Film binder, resin composition, and laminate

Abstract

To provide a film binder containing a polyester resin that can achieve both excellent fluidity and excellent adhesion, an active energy ray curable resin composition, and a laminate. [Solution] A film binder comprising a polyester resin containing sulfur atoms and / or nitrogen atoms is used. More specifically, as the polyester resin, a reaction product of a carboxylic acid compound and a compound (A) containing sulfur atoms and / or nitrogen atoms in its molecule and containing a hydroxyl group is used. Preferably, it is a polyester resin having a thioether group.

Description

Technical Field

[0001] The present invention relates to a film binder, a resin composition, and a laminate, and particularly to a binder suitable for forming a printing ink film using a printing plate.

Background Art

[0002] For printing inks using a printing plate, such as flexographic inks, a polyester resin is used as a binder. Conventionally used polyester resins are, for example, polyester resins having an ester group and an acrylic group, and such resins are widely used in printing inks to exhibit high durability and excellent printing quality (Patent Documents 1 and 2). However, there are also points that need to be improved in conventional polyester resins for specific applications. For example, thixotropy may increase due to compatibility with pigments and monomers, and improvement in fluidity is required. Therefore, there is a demand for a new polyester resin having a dispersing function and capable of improving fluidity.

[0003] On the other hand, while the active energy ray-curable composition has the characteristic of instant curing by photopolymerization, it has been difficult to achieve compatibility with substrates to be coated or printed, particularly with olefin-based substrates such as polyethylene and polypropylene having low polarity. That is, as the pursuit of instant curing progresses, volume shrinkage occurs in the cured film of the ink, or the flexibility of the film is impaired, resulting in a significant decrease in adhesion to the substrate. Therefore, there is a demand for a material that improves the adhesion of the active energy ray-curable composition to various substrates.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Summary of the Invention

[0005] The object of the present invention is to provide a film binder, an active energy ray curable resin composition, and a laminate that contain a polyester resin capable of achieving both excellent fluidity and excellent adhesion. [Means for solving the problem]

[0006] The inventors of the present invention have conducted extensive research to solve the above problems and have found that the above problems can be solved by the coating binder described below, thereby completing the present invention.

[0007] In other words, embodiments of the present invention relate to the following. However, the present invention is not limited to the following embodiments and includes various embodiments. <1> A coating binder comprising a polyester resin containing sulfur atoms and / or nitrogen atoms. <2> The polyester resin has a thioether group. <1> The coating binder described. <3> The polyester resin is a reaction product of a carboxylic acid compound and a compound (A) that contains a sulfur atom and / or a nitrogen atom in its molecule and also contains a hydroxyl group, as described above. <1> or <2> The described coating binder. <4> The total content of the structure derived from compound (A) in the polyester resin is 0.1 to 50% by mass, as described above. <3> The described coating binder. <5> The carboxylic acid compound is rosin acid and / or modified rosin acid, as described above. <3> or <4> The coating binder described. <6> The modified rosinic acid is one or more selected from rosinic acid and an α,β-unsaturated carboxylic acid or its acid anhydride, hydrogenated rosin, and disproportionated rosin, as described above. <5> The coating binder described. <7> Compound (A) containing a sulfur atom and / or a nitrogen atom and a hydroxyl group in its molecule is the same as compound (A1) containing a sulfur atom and a hydroxyl group in its molecule. <3> ~ <6> Any of the listed coating binders. <8> The above includes a compound (A1) containing a sulfur atom and a hydroxyl group in its molecule, which is represented by the following general formula (1). <7> The coating binder described. RS-R'-OH (1) (In general formula (1), R represents a monovalent organic residue, and R' represents a divalent organic residue.) <9> the above <1> ~ <8> An active energy ray curable resin composition comprising a film binder described in any of the above and a (meth)acrylate compound. <10> The above is a flexographic ink. <9> The described active energy ray curable resin composition. <11> The base material and the above <9> A laminate having a cured product of the active energy ray curable resin composition described above. [Effects of the Invention]

[0008] The present invention provides a film binder containing a polyester resin that can achieve both excellent fluidity and excellent adhesion, an active energy ray curable resin composition, and a laminate. [Modes for carrying out the invention]

[0009] The embodiments for carrying out the present invention will be described in detail below. However, the present invention is not limited to the following embodiments and can be implemented in various ways within the scope of its gist.

[0010] <Coating Binder> This invention relates to a film binder. A film binder is a material that acts as a binder for a film when a film is formed. A resin composition, which is a film-forming material containing a film binder, becomes a film when printed or coated.

[0011] <Polyester resin> The film binder of the present invention comprises a polyester resin containing sulfur atoms and / or nitrogen atoms. The inclusion of a polyester resin containing sulfur atoms and / or nitrogen atoms improves the fluidity of the film binder and the fluidity of the composition containing the film binder. This improvement is particularly noticeable when the composition contains particles such as pigments. Furthermore, the adhesion of the composition containing the film binder to the substrate is also improved. This is presumed to be largely due to the electron-donating properties of the lone pairs of electrons possessed by the sulfur atoms and / or nitrogen atoms in the structure. Specifically, it is presumed that the electron-donating lone pairs of electrons interact with the surface structure of particles such as pigments and various substituents, improving particle dispersibility and thus improving fluidity. It is also presumed that the improvement in fluidity due to a reduction in entanglement between polyester resins and the improvement in adhesion due to interaction with substituents on the substrate surface occur concurrently. Furthermore, when comparing polyester resins containing sulfur atoms with polyester resins containing nitrogen atoms, the sulfur-containing polyester resin exhibits superior performance in both fluidity and adhesion. This is presumed to be because the effect of the lone pairs of electrons is greater on sulfur atoms, which have two lone pairs of electrons in the third period, compared to nitrogen atoms, which have one lone pair of electrons in the second period.

[0012] Polyester resin is a dehydration condensation reaction product of a carboxylic acid compound and a compound containing hydroxyl groups. The carboxylic acid compound and the compound containing hydroxyl groups each have multiple carboxyl groups and / or hydroxyl groups, which together form the resin. These carboxylic acid compounds and compounds containing hydroxyl groups can be used individually or in combination of two or more types.

[0013] The polyester resin used in the present invention is characterized by containing sulfur atoms and / or nitrogen atoms. That is, at least one of the raw materials, a carboxylic acid compound and a compound containing a hydroxyl group, contains sulfur atoms and / or nitrogen atoms, thereby resulting in a polyester resin containing sulfur atoms and / or nitrogen atoms.

[0014] The sulfur atom and / or nitrogen atom contained in the polyester resin preferably exists as an atom constituting the polyester main chain. Further, it preferably exists inside the main chain rather than at the end of the main chain. In the case of a sulfur atom, it is preferably a thioether group, and in the case of a nitrogen atom, it is preferably a secondary amino group or a tertiary amino group.

[0015] A preferred form of the polyester resin used in the present invention is a reaction product of a carboxylic acid compound and a compound (A) containing a sulfur atom and / or a nitrogen atom and a hydroxyl group in the molecule. A more preferred form is a reaction product in which the carboxylic acid compound is a polycarboxylic acid and the compound (A) is a polyol.

[0016] The total content of the structure derived from the compound (A) contained in the polyester resin is preferably 0.1 to 50% by mass. More preferably, it is preferably 0.2 to 40% by mass. If it is less than 0.1% by mass, the effects of the present invention may not be obtained. Note that the content of the structure derived from the compound (A) contained in the polyester resin is regarded as the same as the raw material solid content charging ratio during the synthesis of the polyester resin.

[0017] <Carboxylic acid compound> The carboxylic acid compound that can be used in the present invention is not particularly limited as long as it is a compound having a carboxyl group in the molecule. A monobasic acid having one carboxyl group in the molecule, a polybasic acid having two or more carboxyl groups in the molecule, or its acid anhydride, etc. can be used.

[0018] Specific examples of the monobasic acid include saturated fatty acids such as rosin acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachidic acid, and behenic acid. Unsaturated fatty acids such as crotonic acid, lindelic acid, tsuji acid, myristoleic acid, palmitoleic acid, undecylenic acid, oleic acid, elaidic acid, gadleic acid, gondoic acid, cetoleic acid, erucic acid, brassidic acid, linolelaidic acid, linolenic acid, and arachidonic acid, Aromatic monobasic acids such as benzoic acid, methyl benzoic acid, tertiary butyl benzoic acid, naphthoic acid, orthobenzoyl benzoic acid, Examples include compounds having a conjugated double bond but not having a cyclic diterpene skeleton, such as conjugated linoleic acid, eleostearic acid, parinaric acid, calendic acid, etc.

[0019] Specific examples of polybasic acids include 1,2,3,6 - tetrahydrophthalic acid, 3 - methyl - 1,2,3,6 - tetrahydrophthalic acid, 4 - methyl - 1,2,3,6 - tetrahydrophthalic acid, 1,2 - cyclohexanedicarboxylic acid, 1,3 - cyclohexanedicarboxylic acid, 1,4 - cyclohexanedicarboxylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, pimelic acid, sebacic acid, azelaic acid, alkenyl succinic acids such as dodecenyl succinic acid, pentadecenyl succinic acid, o - phthalic acid, terephthalic acid, isophthalic acid, trimellitic acid, pyromellitic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, crotonic acid, isocrotonic acid, dihydroagat acid and their acid anhydrides, etc.

[0020] From the viewpoint of achieving both fluidity and adhesion, it is preferable to use rosin acid and / or modified rosin acid (hereinafter, the combined ones are also referred to as rosin acids).

[0021] The rosin acid that can be used in the present invention is a monobasic acid having a cyclic diterpene skeleton, such as rosin acid or an alkali metal salt of the said compound. Specifically, examples include organic acids having a conjugated double bond, such as abietic acid and its conjugated compounds, such as neoabietic acid, palastic acid, and levopimaric acid, and organic acids without a conjugated double bond, such as pimaric acid, isopimaric acid, sandaracopimalic acid, and dehydroabietic acid. Examples of natural resins containing these rosin acids include gum rosin, wood rosin, and tall oil rosin.

[0022] A preferred form of the modified rosin acid that can be used in the present invention is a Diels-Alder addition product of a rosin acid having a conjugated double bond and an α,β-unsaturated carboxylic acid or its acid anhydride. It is preferable that the rosin acid having a conjugated double bond be contained in 40% by mass or more, and more preferably 50% by mass or more, of the total rosin acids. If the organic acid having a conjugated double bond in the rosin acids is less than 40% by mass, the amount of the Diels-Alder addition product with an α,β-unsaturated carboxylic acid or its acid anhydride decreases, and as a result, the pigment dispersibility tends to deteriorate. Furthermore, disproportionated rosin and hydrogenated rosin can also be suitably used, as they reduce the number of conjugated double bonds in rosin acid.

[0023] The amount of rosin acid used to obtain modified rosin acid is preferably 35 to 60% by mass, and more preferably 35 to 50% by mass, based on the total amount of modified rosin acid raw materials. When the amount of rosin acid is 35% by mass or more, the curability of the active energy ray-curable ink containing modified rosin acid tends to be good, and when the amount is 60% by mass or less, the solvent resistance of the active energy ray-curable ink composition tends to be good.

[0024] When using a carboxylic acid compound containing a sulfur atom and / or a nitrogen atom, examples include thiocarboxylic acids, amino acids, or their derivatives.

[0025] <Compounds containing hydroxyl groups> <A compound containing a sulfur atom and / or a nitrogen atom in its molecule and a hydroxyl group> The compounds (A) in the present invention that contain a sulfur atom and / or a nitrogen atom and a hydroxyl group in their molecule include a compound (A1) that contains a sulfur atom and a hydroxyl group in its molecule, and a compound (A2) that contains a nitrogen atom and a hydroxyl group in its molecule (except when it contains a sulfur atom). In the present invention, it is preferable that the compound (A1) contains a sulfur atom and a hydroxyl group in its molecule, as this tends to result in better fluidity and adhesion, as well as better storage stability. As the compound (A1) containing a sulfur atom and a hydroxyl group in its molecule, a compound containing a thioether group and a hydroxyl group is preferred, and for example, a compound represented by the following general formula (1) is preferred.

[0026] RS-R'-OH (1) (In general formula (1), R represents a monovalent organic residue, and R' represents a divalent organic residue.)

[0027] Here, an organic residue refers to an atomic group containing carbon and hydrogen atoms, and may have substituents such as hydroxyl groups. If R or R' has a hydroxyl group, the compound is a polyol.

[0028] Specifically, compounds represented by general formula (1) include, as monohydric alcohols, 2-(ethylthio)ethanol, 2-methylthioethanol, benzylthioethanol, 3-(ethylthio)propanol, 2-(phenylthio)ethanol, etc.; as dihydric alcohols, linear alkylene dihydric alcohols such as 1,2-ethanethiol, 1,2-propanethiol, 1,2-butanethiol, 1,3-propanethiol, 1,4-butanethiol, 1,2-pentanethiol, 1,5-pentanethiol, 1,6-hexanethiol, 2,2'-thiodiethanol, bis(4-hydroxyphenyl) sulfide, 3,6-dithia-1,8-octanediol, etc.; and branched alkylene dihydric alcohols such as 2-methyl-2,4-pentanethiol, 3-methyl-1,5-pentanethiol, 2-methyl-2-propyl-1,3-propanethiol, etc. Examples of cyclic alkylene dihydric alcohols include 1,2-cyclohexanethiol, 1,4-cyclohexanethiol, 1,4-cyclohexanedisulfide, and 1,2-cycloheptanethiol. Furthermore, examples of trivalent or higher alcohols include trimethylolsulfanylpropane, tripentaerythritol thiol, and diglycerin sulfate. Examples of polyether polyols include polyethylene sulfanyl glycol (n=2-20), polypropylene sulfanyl glycol (n=2-20), and polytetramethylene sulfanyl glycol (n=2-20).

[0029] Furthermore, as compounds (A2) containing a nitrogen atom and a hydroxyl group in the molecule, amine compounds having one substituent with a hydroxyl group, such as ethanolamine, propanolamine, and butanolamine, Amine compounds having two substituents with hydroxyl groups, such as diethanolamine, dipropanolamine, and dibutanolamine. Amine compounds having one substituent with a hydroxyl group and one substituent without a hydroxyl group, such as N-methylaminoethanol, N-ethylaminoethanol, N-butylaminoethanol, N-methylaminopropanol, N-ethylaminopropanol, N-butylaminopropanol, N-methylaminobutanol, N-ethylaminobutanol, N-butylaminobutanol, and 2-(2-ethylamino)ethoxyethanol. Amine compounds having one substituent with a hydroxyl group and two substituents without a hydroxyl group, such as N,N-dimethylaminoethanol, N,N-diethylaminoethanol, N,N-dibutylaminoethanol, N,N-dimethylaminopropanol, N,N-diethylaminopropanol, N,N-dibutylaminopropanol, N,N-dimethylaminobutanol, N,N-diethylaminobutanol, N,N-dibutylaminobutanol, and 2-(2-diethylamino)ethoxyethanol. Amine compounds having two substituents with hydroxyl groups and one substituent without a hydroxyl group, such as N-methyldiethanolamine, N-ethyldiethanolamine, N-butyldiethanolamine, N-tert-butyldiethanolamine, N-methyldipropanolamine, N-ethyldipropanolamine, N-butyldipropanolamine, N-tert-butyldipropanolamine, N-methyldibutanolamine, N-ethyldibutanolamine, N-butyldibutanolamine, N-tert-butyldibutanolamine, and N-pentyldibutanolamine. Examples include amine compounds having three substituents with hydroxyl groups, such as trimethanolamine, triethanolamine, and tributanolamine.

[0030] In addition, as the compound (A) in the present invention, which contains a sulfur atom and / or a nitrogen atom and a hydroxyl group in its molecule, compounds containing a hydroxyl group other than (A) below, in which the hydrogen atoms are substituted with alkylthio groups, alkylamino groups, and / or dialkylamino groups, can also be used.

[0031] <Compounds containing hydroxyl groups other than (A)> Compounds containing hydroxyl groups other than (A) that can be used as raw materials for polyester resin include, as dihydric alcohols, linear alkylene dihydric alcohols such as 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,5-pentanediol, 1,6-hexanediol, 1,2-hexanediol, and 1,5-hex Sane diol, 2,5-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,2-octanediol, 1,9-nonanediol, 1,2-decanediol, 1,10-decanediol, 1,12-dodecanediol, 1,2-dodecanediol, 1,14-tetradecanediol, 1,2-tetradecanediol, 1,16-hexadecanediol, 1,2-hexadecanediol, etc. Branched alkylene dihydric alcohols such as 2-methyl-2,4-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-2-propyl-1,3-propanediol, 2,4-dimethyl-2,4-dimethylpentanediol, 2,2-diethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, dimethyloloctane, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 2-methyl-1,8-octanediol, 2-butyl-2-ethyl-1,3-propanediol, and 2,4-diethyl-1,5-pentanediol are examples of branched alkylene dihydric alcohols. Examples of cyclic alkylene dihydric alcohols include 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,2-cycloheptanediol, tricyclodecanedimethanol, hydrogenated catechol, hydrogenated resorcinol, and hydrogenated hydroquinone. Furthermore, examples include polyether polyols such as polyethylene glycol (n=2~20), polypropylene glycol (n=2~20), and polytetramethylene glycol (n=2~20), as well as polyester polyols.

[0032] Furthermore, examples of trivalent or higher alcohols include glycerin, trimethylolpropane, pentaerythritol, 1,2,6-hexanetriol, 3-methylpentane-1,3,5-triol, hydroxymethylhexanediol, trimethyloloctane, diglycerin, ditrimethylolpropane, dipentaerythritol, sorbitol, inositol, and tripentaerythritol.

[0033] <Synthesis of polyester resin> Polyester resins are synthesized by known synthesis methods. The polyester resin is a reaction product of the carboxylic acid compound and the compound containing a hydroxyl group. Since the same product can ultimately be obtained through a transesterification reaction, even if a carboxylic acid compound containing a carboxyl group, an acid anhydride group, or a carboxylic acid ester is used as a raw material, in this invention, the reaction product is defined as a reaction product of the carboxylic acid compound and the compound containing a hydroxyl group.

[0034] <Weight-average molecular weight of polyester resin> The polyester resin of the present invention preferably has a weight-average molecular weight of 800 to 30,000, and more preferably 1,000 to 20,000. A weight-average molecular weight of 1,000 to 2,000 allows for improved adhesion and fluidity. In this invention, the weight-average molecular weight was measured using a gel permeation chromatography (HLC-8320) manufactured by Tosoh Corporation. A calibration curve was prepared using standard polystyrene samples. Tetrahydrofuran was used as the eluent, and three TSKgel SuperHM-M columns (manufactured by Tosoh Corporation) were used. The measurements were performed under conditions of a flow rate of 0.6 mL / min, an injection volume of 10 μL, and a column temperature of 40°C.

[0035] <Active energy ray curable resin composition> The film binder of the present invention is suitably used as a raw material for active energy ray curable resin compositions. The active energy ray-curable resin composition of the present invention, by comprising a (meth)acrylate compound and a polyester resin containing sulfur atoms and / or nitrogen atoms as previously described, provides a composition with excellent fluidity, possesses high film properties characteristic of active energy ray-curable resin compositions, and also exhibits excellent adhesion.

[0036] The active energy ray curable resin composition of the present invention may also contain a binder other than the film binder of the present invention.

[0037] Other binders besides the film binder of the present invention are not particularly limited as long as they have film-forming ability and excellent durability. Specific examples include synthetic resin binders such as diallyl phthalate resin, non-phthalate allyl resin, polyvinyl chloride, poly(meth)acrylic acid ester, epoxy resin, polyester resin, styrene acrylic resin, polyurethane resin, cellulose derivatives (e.g., ethylcellulose, cellulose acetate, nitrocellulose), vinyl chloride-vinyl acetate copolymer, polyamide resin, polyvinyl acetal resin, petroleum resin, alkyd resin, urea resin, and synthetic rubber such as butadiene-acrylonitrile copolymer; natural resin binders such as shellac, rosin, and gum arabic; and inorganic binders such as hydrotalcite and ceramics. Multiple binders may be used.

[0038] The (meth)acrylate compounds used in the present invention include monofunctional (meth)acrylate compounds such as 2-ethylhexyl acrylate, methoxydiethylene glycol acrylate, diethylene glycol monophenyl ether acrylate, tetraethylene glycol monophenyl ether acrylate, and acryloyl morpholine. Difunctional (meth)acrylate compounds such as ethylene glycol diacrylate, polyethylene glycol diacrylate (n=2-20), propylene glycol diacrylate, polypropylene glycol diacrylate (n=2-20), alkylene (C4-C12) glycol diacrylate, alkylene (C4-C12) glycol ethylene oxide adduct (2-20 mol) diacrylate, alkylene (C4-C12) glycol propylene oxide adduct (2-20 mol) diacrylate, hydroxypivalyl hydroxypivalate diacrylate, tricyclodecane dimethylol diacrylate, hydrogenated bisphenol A diacrylate, bisphenol A ethylene oxide adduct (2-20 mol) diacrylate, and hydrogenated bisphenol A propylene oxide adduct (2-20 mol) diacrylate. Trifunctional (meth)acrylate compounds such as glycerin triacrylate, glycerin ethylene oxide adduct (3-30 mol) triacrylate, glycerin propylene oxide adduct (3-30 mol) triacrylate, trimethylolpropane triacrylate, trimethylolpropane ethylene oxide adduct (3-30 mol) triacrylate, and trimethylolpropane propylene oxide adduct (3-30 mol) triacrylate. Tetrafunctional (meth)acrylate compounds such as pentaerythritol tetraacrylate, pentaerythritol ethylene oxide adduct (4-40 mol) tetraacrylate, pentaerythritol propylene oxide adduct (4-40 mol) tetraacrylate, diglycerin tetraacrylate, diglycerin ethylene oxide adduct (4-40 mol) tetraacrylate, diglycerin propylene oxide adduct (4-40 mol) tetraacrylate, ditrimethylolpropane tetraacrylate, ditrimethylolpropane ethylene oxide adduct (4-40 mol) tetraacrylate, and ditrimethylolpropane propylene oxide adduct (4-40 mol) tetraacrylate. Examples include polyfunctional (meth)acrylate compounds such as dipentaerythritol hexaacrylate, dipentaerythritol ethylene oxide adduct (6-60 mol) hexaacrylate, and dipentaerythritol propylene oxide adduct (6-60 mol) hexaacrylate. In addition, urethane (meth)acrylate, polyester (meth)acrylate, epoxy (meth)acrylate, and the like can also be used as (meth)acrylate compounds. The (meth)acrylate compounds exemplified may be used individually or in combination of two or more.

[0039] The active energy ray curable resin composition of the present invention may contain a film binder and components other than (meth)acrylate compounds.

[0040] <Ingredients other than the film binder and (meth)acrylate compounds> In addition to the film binder and (meth)acrylate compound, various additives may be added. Specifically, these include pigments, pigment dispersants, photopolymerization initiators, polymerization inhibitors, preservatives, UV absorbers, plasticizers, fillers, defoamers, and lubricants.

[0041] <Pigments> Known organic pigments and / or inorganic pigments can be used as pigments. For example, inorganic pigments include lead yellow, zinc yellow, Prussian blue, barium sulfate, cadmium red, titanium dioxide, zinc oxide, iron oxide, ultramarine, carbon black, graphite, aluminum powder, and iron oxide.

[0042] Examples of organic pigments include soluble azo pigments such as β-naphthol-based, β-oxynaphthoic acid-based, β-oxynaphthoic acid-based anilide-based, acetoacetate anilide-based, and pyrazolone-based pigments; insoluble azo pigments such as β-naphthol-based, β-oxynaphthoic acid-based anilide-based, acetoacetate anilide-based monoazo, acetoacetate anilide-based disazo, and pyrazolone-based pigments; phthalocyanine-based pigments such as copper phthalocyanine blue, halogenated (chlorinated or brominated) copper phthalocyanine blue, sulfonated copper phthalocyanine blue, and metal-free phthalocyanine; polycyclic pigments and heterocyclic pigments such as quinacridone-based, dioxazine-based, slene-based (pyrantrone, anthantrone, indanthrone, anthrapyrimidine, flavanthrone, thioindigo-based, anthraquinone-based, perinone-based, perylene-based, etc.); isoindolone-based, metal complex-based, and quinophthalone-based pigments.

[0043] In the present invention, the pigment can be used in any amount as long as the desired concentration can be reproduced on the printed paper surface, and is preferably 5 to 30% by mass, and more preferably 10 to 25% by mass, based on the total mass of the composition.

[0044] <Pigment dispersant> Known pigment dispersants can be used. Examples include polymeric dispersants mainly composed of polyoxyalkylene, polyalkylene, polyamine, vinyl polymers and copolymers, acrylic polymers and copolymers, polyesters, polyamides, polyimides, polyurethanes, and amine polymers. Commercially available products include the Azisper series from Ajinomoto Fine Techno Co., Ltd. (Azisper PB821, PB822, PB824, etc.), the Solsperse series from Lubrizol Corporation (Solsperse 24000, Solsperse 32000, Solsperse 38500, etc.), and the Disperbice series from Bic Chemie Corporation (BYK-162, BYK-168, BYK-183, etc.).

[0045] The pigment dispersant content is preferably 0.1 to 10% by mass relative to the total mass of the composition.

[0046] <Photopolymerization initiator> Known photocleavage-type polymerization initiators and hydrogen abstraction-type polymerization initiators can be used as photoinitiators. For example, acetophenone compounds and acylphosphine oxide compounds are examples of photocleavage-type polymerization initiators.

[0047] More specifically, examples of acetophenone compounds include 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone, 2-benzyl-2-(dimethylamino)-1-[4-(morpholino)phenyl]-1-butanone, and 2-(dimethylamino)-2-(4-methylbenzyl)-1-[4-(morpholino)phenyl]-1-butanone. Examples of acylphosphine oxide compounds include diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, ethylphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, and ethoxyphenyl(2,4,6-trimethylbenzoyl)phosphine oxide. These can be used individually or in combination of two or more types.

[0048] Furthermore, examples of hydrogen abstraction type polymerization initiators include dialkylaminobenzophenone compounds and thioxanthone compounds.

[0049] More specifically, examples of dialkylaminobenzophenone compounds include 4,4'-dialkylaminobenzophenones such as 4,4'-bis-(dimethylamino)benzophenone and 4,4'-bis-(diethylamino)benzophenone, and 4-benzoyl-4'-methyldiphenyl sulfide. These can be used individually or in combination of two or more types.

[0050] Examples of thioxanthone compounds include 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-diethylthioxanthe-9-one, 2-isopropylthioxanthone, 4-diisopropylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2-chlorothioxanthone, 1-chloro-4-propoxythioxanthone, and 2-hydroxy-3-(3,4-dimethyl-9-oxo-9Hthioxanthone-2-yloxy-N,N,N-trimethyl-1-propanamine hydrochloride. These can be used individually or in combination of two or more types.

[0051] In the present invention, the content of the photopolymerization initiator is preferably 0.5 to 20% by mass, and more preferably 5 to 15% by mass, based on the total mass of the composition.

[0052] When ultraviolet light is used as the active energy ray for curing the composition of the present invention, a photosensitizer may also be used in combination to further improve curability. Examples of photosensitizers include benzophenone, 4-methyl-benzophenone, 2,4,6-trimethylbenzophenone, 2,3,4-trimethylbenzophenone, 4-phenylbenzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 4,4'-bis(diethylamino)benzophenone, 4-(1,3-acryloyl-1,4,7,10,13-pentaoxotridecyl)benzophenone, methyl-o-benzoylbenzoate, [4-(methylphenylthio)phenyl]phenylmethanone, and (4-benzoylbenzyl)trimethylammonium chloride. Examples include monoium, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-styrylpropan-1-one polymer, diethoxyacetophenone, dibutoxyacetophenone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzoin n-butyl ether. These can be used individually or in combination of two or more types.

[0053] [Polymerization inhibitor] Examples of polymerization inhibitors, from the standpoint of storage stability, include nitroso compounds, phenolic compounds, quinone compounds, and piperidine compounds.

[0054] Examples of nitroso compounds include nitrosobenzene, aluminum N-nitrosophenylhydroxylamine, tri-p-nitrophenylmethyl, picric acid, cuperone, butyraldoxime, methyl ethyl ketoxime, and cyclohexanone oxime.

[0055] Examples of phenolic compounds include (alkyl)phenol, p-methoxyphenol, o-isopropylphenol, catechol, resorcinol, t-butylcatechol, pyrogallol, dibutylcresol, and guaiacol.

[0056] Examples of quinone compounds include hydroquinone, t-butylhydroquinone, p-benzoquinone, and 2,5-di-tert-butyl-p-benzoquinone.

[0057] Examples of piperidine compounds include 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl and phenothiazine.

[0058] Furthermore, polymerization inhibitors other than the nitroso compounds, phenol compounds, quinone compounds, and piperidine compounds mentioned above (also called "other photopolymerization inhibitors") can be used in combination. Specific examples of other polymerization inhibitors include 1,1-picrylhydrazyl, dithiobenzoyl disulfide, N-(3-oxyanilino-1,3-dimethylbutylidene)aniline oxide, cyclohexanone oxime cresol, and the like.

[0059] The amount of polymerization inhibitor is preferably 0.01 to 5% by mass of the total composition.

[0060] <Manufacturing of activated energy ray curable resin compositions> An active energy ray-curable resin composition can be produced by mixing a film binder and a (meth)acrylate compound using a known method.

[0061] <Flexographic Ink> A preferred embodiment of the active energy ray-curable resin composition of the present invention is to be used as a flexographic ink for flexographic printing. Specifically, the high fluidity provided by the polyester resin containing sulfur atoms and / or nitrogen atoms improves ink transferability in flexographic printing, resulting in improved print stability.

[0062] <Manufacturing of flexographic inks> For example, by mixing 3 to 50% by mass of the above-mentioned film binder, 15 to 70% by mass of the above-mentioned (meth)acrylate compound, and optionally a pigment, a pigment dispersant, a photopolymerization initiator, a polymerization inhibitor, the above-mentioned additives, and a solvent in an existing mixing apparatus, an active energy ray curable resin composition, which is a flexographic ink of the present invention, can be obtained.

[0063] <Laminate> The laminate of the present invention comprises a substrate and a cured product of the active energy ray curable resin composition.

[0064] <Base material> The substrate used in this invention can be any substrate used for printing or coating. Specifically, this includes paper, plastic film, metal foil, cloth, glass, ceramics, and the like.

[0065] <Cured product of an activated energy ray-curable resin composition> The active energy ray-curable resin composition of the present invention is formed as a film on a substrate, and then cured with active energy rays to become a cured product. There are no particular limitations on the method of forming the film; for example, spray coating, roller coating, dipping, brush coating, resin relief printing, offset printing (conventional lithographic printing using dampening solution and waterless lithographic printing without dampening solution), flexographic printing, gravure printing, screen printing, or other common coating methods can be used. This allows for the formation of a uniform resin layer on the substrate surface, enabling rapid and efficient acquisition of a cured product in the subsequent curing process. In particular, flexographic printing is preferred due to its low viscosity and high fluidity.

[0066] <Activated energy rays, curing conditions> The active energy rays used in this invention may include ultraviolet rays (UV rays), electron beams (EB rays), infrared rays (IR rays), visible light, X-rays, or a combination of these energy sources. In particular, ultraviolet rays (UV rays) and electron beams (EB rays) are widely used to accelerate and effectively promote curing, and their use is recommended in this invention as well. [Examples]

[0067] The present invention will be described in more detail below with reference to examples, but these examples do not limit the scope of the present invention in any way. In this invention, "parts" refers to "parts by mass," and "%" refers to "percent mass."

[0068] <Synthesis of polyester resins. (Synthesis of resins 1-20. Examples 1-19, Comparative Example 1)> (Example 1) A reaction mixture was obtained by charging 44.5 parts of gum rosin and 16.0 parts of maleic anhydride into a three-necked flask equipped with a stirrer, a reflux condenser with a water separator, and a thermometer, and heating it at 180°C for 1 hour while blowing in nitrogen gas. Next, gas chromatography-mass spectrometry of the reaction mixture confirmed that the Diels-Alder addition reaction had been completed. Next, to the above reaction mixture, 1.0 part of 2,2'-thiodiethanol was added as compound (A), which contains a sulfur atom and / or a nitrogen atom in its molecule and also contains a hydroxyl group; 38.5 parts of 1,6-hexanediol was added as a compound containing a hydroxyl group other than (A); and 0.05 parts of p-toluenesulfonic acid monohydrate was added as a catalyst. A dehydration condensation reaction was carried out at 220°C for 5 hours to obtain resin 1. The weight-average molecular weight (Mw) of resin 1 was 2000.

[0069] (Examples 2-11, 13-18, Comparative Example 1) Resins 2-11, 13-18, and 20 were obtained by performing the same procedure as in Example 1, except that the formulations shown in Table 1 were replaced.

[0070] (Example 12) A reaction mixture was obtained by charging 44.5 parts of gum rosin and 16.0 parts of maleic anhydride into a three-necked flask equipped with a stirrer, a reflux condenser with a water separator, and a thermometer, and heating it at 180°C for 1 hour while blowing in nitrogen gas. Next, gas chromatography-mass spectrometry of the reaction mixture confirmed that the Diels-Alder addition reaction had been completed. Next, 1.0 part of 2,2'-thiodiethanol was added to the above reaction mixture as compound (A), which contains a sulfur atom and / or a nitrogen atom in its molecule and also contains a hydroxyl group, and 38.5 parts of 1,6-hexanediol was added as a compound containing a hydroxyl group other than (A). A dehydration condensation reaction was carried out at 220°C for 12 hours to obtain resin 12. The weight-average molecular weight (Mw) of resin 12 was 2100.

[0071] (Example 19) Resin 19 was obtained by performing the same procedure as in Example 12, except that the formulation shown in Table 1 was replaced.

[0072] In Table 1, PEG200 refers to polyethylene glycol 200 (using polyethylene glycol 200 manufactured by Tokyo Chemical Industry Co., Ltd.).

[0073] [Table 1]

[0074] [Table 1]

[0075] <Varnish manufacturing. (Manufacturing of varnishes 1-21. Examples 20-39, Comparative Example 2)> (Example 20) Varnish 1 was produced by mixing 60.0 parts of resin 1, 39.8 parts of TMP(EO)3TA (EO(3mol) modified trimethylolpropane triacrylate, Miramer M3130, manufactured by MIWON Co., Ltd.) as a (meth)acrylate compound, 0.1 parts of Polystop 7300P (manufactured by Hakuto Co., Ltd.) as a polymerization inhibitor, and 0.1 parts of hydroquinone, and heating and melting these at 100°C.

[0076] (Examples 21-39, Comparative Example 2) Varnishes 2-21 were manufactured using the same procedure as in Example 20, except that the formulations shown in Table 2 were replaced.

[0077] In Table 2, HDDA represents 1,6-hexanediol diacrylate (using BASF's Laromer HDDA).

[0078] [Table 2]

[0079] [Table 2]

[0080] <Manufacturing of Inks 1-22. (Examples 40-59, Comparative Examples 3, 4)>

[0081] (Example 40) 15.0 parts of varnish 1, 20.0 parts of Sudacolor Red 602 (a red pigment from Sudarshan) as a pigment, 51.5 parts of TMP(EO)3TA (EO(3mol) modified trimethylolpropane triacrylate, Miramer M3130, from MIWON) as a (meth)acrylate compound, 4.0 parts of 379 (2-(dimethylamino)-2-(4-methylbenzyl)-1-[4-(morpholino)phenyl]-1-butanone, from Tokyo Chemical Industry Co., Ltd.) as a photopolymerization initiator, 2.0 parts of EMK (4,4'-bis(diethylamino)benzophenone, from Arkema) and 2.0 parts of DETX (2,4-diethylthioxanthone, from Tokyo Chemical Industry Co., Ltd.) as photopolymerization initiators, 0.5 parts of butyl-4-methylphenol as a polymerization inhibitor, and Solsperse as a pigment dispersant. Ink 1 was manufactured by mixing 5.0 parts of J180 (a polyalkylene imine-based basic resin dispersant manufactured by Lubrizol) and continuously milling it in a three-roll mill.

[0082] (Examples 41-59, Comparative Examples 3 and 4) Inks 2-22 were manufactured using the same procedure as in Example 40, except that the formulations shown in Table 3 were replaced.

[0083] [Table 3]

[0084] [Table 3]

[0085] (Liquidity) For inks 1-22, 2.1cc of ink was placed in a metal plate with a hemispherical indentation, left to stand for 15 minutes, then tilted at a 60-degree angle, and the length flowed over 60 seconds was measured. The ink was then evaluated based on the following criteria. A higher value indicates less ink clumping and better fluidity. ◎ to △ are practically preferable. (Evaluation Criteria) ◎: 180mm or more, ○: 150mm or more, less than 180mm, △: 120mm or more, less than 150mm, ×: Less than 120mm

[0086] (Adhesion) Ink 1 to 22 were tested using a Neil Peter FA-17 flexographic printing press at a speed of 50 m / min on biaxially oriented polypropylene film (product name: RGN-30, thickness 30 μm) manufactured by Innovia Films, and printed materials 1 to 22 were obtained. For printed materials 1-22, a cellophane tape peel test was performed on polypropylene film to evaluate the adhesion of the ink film to the polypropylene film. After the test, the surface of the printed materials was visually observed, and the adhesion was evaluated on a 5-point scale according to the following criteria. 5, 4, and 3 are practically preferable. 5: No change in the printed surface. 4: Peeling is observed in less than 10% of the printed surface area. 3: Peeling is observed in 10% to less than 30% of the printed surface area. 2: Peeling is observed on 30% or more but less than 60% of the printed surface area. 1: Peeling is observed over 60% or all of the printed surface area.

[0087] All of the inks in the examples exhibited excellent fluidity and adhesion, and those using a polyester resin containing sulfur atoms as a film binder yielded particularly good results. On the other hand, Comparative Example 3, which used a polyester resin that did not contain sulfur or nitrogen atoms as a film binder, and Comparative Example 4, which did not use any resin, both exhibited insufficient fluidity and adhesion.

[0088] From the above, it can be seen that the coating binder of the present invention has excellent effects.

Claims

1. A coating binder comprising a polyester resin containing sulfur atoms and / or nitrogen atoms.

2. The film binder according to claim 1, wherein the polyester resin has a thioether group.

3. The film binder according to claim 1, wherein the polyester resin is a reaction product of a carboxylic acid compound and a compound (A) that contains a sulfur atom and / or a nitrogen atom in its molecule and also contains a hydroxyl group.

4. The coating binder according to claim 3, wherein the total content of the structure derived from compound (A) in the polyester resin is 0.1 to 50% by mass.

5. The film binder according to claim 3, wherein the carboxylic acid compound is rosinic acid and / or modified rosinic acid.

6. The film binder according to claim 5, wherein the modified rosinic acid is one or more selected from rosinic acid and an α,β-unsaturated carboxylic acid or its acid anhydride, hydrogenated rosin, and disproportionated rosin.

7. The film binder according to claim 3, wherein compound (A) contains a sulfur atom and / or a nitrogen atom and a hydroxyl group in its molecule, and is compound (A1) contains a sulfur atom and a hydroxyl group in its molecule.

8. The film binder according to claim 7, wherein the compound (A1) containing a sulfur atom and a hydroxyl group in its molecule comprises a compound represented by the following general formula (1). R-S-R'-OH (1) (In general formula (1), R represents a monovalent organic residue, and R' represents a divalent organic residue.)

9. An active energy ray curable resin composition comprising a film binder according to any one of claims 1 to 8 and a (meth)acrylate compound.

10. The active energy ray curable resin composition according to claim 9, which is a flexographic ink.

11. A laminate comprising a base material and a cured product of the active energy ray curable resin composition described in claim 9.

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