufactured by Adeka Co., Ltd.), etc., Solgen 30V, 40, TW-20, TW -80, Noigen CX-100 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), etc., and as a fluorine-based surfactant, it is preferable to use a fluorine-modified polymer. ) and the like, it is preferable to use polyester-modified silicone or polyether-modified silicone as the silicone-based surfactant having a siloxane skeleton. Specific examples of acetylene glycol surfactants such as BYK-UV3500, 3510, 3530, 3570 (all manufactured by BYK-Chemie Japan) include Surfynol (registered trademark) 82, 104, 465, 485, TG (any (also manufactured by Air Products Japan), Olfin (registered trademark) STG, E1010 (both manufactured by Nissin Kagaku Co., Ltd.), and the like. Surfactants are not limited to those described above, and any of anionic, cationic, amphoteric or nonionic surfactants can be used.

Among these, the surfactant preferably contains a surfactant having a siloxane skeleton.

As the surfactant having a siloxane skeleton, it is preferable to use polyester-modified silicone or polyether-modified silicone. Specific examples include BYK-313, 315N, 322, 326, 331, 347, 348, BYK-UV3500 and 3510. , 3530, 3570 (both manufactured by BYK-Chemie Japan) and the like can be used.

The non-aqueous adhesive composition according to the present embodiment may contain a surfactant having a siloxane skeleton and a surfactant different from the surfactant having a siloxane skeleton.

In the non-aqueous adhesive composition according to the present embodiment, when a surfactant is contained, the content of the surfactant is not particularly limited, but the lower limit of the content of the surfactant is It is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.07% by mass or more, based on the total amount of the composition. The upper limit of the surfactant content is preferably 1.0% by mass or less, more preferably 0.9% by mass or less, and 0.8% by mass or less in the total amount of the non-aqueous adhesive composition. is more preferable.

[Color material]
The non-aqueous adhesive composition according to this embodiment may contain a coloring material. The coloring material is not particularly limited, and may be dye-based or pigment-based.

Specific organic pigments include, for example, insoluble azo pigments, soluble azo pigments, derivatives from dyes, phthalocyanine-based organic pigments, quinacridone-based organic pigments, perylene-based organic pigments, perinone-based organic pigments, azomethine-based organic pigments, and anthraquinone-based pigments. Organic pigments (anthrone-based organic pigments), xanthene-based organic pigments, diketopyrrolopyrrole-based organic pigments, dioxazine-based organic pigments, nickel azo-based pigments, isoindolinone-based organic pigments, pyranthrone-based organic pigments, thioindigo-based organic pigments, condensed azo organic solid solution pigments such as organic pigments, benzimidazolone organic pigments, quinophthalone organic pigments, isoindoline organic pigments, quinacridone solid solution pigments, perylene solid solution pigments, and other pigments such as lake pigments and carbon black. be done.

When organic pigments are exemplified by color index (C.I.) numbers, C.I. I. Pigment Yellow 1, 2, 3, 12, 13, 14, 16, 17, 20, 24, 73, 74, 75, 83, 93, 95, 97, 98, 109, 110, 114, 117, 120, 125, 128, 129, 130, 137, 138, 139, 147, 148, 150, 151, 153, 154, 155, 166, 168, 180, 185, 213, 214, C.I. I. Pigment Red 5, 7, 9, 12, 48, 49, 52, 53, 57: 1, 97, 112, 122, 123, 146, 149, 150, 168, 177, 180, 184, 192, 202, 206, 208, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 238, 240, 254, 255, 269, 291, C.I. I. Pigment Orange 16, 36, 43, 51, 55, 59, 61, 64, 71, 73, C.I. I. pigment violet 19, 23, 29, 30, 37, 40, 50, C.I. I. Pigment Blue 15, 15:1, 15:3, 15:4, 15:6, 16, 22, 60, 64, C.I. I. Pigment Green 7, 36, 58, 59, 62, 63, C.I. I. Pigment Brown 23, 25, 26, C.I. I. Pigment Black 7 and the like.

Specific examples of dyes that can be used in the non-aqueous adhesive composition according to the present embodiment include azo dyes, benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, cyanine dyes, squarylium dyes, and croconium. dyes, merocyanine dyes, stilbene dyes, diarylmethane dyes, triarylmethane dyes, fluorane dyes, spiropyran dyes, phthalocyanine dyes, indigo dyes such as indigoids, fulgide dyes, nickel complex dyes, and azulene dyes.

Specific examples of inorganic pigments that can be used in the non-aqueous adhesive composition according to the present embodiment include titanium oxide, barium sulfate, calcium carbonate, zinc oxide, barium carbonate, silica, talc, clay, synthetic mica, Alumina, zinc white, lead sulfate, yellow lead, zinc yellow, red iron oxide (iron(III) oxide), cadmium red, ultramarine blue, Prussian blue, chromium oxide green, cobalt green, amber, titanium black, aluminum, titanium, indium, synthetic Iron black, inorganic solid solution pigments and the like can be mentioned.

It is preferable that these coloring materials be appropriately selected according to the base material (recording medium), the type and shape of the solid matter, the function and properties of the recorded matter, and the like.

Among these coloring materials, it is preferable to contain a black pigment or a white pigment from the viewpoint of improving the concealability of the adhesive layer formed from the non-aqueous adhesive composition. In particular, when the non-aqueous adhesive composition according to the present embodiment is used to transfer a metal foil or fix a metal powder to a substrate, the inclusion of a black pigment improves the brightness of the metal foil (or metal powder). becomes possible.

The average dispersed particle diameter of the pigment that can be contained in the non-aqueous adhesive composition according to the embodiment is not particularly limited as long as the desired color development is possible. Although it varies depending on the type of pigment used, the volume average particle diameter is preferably 5 nm or more, preferably 20 nm or more, from the viewpoint of good dispersibility and dispersion stability of the pigment and obtaining sufficient coloring power. is more preferable, and 30 nm or more is even more preferable. When the volume average particle size is at least the above lower limit, the light resistance of the non-aqueous adhesive composition can be improved. The volume average particle size is preferably 500 nm or less, more preferably 400 nm or less, and even more preferably 350 nm or less. In the non-aqueous adhesive composition according to the present embodiment, the volume-average particle size of the pigment is equal to or less than the above upper limit, so that the inkjet ejection stability can be made extremely high. In the present embodiment, the volume-average particle size of the pigment is measured at 25° C. using a particle size distribution measuring device (particle size analyzer NANOTRACWAVE manufactured by Microtrack Bell Co., Ltd.). diameter (D50). In this specification, "volume-based cumulative 50% particle diameter (D50)" means a particle diameter at which the cumulative volume calculated from the smaller diameter side becomes 50%. "Volume-based cumulative 50% particle size (D50)" may also be referred to as "volume average particle size D50" or "median (median) size".

In the non-aqueous adhesive composition according to the present embodiment, when a coloring material (pigment) is contained, the content of the coloring material (pigment) is not particularly limited, but the lower limit of the content of the coloring material (pigment) is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.5% by mass or more, based on the total amount of the non-aqueous adhesive composition. In particular, when a black pigment or white pigment is contained as a coloring material, it is possible to improve the concealability of the adhesive layer. In particular, when a metal foil is transferred or a metal powder is fixed to a substrate with the non-aqueous adhesive composition according to the present embodiment, the black pigment containing 0.01% by mass or more as a coloring material is more It is possible to effectively improve the brightness of the metal foil (or metal powder).

The upper limit of the content of the coloring material (pigment) is preferably 20.0% by mass or less, more preferably 10.0% by mass or less, and 5.0% by mass in the total amount of the non-aqueous adhesive composition. % or less, and even more preferably 1.0 mass % or less. As a result, the content of the resin in the non-aqueous pressure-sensitive adhesive composition is relatively increased in the same viscosity range, so that the fixability of the solid matter to be fixed on the substrate is more effectively improved.

[Pigment Dispersant]
When the non-aqueous adhesive composition according to the present embodiment contains a coloring material (pigment), a pigment dispersant may be used. Any pigment dispersant used in non-aqueous ink compositions can be used as the dispersant. A polymer dispersant may be used as the pigment dispersant. Such a dispersant has a polyester-based, polyacrylic-based, polyurethane-based, polyamine-based, polycaprolactone-based, or the like main chain, and has a polar group such as an amino group, a carboxyl group, a sulfone group, or a hydroxyl group as a side chain. is. For polyacrylic dispersants, for example, Disperbyk-2000, 2001, 2008, 2009, 2010, 2020, 2020N, 2022, 2025, 2050, 2070, 2095, 2150, 2151, 2155, 2163, 2164, BYKJET-9130, 9131 , 9132, 9133, 9151 (manufactured by Vic Chemie), Efka PX4310, PX4320, PX4330, PA4401, 4402, PA4403, 4570, 7411, 7477, PX4700, PX4701 (manufactured by BASF), TREPLUS D-1200, D-1410, D-1420, MD-1000 (manufactured by Otsuka Chemical Co., Ltd.), Floren DOPA-15BHFS, 17HF, 22, G-700, 900, NC-500, GW-1500 (manufactured by Kyoeisha Chemical Co., Ltd.), and the like are used. Polycaprolactone-based dispersants include, for example, Ajisper PB821, PB822, PB881 (manufactured by Ajinomoto Fine-Techno Co., Ltd.), Hinoact KF-1000, T-6000, T-7000, T-8000, T-8000E, T-9050 ( Kawaken Fine Chemicals Co., Ltd.), Solsperse 20000, 24000, 32000, 32500, 32550, 32600, 33000, 33500, 34000, 35200, 36000, 37500, 39000, 71000, 76400, 76500, 86000, 88000, J10 TEGO Dispers 652, 655, 685, 688, 690 (manufactured by Evonik Japan) and the like are used.好ましい分散剤としては、ＢＹＫＪＥＴ－９１３０、９１３１，９１３２，９１３３，９１５１、ＥｆｋａＰＸ４３１０、ＰＸ４３２０、ＰＸ４３３０、ＰＸ４７００、ＰＸ４７０１、Ｓｏｌｓｐｅｒｓｅ２００００、２４０００、３２０００、３３０００、３３５００、３４０００、３５２００、３９０００、７１０００、７６５００、８６０００、 88000, J180, J200, TEGO Dispers 655, 685, 688, 690, etc. are used. These individual or mixtures thereof can be used.

The content of the pigment dispersant is not particularly limited, but the lower limit of the content of the pigment dispersant is preferably 5 parts by mass or more with respect to 100 parts by mass of the pigment in the non-aqueous adhesive composition, It is more preferably 20 parts by mass or more, more preferably 20 parts by mass or more. The upper limit of the content of the pigment dispersant is preferably 150 parts by mass or less, more preferably 125 parts by mass or less, and 100 parts by mass or less with respect to 100 parts by mass of the pigment in the non-aqueous adhesive composition. is more preferable.

[Dispersing aid]
A dispersing aid may be used as necessary in the non-aqueous adhesive composition according to the present embodiment. The dispersing aid is adsorbed on the surface of the coloring material (pigment), and the functional group increases the affinity with the organic solvent and dispersant in the non-aqueous adhesive composition, thereby improving the dispersion stability. As the dispersing aid, a known pigment derivative having a functional group such as an acidic group, a basic group, or a neutral group in the organic pigment residue can be used.

[Other ingredients]
The non-aqueous adhesive composition according to the present embodiment includes light stabilizers such as antioxidants and ultraviolet absorbers, epoxides and the like, polyvalent carboxylic acids, surface conditioners, slip agents, leveling agents (acrylic and silicon system, etc.), antifoaming agents, pH adjusters, bactericides, preservatives, deodorants, charge control agents, wetting agents, and other known additives as optional components. Specific examples of antioxidants include hindered phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, hydrazine-based antioxidants, and the like. Specific examples include BHA (2,3-butyl-4-oxyanisole) and BHT (2,6-di-t-butyl-p-cresol). Moreover, a benzophenone-based compound or a benzotriazole-based compound can be used as the ultraviolet absorber. Specific examples of the epoxidized product include epoxy glyceride, epoxy fatty acid monoester, and epoxy hexahydrophthalate, and specific examples include ADEKA CIZER O-130P and ADEKA CIZER O-180A (manufactured by ADEKA). exemplified. Specific examples of polycarboxylic acids include citric acid and maleic acid.

(Viscosity and surface tension of non-aqueous adhesive composition)
The viscosity of the non-aqueous adhesive composition according to the present embodiment is not particularly limited, and is preferably selected as appropriate according to the discharge method. For example, when the non-aqueous adhesive composition according to the present embodiment is ejected by an inkjet method, the viscosity at 25° C. should be 15.0 mPa·s or less from the viewpoint of inkjet ejection property and ejection stability. is preferred, 13.0 mPa·s is more preferred, and 10.0 mPa·s or less is even more preferred. Further, the viscosity of the non-aqueous adhesive composition according to the present embodiment is preferably 1.0 mPa·s or more, more preferably 2.0 mPa·s or more, and 3.0 mPa·s or more. It is even more preferable to have

In addition, the surface tension of the non-aqueous adhesive composition according to the present embodiment is not particularly limited, and is preferably selected as appropriate according to the discharge method. For example, when the non-aqueous adhesive composition according to the present embodiment is ejected by an inkjet method, the surface tension at 25° C. is It is preferably 20 mN/m or more, more preferably 22 mN/m or more, and even more preferably 24 mN/m or more. Further, the surface tension of the non-aqueous adhesive composition according to the present embodiment is preferably 40 mN/m or less, more preferably 37 mN/m or less, and even more preferably 35 mN/m or less. .

≪2. Method for producing non-aqueous adhesive composition»
The method for producing a non-aqueous adhesive composition according to the present embodiment comprises mixing an organic solvent, a resin, and optionally other components (for example, a surfactant, etc.) using a paint shaker. can be done. At this time, each component may be dispersed with zirconia beads. Moreover, the obtained non-aqueous pressure-sensitive adhesive composition may be adjusted to a desired dissolved oxygen content and dissolved nitrogen content by performing a deaeration treatment or the like as necessary.

At this time, it is preferable to dry the organic solvent in advance. By drying the organic solvent in advance, the amount of water contained in the non-aqueous adhesive composition can be reduced. As a method for drying the organic solvent, for example, a method of spraying an inert gas (e.g., nitrogen gas) dried in an inert gas atmosphere such as nitrogen for a predetermined time, a method of distilling and refining the organic solvent, and water are selected. Examples include a method of allowing the organic solvent to permeate through a semi-permeable membrane that selectively permeates the organic solvent, and a method of selectively adsorbing water mixed in the organic solvent with a water adsorbent that adsorbs water.

≪3. Method for producing recorded matter≫
A method for producing a recorded matter according to the present embodiment is a method for producing a recorded matter in which the non-aqueous adhesive composition described above is ejected from a nozzle. The above-mentioned non-aqueous adhesive composition becomes adhesive at a predetermined temperature by volatilizing the solvent, and the adhesiveness allows the solid material to be fixed to the substrate. Also in the method of manufacturing a recorded matter according to the embodiment, a recorded matter on which a solid matter is fixed can be manufactured. The same applies to a recording method using a non-aqueous adhesive composition, which will be described later.

As a recording method for ejecting from a nozzle, an inkjet method or a dispenser method is preferable, and among these, an inkjet method is particularly preferable. If it is an inkjet method or a dispenser method, it is possible to discharge to a desired position on the surface of the object (base material), so solid objects such as powders and foils can be applied to the desired position on the surface of the object (base material). It can be fixed. Therefore, for example, it is possible to obtain a patterned recorded matter in which a solid object is fixed at a desired position.

In the following, as an example of a method for producing a recorded matter according to the present embodiment, a non-aqueous adhesive composition is ejected onto a substrate by an inkjet method, and a metal foil is transferred (fixed) to the substrate to produce a recorded matter. A manufacturing method will be described. The method for producing a recorded matter of the present invention is not limited to this method. A recorded matter may be produced by fixing a solid substance different from the metal foil to the substrate.

[Step 1]
In this step 1, first, the non-aqueous adhesive composition is discharged onto a substrate by an inkjet method. If it is an inkjet method, it is possible to eject to a desired position on the surface of the object (base material), so it is possible to transfer the metal foil to a desired position on the base material surface. It is also possible to obtain a patterned recorded matter in which a metal foil is fixed at a desired position. In addition, in order to transfer the metal foil to the entire surface of the substrate, the non-aqueous adhesive composition may be discharged onto the entire surface of the substrate.

The above-mentioned non-aqueous adhesive composition may be ejected onto a desired position on the surface of the body (substrate), and a so-called normal inkjet ink composition may also be ejected. For example, by ejecting an ink composition containing colors such as yellow, magenta, cyan, and black, it is also possible to produce recorded matter on which a color image containing metal foil is recorded.

When the above non-aqueous adhesive composition is ejected by an inkjet method, a conventional non-aqueous (sometimes referred to as non-aqueous or oily) ink for inkjet is used as an inkjet recording apparatus used in the inkjet method. An inkjet recording device used for the composition can be used. For example, inkjet printers such as Roland DG VersaArt RE-640 and MasterMind MMP-F13 can be used.

The method of ejecting ink by the inkjet method may be a piezo method using a piezoelectric element or a thermal method using a heating element, and is not particularly limited.

In addition, the inkjet recording device preferably has a heating mechanism. As described later, the substrate surface temperature is controlled by a heating mechanism provided in the inkjet recording apparatus, and the non-aqueous adhesive composition ejected onto the substrate (recording medium) is dried to remove components such as resins. It becomes possible to fix on the material (recording medium). Furthermore, it becomes possible to easily control the temperature at which the resin contained in the non-aqueous adhesive composition has adhesiveness by means of the heating mechanism.

[Step 2]
In this step, the metal foil is transferred to the surface of the substrate coated with the non-aqueous adhesive composition. At this time, it is preferable to heat the non-aqueous adhesive composition so that the non-aqueous adhesive composition reaches a predetermined temperature.

The heating temperature at this time is preferably determined by the glass transition temperature of the resin A contained in the non-aqueous adhesive composition. Specifically, when the heating temperature is _T1 and the glass transition temperature of resin A is _T2 , the difference ( _T1 - _T2 ) between T1 _° C and _T2 °C is 0°C or more and 60°C or less. It is preferable to determine the heating temperature so as to fall within the range of By heating the non-aqueous adhesive composition at such a temperature, the resin A reaches the glass transition temperature, so that the flexibility is improved. can be transferred (fixed) to transfer the metal foil more effectively.

Furthermore, by heating the substrate containing the non-aqueous adhesive composition, it is possible to effectively dry the composition ejected onto the substrate, thereby improving the production speed of recorded matter. effective for When the glass transition temperature _T2 of Resin A is room temperature or lower, it is not necessary to heat the non-aqueous adhesive composition on the substrate.

The lower limit of the difference between T ₁ °C and T ₂ °C (T ₁ -T ₂ ) is preferably 5°C or more, more preferably 10°C or more. The upper limit of the difference between T ₁ °C and T ₂ °C (T ₁ -T ₂ ) is preferably 55°C or less, more preferably 50°C or less.

A method of heating the non-aqueous adhesive composition includes a method of heating a substrate including the non-aqueous adhesive composition by a heating mechanism provided in an inkjet recording apparatus. The heating mechanism provided in the inkjet recording apparatus may be a preheater, a platen heater, an afterheater, or the like, or may be a mechanism for blowing warm air to the composition on the substrate. Also, a plurality of these heating mechanisms may be combined.

When transferring the metal foil to the surface of the substrate with the non-aqueous adhesive composition, for example, a metal foil containing a release paper is prepared, the metal foil is superimposed on the surface of the non-aqueous adhesive composition of the substrate, and the metal is A method of applying a predetermined pressure from the foil side or the base material side for a predetermined period of time and then peeling off the release paper can be used. Alternatively, the metal foil can be effectively fixed to the base material from the base material side or the metal foil side.

A method of applying pressure includes a method of applying pressure from the metal foil side or the base material side with a transfer roll or the like. Although the pressure applied to the metal foil at this time is not particularly limited, it is preferably 10 kPa or more and 800 kPa or less. At this time, the time for applying pressure (crimping time) is not particularly limited, but is preferably 0.1 seconds or more, for example. When applying pressure with a transfer roll or the like, it is preferable to apply pressure to the metal foil while the roller is heated to a predetermined temperature. As a result, the resin on the substrate can be heated more effectively, and the metal foil can be transferred more beautifully. The material of the transfer roll is not particularly limited, and examples thereof include metals (including alloys) and resins (including elastomers).

In addition, when the metal foil is placed on the non-aqueous adhesive composition of the base material, the degree of drying of the non-aqueous adhesive composition is not particularly limited. There is a tendency for the surface condition to deteriorate, such as the occurrence of cracks in the foil. On the other hand, if the non-aqueous adhesive composition is too dry, there is a tendency for uneven transfer to occur on the metal foil. Therefore, when the metal foil is placed on the non-aqueous adhesive composition on the substrate, the non-aqueous adhesive composition on the substrate is almost dry, but not completely dry. preferable. Therefore, for example, it is preferable to overlap the metal foil on the solvent-based non-aqueous adhesive composition of the substrate in a state where the volatilization amount of all the solvents contained in the non-aqueous adhesive composition is 30% or more and 99% or less. For this purpose, for example, after the non-aqueous adhesive composition is discharged onto the surface of the base material, it is preferable to heat it at a predetermined temperature within the range of 1 minute or more and 6 minutes or less.

A recorded matter having a metal foil can be obtained through such steps 1 and 2.

≪4. Recording Method Using Non-Aqueous Adhesive Composition>>
The method for producing a recorded matter using the non-aqueous adhesive composition can also be defined as a recording method. By volatilizing the solvent, the above non-aqueous adhesive composition becomes adhesive at a predetermined temperature, and the adhesiveness allows solid substances such as powders and foils to be fixed to the substrate. Therefore, a recorded matter on which a solid matter is fixed can be obtained also in the recording method according to the present embodiment.

≪5. Set of compositions»
A set of compositions according to the present embodiment includes the above non-aqueous adhesive composition as a first composition, and an ink composition as a second composition. Such a composition set includes, for example, a color ink composition as the second composition, and the non-aqueous adhesive composition is ejected onto the substrate and the color ink composition is ejected. By doing so, it is possible to produce a recorded matter on which a color image containing the metal foil is recorded. In the present specification, the second composition, which is an ink composition, refers to a plurality of ink compositions containing colors such as yellow, magenta, cyan, black, white, and intermediate colors thereof, even if there is only one composition. may be used as a concept including all of them.

At this time, it is preferable that the first composition (non-aqueous adhesive composition) has adhesiveness and the second composition (ink composition) does not have adhesiveness at a predetermined temperature. . As a result, for example, when transferring a solid object such as a metal foil onto a substrate, only the surface of the substrate coated with the first composition (non-aqueous adhesive composition) can be coated with the solid object such as the metal foil. is selectively adhered, and a patterned metal foil is formed by preventing solid objects such as metal foil from adhering to the surface of the substrate on which the second composition (ink composition) is applied. A recording can be produced containing:

For example, the monomer (a ) is 50% by mass or less of the total amount of the monomers constituting the resin A (ink composition). By reducing the proportion of the tacky resin in the second composition (ink composition), the second composition (ink composition) does not have tackiness at a predetermined temperature. A solid object such as a metal foil can be adhered only to the surface of the substrate coated with the composition of No. 1 (non-aqueous adhesive composition). In order to prevent the second composition (ink composition) from having stickiness at a predetermined temperature, the content of a resin having a high glass transition temperature (for example, over 40°C and 120°C or less) is 50% by mass or more. It may be a ratio of

Since the first composition (non-aqueous adhesive composition) is a composition that does not intentionally contain water, this second composition (ink composition) also contains an organic solvent and does not contain water. It is preferably a non-aqueous (sometimes referred to as non-aqueous or oil-based) ink composition that does not contain intentionally.

The type of resin in the second composition (ink composition) can be the same as the resin contained in the non-aqueous adhesive composition described above.

The lower limit of the content of the resin in the second composition (ink composition) is preferably in the range of 1.0% by mass or more based on the total amount of the second composition (ink composition), and 2.0% by mass. It is more preferably contained in the range of 3.0% by mass or more, more preferably in the range of 3.0% by mass or more. The upper limit of the content of the resin in the second composition (ink composition) is preferably in the range of 30.0% by mass or less based on the total amount of the second composition (ink composition), and 20.0% by mass. It is more preferably contained in the range of 15.0% by mass or less, more preferably in the range of 15.0% by mass or less.

As the organic solvent contained in the second composition (ink composition), those contained in conventional non-aqueous ink compositions for inkjet (sometimes referred to as non-aqueous or oil-based ink compositions) are used. Alternatively, for example, an organic solvent contained in the non-aqueous adhesive composition described above may be used.

The second composition (ink composition) may contain a coloring material, for example, the coloring material that may be contained in the non-aqueous adhesive composition described above can be used.

≪6. Device≫
The apparatus according to this embodiment is an apparatus for discharging the non-aqueous adhesive composition from a nozzle onto a substrate. By volatilizing the solvent, the above non-aqueous adhesive composition becomes adhesive at a predetermined temperature, and the adhesiveness allows solid substances such as powders and foils to be fixed to the substrate. Therefore, the apparatus according to the present embodiment can also produce recorded matter on which a solid matter is fixed.

When the above non-aqueous adhesive composition is ejected by an inkjet method, such an apparatus may be an inkjet recording apparatus used for the inkjet method, and the above non-aqueous adhesive composition is ejected by a dispenser method. In that case, a dispenser recording device used for the dispenser method may be used.

These devices preferably have a heating mechanism. A non-aqueous adhesive composition ejected onto a substrate (recording medium) is dried by controlling the surface temperature of the substrate with a heating mechanism to fix components such as a resin onto the substrate (recording medium). becomes possible. Furthermore, it becomes possible to easily control the temperature at which the resin contained in the non-aqueous adhesive composition has adhesiveness by means of the heating mechanism.

≪7. Records≫
Each layer constituting the non-aqueous adhesive composition and the recorded matter produced by the method for producing the recorded matter will be described. In the present specification, the term "recorded matter" includes any adhesive layer formed by ejecting a non-aqueous adhesive composition onto the surface of a substrate (substrate), and is particularly limited. isn't it. The "layer" described later may be formed on the entire surface of the substrate (recording medium), or may be formed on a part of it (patterned). good.

Then, a solid layer is formed on the adhesive layer. By selecting the material of the solid substance described later, it is possible to form a recorded matter having a layer of the solid substance. For example, it is possible to obtain a recorded matter having desired characteristics by using a recorded matter having a layer of a solid material.

[Base material (recording medium)]
The substrate (recording medium) is not particularly limited, and may be a non-absorbent substrate such as a resin substrate or metal plate glass, or an absorbent substrate such as paper or fabric, and the receiving layer may be used. It may be a substrate with a surface coating, such as a substrate provided, and various substrates can be used.

Non-absorbent base materials include polyester-based resin, polypropylene-based synthetic paper, polyolefin-based resin (polypropylene-based resin, polyethylene-based resin, etc.), acrylic-based resin, styrene-based resin, polycarbonate-based resin, ABS resin, and vinyl chloride-based resin. , resin substrates such as polyimide resin, metals, metal foil-coated paper, glass, synthetic rubber, natural rubber, and the like.

Examples of absorbent substrates include dry paper, medium-quality paper, high-quality paper, synthetic paper, cotton, synthetic fiber fabric, silk, hemp, fabric, non-woven fabric, leather, and the like.

Examples of surface-coated substrates include coated paper, art paper, cast paper, lightweight coated paper, and lightly coated paper.

Among these, since the non-aqueous adhesive composition is a non-aqueous adhesive composition that does not intentionally contain water, it is preferable that the surface is mainly made of a resin. Examples of resins include polyvinyl chloride-based polymers, acryl, PET, polycarbonate, PE, and PP. Further, it may be used for a resin base material (so-called resin base material for lamination) on the premise that a film is attached to the recording surface of a recorded matter. In particular, the non-aqueous adhesive composition contains "an alkylamide solvent represented by formula (5), a cyclic amide solvent represented by formula (6), and a lactone solvent represented by formula (7)". When contained, these organic solvents have particularly high permeability to the polyvinyl chloride polymer, and dry quickly on the resin substrate after ejection. When the non-aqueous adhesive composition according to the present embodiment is discharged onto a resin substrate and the metal foil is transferred (fixed) to the resin substrate by the non-aqueous adhesive composition, drying on the resin substrate Since the transfer speed is fast, it is possible to transfer the metal foil particularly cleanly, and the surface shape of the metal foil on the obtained recorded matter is good, and the fineness is also good. Fine fixing is possible. Examples of the substrate (recording medium) whose surface is made of a polyvinyl chloride polymer include polyvinyl chloride substrates (films or sheets).

[Adhesive layer]
The adhesive layer is a layer formed by volatilization of the organic solvent contained in the above-mentioned non-aqueous adhesive composition, and its adhesiveness allows solid substances such as powders and foils to be fixed to the substrate. have a function.

This adhesive layer contains a resin derived from the above non-aqueous adhesive composition, the resin contains a resin A containing the monomer (a) as a configuration, and the content of the resin A is included in the adhesive layer. It is 50% by mass or more in the total amount of the resin. By including the resin A containing the monomer (a) as a constitution in this way, solid substances such as powders and foils can be fixed to the base material.

The adhesive layer may be formed on the entire surface of the base material, or may be patterned on part of the surface of the base material.

[Solid layer]
The layer of solid matter is a layer formed on the surface of the adhesive layer, and is a layer of solid matter such as powder or foil fixed by the adhesive layer.

The solid material is not particularly limited, and may be metal (either a single metal or an alloy, may or may not be a magnetic substance, or may be a semiconductor, etc.), metal compounds. (It may be a metal oxide, metal sulfide, metal nitride, etc., may or may not be a magnetic material, may be a semiconductor, etc.), resin (organic compound polymer or silicone) including, thermoplastic resins, thermosetting resins, elastomers, etc.), glittering materials (pearls, etc.), coloring materials (colored and colorless coloring materials (pigments), fluorescent materials, phosphorescent materials, etc.), Examples include paper, glitter, cloth, hologram, sand, and the like. The shape of the solid material may be powder (which may be spherical, flat, or scale-like) or foil (including film-like ones. The film thickness is not particularly limited, and a uniform It may be a foil with a film thickness or a foil with a non-uniform film thickness.). Moreover, the solid object may be surface-treated.

[Ink composition layer]
The layer of the ink composition is a layer formed by volatilization of the solvent contained in the ink composition, and is a layer that forms a desired image. As the ink composition, for example, colored ink compositions such as yellow, magenta, cyan, and black can be used.

A recorded matter in which a layer of a solid material and a layer of an ink composition are patterned is a recorded matter on which a color image containing a metal foil is recorded. It should be noted that such a layer of the ink composition is not essential for the recorded matter of the present invention.

[Other layers]
The recorded matter according to the present embodiment may further include a layer having a desired function on the medium (recording medium) or on the upper surface of the entire recorded matter. For example, an overcoat layer containing at least one of resin and wax may be formed on the entire upper surface of the recorded matter for the purpose of further imparting abrasion resistance and glossiness to the recorded matter. Further, a layer expressing unevenness (matte surface) may be formed on the upper surface of the entire recorded matter by including a filler or changing the film thickness in units of pixels. In order to impart weather resistance to the recorded matter, a weather resistant layer containing an ultraviolet absorber, a light stabilizer, etc., a glittering layer containing a glittering pigment, or the like may be formed on the upper surface of the entire recorded matter. . It should be noted that such other layers are not essential for the recorded matter of the present invention.

Specific embodiments of the non-aqueous adhesive composition, the recording method, the method for producing the recorded matter, the composition set, and the recorded matter of the present invention have been described above. It is not limited, and can be implemented with appropriate modifications within the scope of the object of the present invention.

For example, in a recorded matter comprising a substrate and an adhesive layer, even a non-aqueous adhesive composition for obtaining a recorded matter such that the recorded matter is attached to another object (substrate) is within the scope of the present invention. include.

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these descriptions.

1. Preparation of resin (1) Acrylic resin In 300 g of diethylene glycol diethyl ether kept at 100 ° C., monomer 1 and monomer 2 (total amount of monomer: 200 g) and t-butylperoxy-2- A mixture with 1.20 g of ethylhexanoate (polymerization initiator) was added dropwise over 1.5 hours. After the dropwise addition was completed, the mixture was allowed to react at 100° C. for 2 hours and then cooled to obtain a synthetic resin solution. Thereafter, the solvent was sufficiently distilled off from this solution to obtain a synthetic resin (acrylic resin).

(2) Vinyl chloride-vinyl acetate copolymer resin In an autoclave equipped with a stirrer, after purging with nitrogen, 100 g of deionized water, 40 g of methanol, monomer 1, monomer 2, monomer 3, and monomers shown in Tables 1 and 2 below were added. 4 (monomer total amount 40.8 g), 0.1 g of hydroxypropyl methylcellulose (suspending agent), 0.026 g of di-2-ethylhexylperoxydicarbonate (polymerization initiator), di-3,5,5- 0.58 g of trimethylhexanol peroxide (polymerization initiator) was charged, and the temperature was raised to 63° C. while stirring in a nitrogen gas atmosphere. A mixture of Monomer 3 and Monomer 4 (total amount of monomers: 59.2 g) was injected under pressure for 6 hours to carry out a copolymerization reaction. When the internal pressure of the autoclave reached 0.3 MPa, the residual pressure was released, the autoclave was cooled, and the resin slurry was taken out, filtered and dried to obtain a vinyl chloride copolymer resin.

Tables 1 and 2 list the ratio of the monomer (a) constituting each synthetic resin and the value of the glass transition temperature (Tg) obtained by the FOX formula.

In the table, the numbers in parentheses mean the proportions (mass ratios) of the monomers during synthesis. In the table, "vinyl chloride resin" means vinyl chloride-vinyl acetate copolymer resin.

2. Preparation of non-aqueous adhesive composition Each organic solvent, resin, surface modifier (surfactant), dispersant, and pigment are mixed in the proportions shown in the table below. An adhesive composition was made. Specifically, each component was dispersed with zirconia beads using a paint shaker to prepare a non-aqueous adhesive composition. The unit is % by mass.

3. Evaluation (1) Foil Transferability Test The non-aqueous adhesive compositions of Examples and Comparative Examples were evaluated for foil transferability. Specifically, the non-aqueous adhesive compositions of Examples and Comparative Examples were applied to a recording medium (polyvinyl chloride film with adhesive (IMAGin JT5829R (manufactured by MACtac Co.) was ejected from the nozzle.The resolution at this time was 720 × 2880 dpi, and the printing pattern was solid at a printing rate of 100%.A separate heater was provided at the bottom of this inkjet printer. , A recording medium was placed thereon, and inkjet ejection was performed while maintaining the substrate surface temperature shown in Tables 3 to 8. The substrate surface temperature was measured using a non-contact radiation thermometer MT7 manufactured by Mother Tool. and measured.

Then, while maintaining the substrate surface temperature shown in Tables 3 to 8, after 3 minutes, the metal foil (Glee foil standard metallic foil No. 3 gold manufactured by Murata Gold Leaf Co., Ltd.) is applied to the non-aqueous adhesive composition ejection surface of the substrate. , and a pressure of 50 kPa was applied to the metal foil for 3 seconds to transfer the metal foil to the surface of the substrate to obtain a recorded matter. Then, the transferability of the metal foil on the surface of the recorded matter was visually confirmed (denoted as "foil transferability" in the table).
Evaluation Criteria Evaluation 5: The foil was transferred to the entire printed surface.
Rating 4: The foil was transferred to almost the entire printed surface.
Evaluation 3: The foil was mostly transferred to the printed surface, but some portions were not transferred.
Evaluation 2: Almost no foil was transferred to the printed surface, but some foil transfer was possible.
Rating 1: The foil did not transfer at all.

(2) Metal foil definition test Transfer film definition was evaluated for the non-aqueous adhesive compositions of Examples and Comparative Examples. Specifically, the non-aqueous adhesive compositions of Examples and Comparative Examples were applied to a recording medium (polyvinyl chloride film with adhesive (IMAGin JT5829R : manufactured by MACtac)) was jetted from a nozzle. The resolution at this time was 720 × 2880 dpi, and a predetermined pattern (a square with a side of 1 cm was arranged in a checkered pattern with a printed portion (printing rate 100% solid) and a non-printed portion). Inkjet ejection was performed from a nozzle at .degree. A separate heater was provided at the bottom of this inkjet printer, a recording medium was placed thereon, and inkjet ejection was performed while maintaining the substrate surface temperature at 50°C.

Then, with the substrate surface temperature maintained at 50 ° C., after 3 minutes, a metal foil (Glee foil standard metallic foil No. 3 gold manufactured by Murata Gold Leaf Co., Ltd.) is superimposed on the non-aqueous adhesive composition ejection surface of the substrate, and the metal foil A pressure of 50 kPa was applied to the substrate for 3 seconds to transfer the metal foil to the surface of the substrate. The edges and corners of the metal foil were visually checked, and the presence or absence of missing foil in the printed portion and the presence or absence of excess foil remaining in the non-printed portion were evaluated (see "metal foil definition" in the table). ).
Evaluation Criteria Evaluation 5: Edges and corners of the foil were clean.
Evaluation 4: The edges of the foil were clean, but the corners were partially chipped or excess foil was observed.
Evaluation 3: The edges of the foil were clean, but the corners were chipped or excess foil was found.
Evaluation 2: A part of the edge of the foil was chipped or excessive foil was observed, and many chipped or excessive foil was observed at the corners.
Evaluation 1: The edges and corners of the foil were chipped off or excess foil was observed.

(3) Metal foil surface shape test The metal foil surface shape was evaluated for the non-aqueous adhesive compositions of Examples and Comparative Examples. Specifically, the surface shape of the metal foil was visually checked for the recorded matter (transferred at a substrate surface temperature of 50° C.) obtained in the above (1) foil transferability test, and the metal foil was checked for cracks. It was confirmed whether there was any deviation (indicated as "surface shape" in the table).
Evaluation Criteria Evaluation 5: No cracks or deviations are observed in the foil.
Evaluation 4: Almost no cracks or deviations can be observed in the foil.
Evaluation 3: Some cracks and deviations were observed in the foil.
Evaluation 2: Cracks and deviations were observed over the entire foil, but within the practically acceptable range.
Evaluation 1: A large number of cracks and deviations were observed throughout the foil.

(4) Metal foil transfer unevenness evaluation test The non-aqueous adhesive compositions of Examples and Comparative Examples were evaluated for metal foil transfer unevenness. Specifically, the recorded matter (transferred at a base material surface temperature of 50 ° C.) obtained in the above (1) foil transferability test was checked for uneven transfer of the metal foil (microscopic chipping on the foil surface). It was confirmed visually (denoted as "transfer unevenness" in the table).
Evaluation Criteria Evaluation 5: There is no minute chipping on the foil surface.
Evaluation 4: Less than 10 micro-chips on the foil surface.
Evaluation 3: 10 or more and less than 20 minute defects on the foil surface.
Evaluation 2: 20 or more and less than 30 minute defects on the foil surface.
Evaluation 1: 30 or more minute defects on the foil surface.

(5) Metal Foil Peeling Resistance Evaluation Test The non-aqueous adhesive compositions of Examples and Comparative Examples were evaluated for metal foil abrasion resistance. Specifically, the recorded matter obtained in the above (1) foil transferability test (transferred at a substrate surface temperature of 50 ° C.) was left for 12 hours under conditions of a temperature of 25 ° C. and a humidity of 50%. Adhesive tape (CELLOTAPE CT-18 manufactured by Nichiban Co., Ltd.) was adhered to the surface of the foil, and the presence or absence of peeling of the surface of the metal foil was visually confirmed when the tape was peeled off. ).
Evaluation Criteria Evaluation 5: Peeling does not occur.
Evaluation 4: Although peeling is slightly observed, it is generally within the allowable range.
Evaluation 3: The area of the release surface is less than a quarter of the surface to which the adhesive tape is adhered.
Evaluation 2: The area of the release surface is less than half of the surface to which the adhesive tape is adhered.
Evaluation 1: The area of the release surface is 1/2 or more of the surface to which the pressure-sensitive adhesive tape is adhered.

(6) Metal Foil Abrasion Resistance Evaluation Test The metal foil abrasion resistance of the non-aqueous adhesive compositions of Examples and Comparative Examples was evaluated. Specifically, the recorded matter obtained in the above (1) foil transferability test (transferred at a substrate surface temperature of 50 ° C.) was left for 12 hours under conditions of a temperature of 25 ° C. and a humidity of 50%. The surface of the foil was rubbed with a dry cloth (Kanakin No. 3) with a load of 500 g, and the peeling of the metal foil surface and the adhesion of the foil to the cloth surface were visually confirmed (indicated as "metal foil abrasion resistance" in the table). ).
Evaluation Criteria Evaluation 5: Neither peeling of the foil surface nor adhesion of the foil to the cloth surface is confirmed even after 50 reciprocating rubbings.
Evaluation 4: When rubbed 50 times back and forth, no peeling of the foil surface was observed, but slight adherence of the foil to the cloth surface was confirmed.
Evaluation 3: Peeling of the foil surface was observed when the fabric was rubbed back and forth 50 times, and adhesion of the foil to the cloth surface was confirmed.
Evaluation 2: When rubbed back and forth 30 times, peeling of the foil surface was observed, and adhesion of the foil to the cloth surface was confirmed.
Evaluation 1: When rubbed back and forth 20 times, peeling of the foil surface was observed, and adhesion of the foil to the cloth surface was confirmed.

(7) Ejectability Evaluation Test Ejectability was evaluated for the non-aqueous adhesive compositions of Examples and Comparative Examples. Specifically, the non-aqueous adhesive compositions of Examples and Comparative Examples were applied to a recording medium (polyvinyl chloride film with adhesive (IMAGin JT5829R : manufactured by MACtac)), solid and fine lines are printed by continuous printing at a resolution of 720 x 2880 dpi at a substrate surface temperature of 50 ° C., and the presence or absence of dot missing, flight bending, and scattering of the non-aqueous adhesive composition is visually checked. Observation was made and the number of occurrences was counted (denoted as "dischargeability" in the table).
Evaluation Criteria Evaluation 5: Fine lines are correctly reproduced.
Evaluation 4: Fine lines are generally correctly reproduced.
Evaluation 3: A slight bend is observed in the thin wire.
Evaluation 2: The landing position is displaced and bending is observed.
Evaluation 1: The displacement of the landing position is severe, and fine lines cannot be reproduced.

As can be seen from the above table, a non-aqueous adhesive composition containing a resin containing a specific monomer in a predetermined ratio can be inkjet-discharged onto a substrate from a nozzle, and a metal foil can be used as a substrate. It turns out that it can be transcribed to . From this, if the non-aqueous adhesive composition of the present invention is not limited to the inkjet method, it can be discharged by a method of discharging onto a substrate from a nozzle, and is not limited to the transfer of a metal foil. can be fixed to the substrate.

In particular, in the non-aqueous adhesive compositions of Examples 1 to 6 in which the content ratio of the resin A was changed, the content of the resin A of Examples 1 to 5 contained in the range of 50% by mass or more in the total amount of the resin Compared with the non-aqueous adhesive composition of Example 6, the non-aqueous adhesive composition had good transfer film definition.

Further, in the non-aqueous adhesive compositions of Examples 1, 7 to 17, and 56 to 59 in which the type of resin was changed, Examples 1, 8 to 17, in which the glass transition temperature of Resin A was −50° C. or higher, The non-aqueous adhesive compositions Nos. 56 to 59 were superior to the non-aqueous adhesive composition of Example 7 in transfer film peel resistance and transfer film abrasion resistance.

Furthermore, in the non-aqueous adhesive compositions of Examples 1 and 18 to 22 in which the resin content was changed, the resin content was 5% by mass or more of the total amount of the non-aqueous adhesive composition Examples containing The non-aqueous adhesive compositions of 1 and 19 to 22 are superior to the non-aqueous adhesive composition of Example 18 in terms of foil transferability, transfer film definition, transfer film surface shape, transfer film peel resistance, transfer The abrasion resistance of the film was good. In addition, the non-aqueous adhesive compositions of Examples 1 and 18 to 21 containing the resin content in the range of 20.0% by mass or less in the total amount of the non-aqueous adhesive composition are the non-aqueous adhesive compositions of Example 22. The jettability was also good compared to the composition.

Furthermore, γ-butyrolactone contained in the non-aqueous adhesive composition of Example 1 was used as a solvent represented by formula (5) (alkylamide solvent), a solvent represented by formula (6) (cyclic amide solvent ) and (7) (lactone-based solvents other than γ-butyrolactone) in the non-aqueous adhesive compositions of Examples 34 to 41, the same as the non-aqueous adhesive composition in Example 1. It was a composition exhibiting the effects of the present invention.

On the other hand, the non-aqueous adhesive compositions of Comparative Examples 1 to 4, in which the ratio of the monomer (a) is not 50% by mass or more in the total amount of the monomers constituting the resin A, could not transfer the foil at all in the foil transfer test, The non-aqueous pressure-sensitive adhesive composition does not exhibit the effects of the present invention. In the foil transfer test, the non-aqueous adhesive compositions of Comparative Examples 1 to 4 could not be transferred at all, so other tests other than "dischargeability" were not evaluated.

Claims

A non-aqueous adhesive composition ejected from a nozzle,
including an organic solvent and a resin,
The resin contains a resin A containing the following monomer (a) as a configuration,
The proportion of the monomer (a) constituting the resin A is 50% by mass or more in the total amount of the monomers constituting the resin A. Non-aqueous adhesive composition.

(In formula (1), Ry represents a hydrogen group or an optionally branched hydrocarbon group having 1 to 12 carbon atoms. When Ry is a hydrogen group, Rx may be branched monocyclic represents a hydrocarbon group having 1 to 18 carbon atoms which may be branched, and when Ry is a hydrocarbon group having 1 to 12 carbon atoms which may be branched, Rx is an optionally branched hydrocarbon group having 2 to 18 carbon atoms. represents a hydrocarbon group.)
The non-aqueous adhesive composition according to claim 1, wherein the content of the resin A is 70% by mass or more in the total amount of resins contained in the non-aqueous adhesive composition.
The non-aqueous adhesive composition according to claim 1 or 2, wherein the proportion of the monomer (a) constituting the resin A is 70% by mass or more in the total amount of the monomers constituting the resin A.
4. Any one of claims 1 to 3, wherein the monomer (a) constituting the resin A contains at least one selected from the group consisting of methyl acrylate, cyclohexyl acrylate, n-butyl methacrylate, and 2-ethylhexyl methacrylate. Non-aqueous adhesive composition according to.
The non-aqueous adhesive composition according to any one of claims 1 to 4, wherein the content of the resin contained in the non-aqueous adhesive composition is 1% by mass or more and 30% by mass or less in the total amount of the non-aqueous adhesive composition. thing.
The non-aqueous adhesive composition according to any one of claims 1 to 5, wherein the resin A has a weight average molecular weight Mw of 10,000 or more and 60,000 or less.
The non-aqueous adhesive composition according to any one of claims 1 to 6, wherein the organic solvent contains a glycol ether solvent represented by the following formula (2).
R a —(—OR b ) n —OR c (2)
(In formula (2), R a and R c are each independently hydrogen or an optionally branched alkyl group having 1 to 8 carbon atoms, and R b is a branched alkyl group having 1 to 4 carbon atoms. (n represents an integer of 1 or more and 6 or less).
The non-aqueous adhesive composition according to claim 7, wherein the glycol ether-based solvent contains a glycol ether monoalkyl represented by the following formula (3).
R d —(—OR e ) n —OH (3)
(In Formula (3), R d is an alkyl group having 1 to 8 carbon atoms and may be branched, and R e represents an alkylene group having 1 to 4 carbon atoms and may be branched. n represents an integer of 1 or more and 6 or less.)
The non-aqueous adhesive composition according to claim 7 or 8, wherein the glycol ether-based solvent contains a glycol ether dialkyl represented by the following formula (4).
R f —(—OR g ) n —OR h (4)
(In Formula (4), R f and R h are each independently an optionally branched alkyl group having 1 to 8 carbon atoms, and R g is an optionally branched alkyl group having 1 to 4 carbon atoms. represents a good alkylene group, and n represents an integer of 1 or more and 6 or less.)
The non-aqueous adhesive composition according to any one of claims 1 to 9, wherein the organic solvent contains a solvent represented by general formula (5).

(In Formula (5), R 1 is hydrogen or an alkyl group having 1 to 4 carbon atoms, and R 2 and R 3 each independently represent hydrogen or an alkyl group having 1 to 4 carbon atoms. )
The non-aqueous adhesive composition according to any one of claims 1 to 10, wherein the organic solvent contains a solvent represented by general formula (6).

(In formula (6), R 4 is an alkylene group having 3 to 5 carbon atoms, and R 5 represents hydrogen, an alkyl group having 1 to 4 carbon atoms, or an unsaturated hydrocarbon group.)
The non-aqueous adhesive composition according to any one of claims 1 to 11, wherein the organic solvent contains a solvent represented by general formula (7).

(In formula (7), R6 is an alkylene group having 3 to 5 carbon atoms, and R7 represents hydrogen or an alkyl group having 1 to 4 carbon atoms.)
The non-aqueous adhesive composition according to any one of claims 1 to 12, wherein the organic solvent contains a solvent represented by general formula (8).

(In formula (8), R 8 is hydrogen or an alkyl group having 1 to 4 carbon atoms, and R 9 represents an alkylene group having 1 to 3 carbon atoms.)
The non-aqueous adhesive composition according to any one of claims 1 to 13, wherein the organic solvent contains a solvent represented by general formula (9).

(In formula (9), R 10 , R 11 and R 12 are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms, and R 13 represents an alkylene group having 1 to 4 carbon atoms. .)
The non-aqueous adhesive composition according to any one of claims 1 to 14, wherein the viscosity at 25°C is 1.0 mPa·s or more and 15.0 mPa·s or less.
The non-aqueous adhesive composition according to any one of claims 1 to 15, which has a surface tension of 20 mN/m or more and 40 mN/m or less at 25°C.
17. The non-aqueous adhesive composition according to any one of claims 1 to 16, which is ejected from a nozzle onto a substrate and adheres the solid matter thereon, thereby fixing the solid matter on the substrate.
the solid object is a metal foil,
18. The non-aqueous adhesive composition according to claim 17, which fixes the metal foil to the substrate.
Ejected by an inkjet method by an inkjet recording device,
19. The non-aqueous adhesive composition according to any one of claims 1 to 18, which is installed in the inkjet recording device.
A recording method, comprising discharging the non-aqueous adhesive composition according to any one of claims 1 to 19 onto a substrate.
A method for producing a recorded matter, comprising the step of ejecting the non-aqueous adhesive composition according to any one of claims 1 to 19 onto a substrate.
22. The method for producing a recorded matter according to claim 21, further comprising fixing a solid matter on the surface of the non-aqueous adhesive composition discharged onto the substrate.
23. The method of producing a recorded matter according to claim 22, wherein in the step of fixing the solid matter, the solid matter is fixed to the surface of the non-aqueous adhesive composition while heating.
As the first composition, comprising the non-aqueous adhesive composition according to any one of claims 1 to 19,
A set of compositions comprising an ink composition as a second composition.
The ink composition, which is the second composition,
including an organic solvent and a resin,
The resin may contain a resin A containing the following monomer (a) as a configuration,
25. The composition set according to claim 24, wherein the proportion of the monomer (a) constituting the resin A is 50% by mass or less in the total amount of the monomers constituting the resin A.

(In formula (1), Ry represents a hydrogen group or an optionally branched hydrocarbon group having 1 to 12 carbon atoms. When Ry is a hydrogen group, Rx may be branched monocyclic represents a hydrocarbon group having 1 to 18 carbon atoms which may be branched, and when Ry is a hydrocarbon group having 1 to 12 carbon atoms which may be branched, Rx is an optionally branched hydrocarbon group having 2 to 18 carbon atoms. represents a hydrocarbon group.)
An apparatus for discharging the non-aqueous adhesive composition according to any one of claims 1 to 19 onto a substrate.
a substrate;
an adhesive layer formed on the substrate;
with
The adhesive layer contains a resin,
The resin contains a resin A containing the following monomer (a) as a configuration,
A recorded matter, wherein the content of the resin A is 50% by mass or more in the total amount of the resin contained in the adhesive layer.

(In formula (1), Ry represents a hydrogen group or an optionally branched hydrocarbon group having 1 to 12 carbon atoms. When Ry is a hydrogen group, Rx may be branched monocyclic represents a hydrocarbon group having 1 to 18 carbon atoms which may be branched, and when Ry is a hydrocarbon group having 1 to 12 carbon atoms which may be branched, Rx is an optionally branched hydrocarbon group having 2 to 18 carbon atoms. represents a hydrocarbon group.)
28. The recorded matter according to claim 27, further comprising a solid matter on said adhesive layer.