JP5715914B2 - Ink binder, ink and ink cured product - Google Patents

Description

  The present invention relates to an ink binder, an ink, and an ink cured product, and more particularly, to an ink binder, an ink containing the ink binder, and an ink cured product obtained by curing the ink.

  Polyurethane resins are widely used in various fields, and are known to be used, for example, as dispersants for inks and the like.

  For example, a long-chain polyol having a number average molecular weight of 500 to 10,000 such as adipate-based polyester diol, a chain extender having 20 or less carbon atoms such as cyclohexane-1,4-dimethanol and isophoronediamine, N-methyldiethanolamine and the like For a polyurethane-based printing ink comprising a polyurethane-based resin obtained by reacting a tertiary amino group-containing active hydrogen compound with an organic diisocyanate such as isophorone diisocyanate and having a glass transition temperature of −35 to + 20 ° C. A binder has been proposed (see, for example, Patent Document 1 (Example 1)).

JP-A-11-166148

  However, the cured product of the ink obtained using such an ink binder has high surface tack (that is, poor blocking resistance). For example, when the cured products are brought into contact with each other, they stick to each other. , Handling may be reduced. Further, such inks and cured products thereof may be inferior in durability such as weather resistance and moisture resistance.

  Moreover, as an ink obtained by using such a binder for ink and a cured product thereof, for example, when the substrate is processed and cured, excellent adhesion to the substrate is required.

  Therefore, an object of the present invention is to provide an ink binder and an ink binder for producing an ink that can reduce the surface tackiness and obtain an ink cured product that is excellent in durability and adhesion. It is in providing the ink containing and the ink hardened | cured material obtained by hardening the ink.

  In order to achieve the above object, the ink binder of the present invention is prepared from a main agent containing a polyurethane resin having an active hydrogen group and a curing agent containing pentamethylene diisocyanate and / or a derivative thereof. It is said.

  In the ink binder of the present invention, it is preferable that the polyurethane resin is obtained by a reaction of a resin raw material containing pentamethylene diisocyanate.

  In the ink binder of the present invention, it is preferable that the pentamethylene diisocyanate derivative has an isocyanurate group and / or an allophanate group.

  In the ink binder of the present invention, the active hydrogen group preferably contains an amino group.

  Moreover, in the binder for inks of this invention, it is suitable that the amine value of the said polyurethane resin is 0.2-15 mgKOH / g.

  Moreover, in the binder for inks of this invention, it is suitable that the isocyanate group density | concentration of the said hardening | curing agent is 15-28 mass%.

  The ink of the present invention is characterized by containing the above-mentioned ink binder and a pigment.

  The ink cured product of the present invention is obtained by curing the above ink.

  Since the binder for ink of the present invention is prepared from a main agent containing a polyurethane resin having an active hydrogen group and a curing agent containing pentamethylene diisocyanate and / or a derivative thereof, the ink binder is obtained using this ink binder. According to the ink of the present invention, the surface tackiness is reduced, and the cured ink of the present invention having excellent durability and adhesion can be obtained.

  The ink binder of the present invention is prepared from a main agent and a curing agent.

  The main agent contains a polyurethane resin having an active hydrogen group (for example, a hydroxyl group, an amino group, etc.).

  In the main agent, the polyurethane resin having an active hydrogen group is, for example, an isocyanate component and an active hydrogen group-containing compound component (described in detail later, for example, a polyol component, a polyamine component, etc.), which are active against the isocyanate group of the isocyanate component. It can obtain by making it react so that the ratio of the active hydrogen group (for example, a hydroxyl group, an amino group, etc.) of a hydrogen group containing compound component may exceed 1.

  As an isocyanate component, a polyisocyanate monomer, a polyisocyanate derivative, etc. are mentioned, for example.

  Examples of the polyisocyanate monomer include polyisocyanates such as aromatic polyisocyanate, araliphatic polyisocyanate, and aliphatic polyisocyanate.

  Examples of the aromatic polyisocyanate include tolylene diisocyanate (2,4- or 2,6-tolylene diisocyanate or a mixture thereof) (TDI), phenylene diisocyanate (m-, p-phenylene diisocyanate or a mixture thereof), 4, 4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate (NDI), diphenylmethane diisocyanate (4,4'-, 2,4'- or 2,2'-diphenylmethane diisocyanate or mixtures thereof) (MDI), Examples include aromatic diisocyanates such as 4,4′-toluidine diisocyanate (TODI) and 4,4′-diphenyl ether diisocyanate.

  Examples of the araliphatic polyisocyanate include xylylene diisocyanate (1,3- or 1,4-xylylene diisocyanate or a mixture thereof) (XDI), tetramethylxylylene diisocyanate (1,3- or 1,4-tetra). Methyl xylylene diisocyanate or a mixture thereof (TMXDI), aromatic aliphatic diisocyanates such as ω, ω′-diisocyanate-1,4-diethylbenzene, and the like.

  Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, 1,2-propylene diisocyanate, butylene diisocyanate (tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate), penta Methylene diisocyanate (PDI such as 1,5-pentamethylene diisocyanate), hexamethylene diisocyanate (HDI such as 1,6-hexamethylene diisocyanate), 2,4,4- or 2,2,4-trimethylhexa Examples thereof include aliphatic diisocyanates such as methylene diisocyanate and 2,6-diisocyanate methyl capate.

Aliphatic polyisocyanates include alicyclic polyisocyanates. Examples of the alicyclic polyisocyanate include 1,3-cyclopentane diisocyanate, 1,3-cyclopentene diisocyanate, cyclohexane diisocyanate (1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate), and 3-isocyanatomethyl-3. , 5,5-trimethylcyclohexylisocyanate (isophorodiisocyanate) (IPDI), methylenebis (cyclohexylisocyanate) (4,4′-, 2,4′- or 2,2′-methylenebis (cyclohexylisocyanate) (H ₁₂ MDI) , Methylcyclohexane diisocyanate (methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate), norbornane diisocyanate (various (NBDI), bis (isocyanatomethyl) cyclohexane (1,3- or 1,4-bis (isocyanatomethyl) cyclohexane or a mixture thereof (cis isomer, trans isomer or mixture thereof) ( And alicyclic diisocyanates such as H ₆ XDI).

  These polyisocyanate monomers can be used alone or in combination of two or more.

  Examples of the polyisocyanate derivative include a multimer (for example, dimer, trimer (for example, isocyanurate-modified product, iminooxadiazinedione-modified product), pentamer, 7) of the polyisocyanate monomer described above. ), Allophanate-modified products (for example, allophanate-modified products produced from the reaction of the above-described polyisocyanate monomer and a low molecular weight polyol described below), polyol-modified products (for example, polyisocyanate monomer and below-mentioned). Polyol modified products (alcohol adducts, etc.) produced by reaction with low molecular weight polyols, biuret modified products (for example, biuret modified products produced by reaction of the above polyisocyanate monomer with water or amines, etc.) ), Modified urea (for example, the above-mentioned polyisocyanate monomer and diamine) Urea-modified products produced by the reaction), oxadiazine trione-modified products (for example, oxadiazine trione produced by the reaction of the above-mentioned polyisocyanate monomer and carbon dioxide gas), carbodiimide-modified products (the above-mentioned polyisocyanate). Carbodiimide modified products produced by decarboxylation condensation reaction of monomers), uretdione modified products, uretonimine modified products, and the like.

  Furthermore, examples of the polyisocyanate derivative include polymethylene polyphenyl polyisocyanate (crude MDI, polymeric MDI).

  These polyisocyanate derivatives can be used alone or in combination of two or more.

  Moreover, monoisocyanate can be used together as an isocyanate component as long as the excellent effects of the present invention are not impaired.

  Examples of the monoisocyanate include methyl isocyanate, ethyl isocyanate, n-hexyl isocyanate, cyclohexyl isocyanate, 2-ethylhexyl isocyanate, phenyl isocyanate, benzyl isocyanate, and p-toluenesulfonyl isocyanate.

  These monoisocyanates can be used alone or in combination of two or more.

  These isocyanate components can be used alone or in combination of two or more.

  As the isocyanate component, an aliphatic polyisocyanate is preferable, and pentamethylene diisocyanate is more preferable.

  If pentamethylene diisocyanate is used as the isocyanate component (that is, if the polyurethane resin is prepared by the reaction of a resin raw material containing pentamethylene diisocyanate), the polyurethane resin, pentamethylene diisocyanate and / or a derivative thereof, and a pigment are used. It is possible to improve physical properties such as surface tack, weather resistance, and moisture resistance of an ink cured product obtained by curing the prepared ink.

  In the isocyanate component, the average number of functional groups of the isocyanate group is, for example, 1.5 to 3.0, preferably 1.9 to 2.5, and particularly preferably 2.

  Moreover, the isocyanate group content rate (based on JISK1603-1 (2007)) of an isocyanate component is 31-56 mass%, for example, Preferably, it is 36-56 mass%, More preferably, it is 51-55 mass%. is there. Moreover, the amine equivalent (based on JISK1603-1 (2007)) of this isocyanate component is 75-136, for example, Preferably, it is 75-117, More preferably, it is 76-82.

  Examples of the active hydrogen group-containing compound component include a polyol component and a polyamine component.

  Examples of the polyol component include low molecular weight polyols and high molecular weight polyols.

  The low molecular weight polyol is a compound having two or more hydroxyl groups and a number average molecular weight of less than 400, preferably less than 300, and examples thereof include low molecular weight diols, low molecular weight triols, and low molecular weight polyols having four or more hydroxyl groups. It is done.

  Examples of the low molecular weight diol include ethylene glycol, propylene glycol, trimethylene glycol, 1,4-butylene glycol (1,4-butanediol), 1,3-butylene glycol (1,3-butanediol), 1, 2-butylene glycol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2,2-dimethyl-1,3-propanediol, neopentyl glycol, 1,6-hexanediol, 2,2 C2- such as diethyl-1,3-propanediol, 3,3-dimethylolheptane, 2-ethyl-2-butyl-1,3-propanediol, 1,12-dodecanediol, 1,18-octadecanediol 22 alkanediols such as 2-butene-1,4-diol, 2,6-dimethyl- - aliphatic diols, such as alkene diols such as octene-3,8-diol. Further, examples of the low molecular weight diol include alicyclic diols such as 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, or a C2-4 alkylene oxide adduct thereof. Examples of the low molecular weight diol include aromatics such as resorcin, xylylene glycol, bishydroxyethoxybenzene, bishydroxyethylene terephthalate, bisphenol A, bisphenol S, bisphenol F, and C2-4 alkylene oxide adducts of the above bisphenols. Diols are mentioned. Examples of the low molecular weight diol include ether diols such as diethylene glycol, triethylene glycol, and dipropylene glycol. Examples of the low molecular weight diol include tertiary amino group-containing diols such as N-methyldiethanolamine.

  Examples of the low molecular weight triol include glycerin, 2-methyl-2-hydroxymethyl-1,3-propanediol, 2,4-dihydroxy-3-hydroxymethylpentane, 1,2,6-hexanetriol, and trimethylolethane. , Trimethylolpropane, 2-methyl-2-hydroxymethyl-1,3-propanediol, 2,4-dihydroxy-3- (hydroxymethyl) pentane, 2,2-bis (hydroxymethyl) -3-butanol and others And aliphatic triols (8 to 24 carbon atoms).

  Examples of the low molecular weight polyol having 4 or more hydroxyl groups include tetramethylolmethane, pentaerythritol, dipentaerythritol, D-sorbitol, xylitol, D-mannitol, D-mannitol and the like.

  These low molecular weight polyols can be used alone or in combination of two or more.

  The high molecular weight polyol is a compound having two or more hydroxyl groups and a number average molecular weight of 300 or more, preferably 400 or more, for example, polyether polyol, polyester polyol, polycarbonate polyol, acrylic polyol, epoxy polyol, natural oil polyol, Silicone polyols, fluorine polyols, polyolefin polyols and the like can be mentioned.

  Examples of the polyether polyol include polyethylene glycol and polypropylene glycol obtained by addition reaction of alkylene oxides such as ethylene oxide and / or propylene oxide using the above-described low molecular weight polyol and / or polyamine component described later as an initiator. And polyalkylene oxides such as polyethylene polypropylene glycol (random or block copolymer). Examples thereof include polytetramethylene ether glycol obtained by ring-opening polymerization of tetrahydrofuran.

  As the polyester polyol, for example, a condensation reaction between a polyhydric alcohol selected from one or more of the above-described low molecular weight polyols, a polybasic acid, an alkyl ester thereof, an acid anhydride thereof, and an acid halide thereof. Or the polyester polyol obtained by transesterification is mentioned.

  Examples of the polybasic acid include oxalic acid, malonic acid, succinic acid, methyl succinic acid, glutaric acid, adipic acid, 1,1-dimethyl-1,3-dicarboxypropane, and 3-methyl-3-ethylglutaric acid. , Azelaic acid, sebacic acid, other aliphatic dicarboxylic acids (11 to 13 carbon atoms), hydrogenated dimer acid, maleic acid, fumaric acid, itaconic acid, orthophthalic acid, isophthalic acid, terephthalic acid, toluene dicarboxylic acid, dimer acid And het acid.

  Examples of the alkyl ester of polybasic acid include methyl ester and ethyl ester of polybasic acid described above.

  Examples of the acid anhydride include acid anhydrides derived from the above-mentioned polybasic acids. For example, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, 2-alkyl anhydride (carbon number 12-18) ) Succinic acid, tetrahydrophthalic anhydride, trimellitic anhydride and the like.

  Examples of the acid halide include acid halides derived from the polybasic acids described above, and examples include oxalic acid dichloride, adipic acid dichloride, and sebacic acid dichloride.

  Further, as the polyester polyol, for example, a hydroxyl group-containing vegetable oil fatty acid (for example, castor oil fatty acid containing ricinoleic acid, hydrogenated castor oil fatty acid containing 12-hydroxystearic acid, lactic acid, etc.) using the above-described low molecular weight polyol as an initiator. And vegetable oil-based polyester polyols obtained by condensation reaction of hydroxycarboxylic acids such as those under known conditions.

  Furthermore, the polyester polyol includes, for example, the above-described low molecular weight polyol as an initiator, for example, lactones such as ε-caprolactone and γ-valerolactone, and lactides such as L-lactide and D-lactide. Examples thereof include lactone polyester polyols such as polycaprolactone polyol and polyvalerolactone polyol obtained by ring-opening polymerization.

  Examples of the polycarbonate polyol include polycarbonate polyols obtained by using the above-described low molecular weight polyol as an initiator and carbonates such as ethylene carbonate and dimethyl carbonate. The polycarbonate polyol includes an amorphous polycarbonate diol composed of a copolymer of 1,5-pentanediol and 1,6-hexanediol, and a copolymer of 1,4-butanediol and 1,6-hexanediol. An amorphous polycarbonate diol composed of amorphous polycarbonate diol and 3-methyl-1,5-pentanediol.

  Examples of the acrylic polyol include a copolymer obtained by copolymerizing a polymerizable monomer having one or more hydroxyl groups and another monomer copolymerizable therewith.

  Examples of the polymerizable monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, 2,2-dihydroxymethylbutyl (meth) acrylate, and polyhydroxy. Examples thereof include alkyl maleates and polyhydroxyalkyl fumarate.

  Moreover, as another monomer copolymerizable therewith, for example, (meth) acrylic acid, alkyl (meth) acrylate (C1-12), maleic acid, alkyl maleate, fumaric acid, fumaric acid Alkyl, itaconic acid, alkyl itaconate, styrene, α-methylstyrene, vinyl acetate, (meth) acrylonitrile, 3- (2-isocyanato-2-propyl) -α-methylstyrene, trimethylolpropane tri (meth) acrylate, Examples include pentaerythritol tetra (meth) acrylate.

  The acrylic polyol can be obtained by copolymerizing these monomers in the presence of an appropriate solvent and a polymerization initiator.

  Examples of the epoxy polyol include an epoxy polyol obtained by reacting the above-described low molecular weight polyol with a polyfunctional halohydrin such as epichlorohydrin or β-methylepichlorohydrin.

  Examples of the natural oil polyol include hydroxyl group-containing natural oils such as castor oil and coconut oil.

  As the silicone polyol, for example, in the copolymerization of the acrylic polyol described above, a vinyl group-containing silicone compound such as γ-methacryloxypropyltrimethoxysilane is used as another copolymerizable monomer. Examples include coalesced and terminal alcohol-modified polydimethylsiloxane.

  As the fluorine polyol, for example, in the copolymerization of the above-mentioned acrylic polyol, a copolymer containing a vinyl group-containing fluorine compound, for example, tetrafluoroethylene, chlorotrifluoroethylene, etc., as another copolymerizable monomer Etc.

  Examples of the polyolefin polyol include polybutadiene polyol and partially saponified ethylene-vinyl acetate copolymer.

  These high molecular weight polyols can be used alone or in combination of two or more.

  Moreover, as a polyol component, the polyol component derived from a natural product, specifically, sugar etc. are mentioned.

  Examples of the sugar include dihydroxyacetone, glyceraldehyde, erythrulose, erythrose, threose, ribulose, xylulose, ribose, arabinose, xylose, lyxose, deoxyribose, psicose, fructose, sorbose, tagatose, allose, altrose, glucose, mannose , Growth, idose, galactose, talose, fucose, fucose, rhamnose, cedoheptulose, digitoxose, etc. Disaccharides such as raffinose, melezitose, gentianose, plan Trisaccharides such as oose, maltotriose, cellotriose, manninotriose, panose, for example, tetrasaccharides such as alkaboose, stachyose, cellotetraose, scorodose, such as glycogen, starch, amylose, amylopectin, cellulose, dextrin, dextran , Glucan, fructose, N-acetylglucosamine, chitin, chitosan, caronin, laminaran, inulin, levan, elephant palm mannan, xylan, actinospectinic acid, alginic acid, guaran, mannan, heparin, chondroitin sulfate, hyaluronic acid, pullulan Examples thereof include sugar alcohols such as erythritol, erythritol, maltitol, and sucrose, and oligosaccharides such as cyclodextrin. Examples of the sugar alcohol include glycerin described above, sorbitol described above, xylitol described above, mannitol described above, and mannitol described above.

  These sugars can be used alone or in combination of two or more.

  These polyol components can be used alone or in combination of two or more.

  As a polyol component, Preferably, high molecular weight polyol or combined use of high molecular weight polyol and low molecular weight diol is mentioned.

  The polyamine component is a compound having two or more amino groups, for example, an aromatic polyamine, an araliphatic polyamine, an alicyclic polyamine, an aliphatic polyamine, a primary amino group, or a primary amino group and Examples include alkoxysilyl compounds having a secondary amino group, polyoxyethylene group-containing polyamines, and the like.

  Examples of the aromatic polyamine include 4,4'-diphenylmethanediamine and tolylenediamine.

  Examples of the araliphatic polyamine include 1,3- or 1,4-xylylenediamine or a mixture thereof.

  Examples of the alicyclic polyamine include 3-aminomethyl-3,5,5-trimethylcyclohexylamine (also known as isophoronediamine), 4,4′-dicyclohexylmethanediamine, 2,5 (2,6) -bis ( Aminomethyl) bicyclo [2.2.1] heptane, 1,4-cyclohexanediamine, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, bis- (4-aminocyclohexyl) methane, diaminocyclohexane 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] undecane, 1,3- and 1,4-bis (aminomethyl) cyclohexane and mixtures thereof Etc.

  Examples of the aliphatic polyamine include ethylenediamine, propylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexamethylenediamine, and hydrazine (including hydrates). ), Diethylenetriamine, triethylenetetramine, tetraethylenepentamine, 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopentane and the like.

  Examples of the alkoxysilyl compound having a primary amino group or a primary amino group and a secondary amino group include γ-aminopropyltriethoxysilane and N-phenyl-γ-aminopropyltrimethoxysilane. Examples include alkoxysilyl group-containing monoamine, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, and the like.

  Examples of the polyoxyethylene group-containing polyamine include polyoxyalkylene ether diamines such as polyoxyethylene ether diamine. More specifically, for example, PEG # 1000 diamine manufactured by Nippon Oil & Fats, Jeffamine ED-2003, EDR-148, XTJ-512 manufactured by Huntsman, and the like can be mentioned.

  These polyamine components can be used alone or in combination of two or more.

  In addition, examples of the active hydrogen group-containing compound component include a hydroxyl group-amino group combined component.

  The hydroxyl group-amino group coexisting component is a compound having one or more hydroxyl groups and one or more amino groups, and examples thereof include amino alcohols such as monoethanolamine and N- (2-aminoethyl) ethanolamine. Is mentioned.

  Further, examples of the hydroxyl group-amino group-containing component further include a hydroxyl group-amino group-containing component derived from a natural product, specifically, an amino acid and the like.

  Examples of amino acids include alanine, arginine, asparagine, aspartic acid, cysteine, cystine, methionine, glutamine, glutamic acid, glycine, histidine, isoleucine, leucine, lysine, hydroxylysine, phenylalanine, proline, serine, threonine, tryptophan, proline, Oxyproline, hydroxyproline, tyrosine, valine, glucosamine, monatin, taurine, β-alanine, β-aminopropionic acid, γ-aminobutyric acid, anthranilic acid, aminobenzoic acid, thyroxine, phosphoserine, desmosine, ortinin, creatine, theanine, etc. Is mentioned.

  These hydroxyl group-amino group coexisting components can be used alone or in combination of two or more. In addition, a hydroxyl-amino group combined component can also be used, for example in order to adjust the molecular weight of a polyurethane resin.

  In addition to the above, examples of the active hydrogen group-containing compound include novolaks, phenol resins typified by cresols, polyphenols, polylactic acid, polyglycolic acid, lactic acid, and copolymers of glycolic acid.

  Further, as the active hydrogen group-containing compound component, further, as an active hydrogen compound component derived from natural products, for example, urushiol, curcumin, lignin, cardanol, cardol, 2-methylcardol, 5-hydroxymethylfurfural, resorcinol, Catechol, pyrogallol, terpene, rackol, thiol, phenol, naphthol, acetyl-CoA (acetylcoenzyme), acetoacetyl-CoA (acetoacetylcoenzyme), D-(-)-3-hydroxybutyryl-CoA, succinyl- Examples include CoA, (R) -3-hydroxybutyrate, isoeugenol, polybutylene succinate adipate, polyhydroxybutyrate, sophorolipid, emalzan and the like.

  Furthermore, examples of the active hydrogen group-containing compound component derived from a natural product include acids such as fatty acids.

  Examples of fatty acids include sebacic acid, azelaic acid, fumaric acid, succinic acid, oxaloacetic acid, itaconic acid, mesaconic acid, citraconic acid, malic acid, citric acid, isocitric acid, gluconic acid, gallic acid, tartaric acid, malic acid, Undecylenic acid, 11-aminoundecanoic acid, heptyl acid, 12-hydroxystearic acid, 12-hydroxydodecanoic acid, linolenic acid, linoleic acid, ricinoleic acid, oleic acid, crotonic acid, myristoleic acid, palmitoleic acid, elaidic acid, Vaccenoic acid, gadoleic acid, eicosenoic acid, erucic acid, nervonic acid, 3-hydroxybutyric acid, levulinic acid, abietic acid, neoamitic acid, parastrinic acid, pimaric acid, isopimaric acid, dehydroabietic acid, anacardic acid, palmitic acid, 3- Hydroxypropionic acid Examples include 3-hydroxyhexanoic acid, 3-hydroxyvaleric acid, 3-hydroxybutanoic acid, 4-hydroxybutanoic acid, pyruvic acid, phosphoenolpyruvic acid, glyoxylic acid, oxoglutanic acid, dihydroxyacetone phosphoric acid, and spikulsporic acid. .

  Furthermore, as the active hydrogen group-containing compound component, monool and / or monoamine can be used in combination when adjusting the molecular weight of the polyurethane resin.

  Examples of monools include methanol, ethanol, propanol, isopropanol, butanol, 2-ethylhexyl alcohol, other alkanols (C5 to 38) and aliphatic unsaturated alcohols (C9 to 24), alkenyl alcohol, and 2-propene-1. -Ol, alkadienol (C6-8), 3,7-dimethyl-1,6-octadien-3-ol and the like.

  These monools can be used alone or in combination of two or more.

  Examples of the monoamine include dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-t-butylamine, dihexylamine, 2-ethylhexylamine, 3-methoxypropylamine, Examples include 3-ethoxypropylamine, 3- (2-ethylhexyloxypropylamine), 3- (dodecyloxy) propylamine, morpholine, and the like.

  These monoamines can be used alone or in combination of two or more.

  These active hydrogen group-containing compound components can be used alone or in combination of two or more.

  And as a manufacturing method of a polyurethane resin, if a polyurethane resin can be prepared so that an active hydrogen group (for example, a hydroxyl group, an amino group, etc.) may be introduce | transduced into a molecule terminal, it will not restrict | limit in particular, A well-known method will be used. Such a method is preferably a prepolymer method.

  In the prepolymer method, for example, first, an isocyanate component and a part of the active hydrogen group-containing compound component are reacted to synthesize an isocyanate group-terminated prepolymer having an isocyanate group at the molecular end.

  In the synthesis of the isocyanate group-terminated prepolymer, the above-mentioned aliphatic aliphatic polyisocyanate, more preferably pentamethylene diisocyanate, can be mentioned as the isocyanate component.

  Further, in the synthesis of the isocyanate group-terminated prepolymer, as a part of the active hydrogen group-containing compound component, a high molecular weight polyol (and a low molecular weight polyol if necessary) is preferably used. Further, as the high molecular weight polyol, preferably, a polyester polyol is used, and as a low molecular weight polyol to be blended as necessary, preferably a low molecular weight diol, more preferably a combination of an aliphatic diol and a tertiary amino group-containing diol is used. Can be mentioned.

  When the high molecular weight polyol and the low molecular weight polyol are used in combination as the active hydrogen group-containing compound component, the blending ratio of the high molecular weight polyol and the low molecular weight polyol is 100 parts by mass with respect to the total amount of the high molecular weight polyol, For example, 80 parts by mass or more, preferably 90 parts by mass or more, usually less than 100 parts by mass, and the low molecular weight polyol is, for example, 20 parts by mass or less, preferably 10 parts by mass or less, usually 0 parts by mass. To exceed.

  In order to synthesize the isocyanate group-terminated prepolymer, the isocyanate component and a part of the active hydrogen group-containing compound component are mixed with the isocyanate group in the isocyanate component relative to the active hydrogen group in a part of the active hydrogen group-containing compound component. Formulation is made so that the equivalent ratio R (NCO / active hydrogen group) is, for example, 1.1 to 5.5, preferably 1.3 to 4.5, and more preferably 1.5 to 3.5. Mixing) in the reaction vessel until reaching a predetermined isocyanate group concentration (described later), for example, room temperature to 150 ° C., preferably 50 to 120 ° C., for example, 0.5 to 18 hours, preferably React for 2-10 hours.

  In this reaction, a urethanization catalyst is preferably added.

  Examples of the urethanization catalyst include amines, organometallic compounds, potassium salts and the like.

  Examples of amines include tertiary amines such as triethylamine, triethylenediamine, bis- (2-dimethylaminoethyl) ether, N-methylmorpholine, and quaternary ammonium salts such as tetraethylhydroxylammonium, such as imidazole, Examples thereof include imidazoles such as 2-ethyl-4-methylimidazole.

  Examples of organometallic compounds include tin acetate, tin octylate, tin oleate, tin laurate, dibutyltin diacetate, dimethyltin dilaurate, dibutyltin dilaurate, dibutyltin dimercaptide, dibutyltin maleate, dibutyltin dilaurate, dibutyltin Organic tin compounds such as dineodecanoate, dioctyltin dimercaptide, dioctyltin dilaurate, dibutyltin dichloride, for example, organic lead compounds such as lead octoate and lead naphthenate, for example, organic nickel compounds such as nickel naphthenate, for example And organic cobalt compounds such as cobalt naphthenate, organic copper compounds such as copper octenoate, and organic bismuth compounds such as bismuth octylate and bismuth neodecanoate.

  Examples of the potassium salt include potassium carbonate, potassium acetate, and potassium octylate.

  These urethanization catalysts can be used alone or in combination of two or more.

  The blending ratio of the urethanization catalyst is, for example, 1 to 5000 ppm, preferably 2 to 3000 ppm with respect to the total amount of the isocyanate component and the active hydrogen group-containing compound component.

  In this method, the isocyanate component and the active hydrogen group-containing compound component can be reacted in an organic solvent.

  Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, nitriles such as acetonitrile, alkyl esters such as methyl acetate, ethyl acetate, butyl acetate, and isobutyl acetate, such as n- Aliphatic hydrocarbons such as hexane, n-heptane, and octane, for example, alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, for example, aromatic hydrocarbons such as toluene, xylene, and ethylbenzene, such as methyl cellosolve acetate , Ethyl cellosolve acetate, methyl carbitol acetate, ethyl carbitol acetate, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, 3-methyl-3-methoxy Glycol ether esters such as butyl acetate and ethyl-3-ethoxypropionate, for example, ethers such as diethyl ether, tetrahydrofuran and dioxane, such as methyl chloride, methylene chloride, chloroform, carbon tetrachloride, methyl bromide, iodine Halogenated aliphatic hydrocarbons such as methylene chloride and dichloroethane, for example, polar aprotics such as N-methylpyrrolidone, dimethylformamide, N, N′-dimethylacetamide, dimethylsulfoxide, hexamethylphosphonylamide, etc. .

  Furthermore, as an organic solvent, a nonpolar solvent (nonpolar organic solvent) is mentioned, for example, As these nonpolar solvents, the aniline point containing an aliphatic and a naphthene type hydrocarbon organic solvent is 10--10, for example. Examples include non-polar organic solvents having low toxicity and weak dissolving power at 70 ° C., preferably 12 to 65 ° C., vegetable oils represented by terpene oil, and the like.

  These organic solvents can be used alone or in combination of two or more.

  The blending ratio of the organic solvent is not particularly limited, and is appropriately set according to the purpose and application.

  Moreover, after completion | finish of reaction can also remove an unreacted isocyanate component by well-known removal means, such as distillation and extraction, as needed.

  Furthermore, when an organic solvent is blended, the organic solvent after the reaction of the isocyanate component and the active hydrogen group-containing compound component can also be removed by a known removal means such as distillation or extraction.

  The number average molecular weight (measurement method: GPC method (standard polystyrene conversion)) of the isocyanate group-terminated prepolymer thus obtained is, for example, 1000 to 30000, preferably 2000 to 20000, and the isocyanate group equivalent is For example, it is 500-15000, Preferably, it is 1000-10000.

  Moreover, content of the unreacted (free) isocyanate component in an isocyanate group terminal prepolymer is 0.01-5 mass%, for example, Preferably, it is 0.05-3 mass%.

  In addition, an isocyanate group equivalent is synonymous with an amine equivalent, and can be calculated | required by A method or B method of JISK1603-1 (2007). Moreover, content of an unreacted isocyanate component can be calculated | required by HPLC measurement, for example.

  And the content (isocyanate group content, NCO%) of the isocyanate group of such an isocyanate group terminal prepolymer is 0.3-8 mass%, for example, Preferably, it is 0.6-4 mass%.

  Next, in this method, the obtained isocyanate group-terminated prepolymer is reacted with the remainder of the active hydrogen group-containing compound component. In the prepolymer method, the remainder of the active hydrogen group-containing compound component is used as a chain extender.

  The remainder (chain extender) of the active hydrogen group-containing compound component is preferably a polyamine component, and more preferably an alicyclic polyamine.

  If a polyamine component is used as the remainder (chain extender) of the active hydrogen group-containing compound component, a polyurethane resin having an amino group introduced as a free active hydrogen group at the molecular end, that is, a free active hydrogen group at the molecular end Among them, a polyurethane resin in which at least a part of the active hydrogen groups is an amino group, preferably a polyurethane resin in which all the active hydrogen groups are amino groups can be obtained.

  If the free active hydrogen group at the molecular terminal of the polyurethane resin contains an amino group, a suitable pot life after mixing the two liquids of the main agent and the curing agent can be obtained.

  Moreover, as a remainder (chain extender) of an active hydrogen group containing compound component, in order to adjust the molecular weight of a polyurethane resin, a polyamine component and a hydroxyl-amino group combined component can also be used together.

  When the polyamine component and the hydroxyl group-amino group coexisting component are used in combination as the balance (chain extender) of the active hydrogen group-containing compound component, the blending ratio thereof is the polyamine component and the hydroxyl group-amino group coexisting component. The polyamine component is, for example, 10 parts by mass or more, preferably 60 parts by mass or more, and usually less than 100 parts by mass, and the hydroxyl group-amino group coexisting component is, for example, 90 parts by mass relative to 100 parts by mass. Part by mass, preferably 40 parts by mass or less, usually exceeding 0 parts by mass.

  When the blending ratio of the polyamine component and the hydroxyl group-amino group coexisting component is in the above range, a polyurethane resin having an amino group introduced as a free active hydrogen group at the molecular end can be obtained.

  In order to react the isocyanate group-terminated prepolymer with the remainder of the active hydrogen group-containing compound component (chain extender), the isocyanate group-terminated prepolymer and the remainder of the active hydrogen group-containing compound component (chain extender) The equivalent ratio R (NCO / active hydrogen group) of the isocyanate group in the isocyanate group-terminated prepolymer to the active hydrogen group in the remainder (chain extender) of the active hydrogen group-containing compound component exceeds, for example, 0.75 Preferably, it is formulated (mixed) to exceed 0.9 and less than 1, for example, room temperature to 250 ° C., preferably room temperature to 200 ° C., for example, 5 minutes to 72 hours, preferably For 1 to 24 hours.

  Thereby, the polyurethane resin which has an active hydrogen group can be prepared.

  The number average molecular weight (measurement method: GPC method (standard polystyrene conversion)) of the obtained polyurethane resin is, for example, 3000 to 100000, preferably 5000 to 50000, and the amine value is, for example, 0.1 to 20 mgKOH. / G, preferably 0.2 to 15 mg KOH / g, more preferably 2 to 6 mg KOH / g.

  If the amine value of the polyurethane resin is within the above range, the surface tackiness and weather resistance of the ink cured product obtained by curing the ink prepared from the polyurethane resin, pentamethylene diisocyanate and / or its derivative, and the pigment. In addition, physical properties such as moisture resistance can be improved.

  In addition, the amine value of a polyurethane resin is calculated | required based on an amine equivalent.

  In addition, although the prepolymer method was illustrated and the manufacturing method of the polyurethane resin was demonstrated, as a manufacturing method of a polyurethane resin, if the polyurethane resin which has an active hydrogen group (preferably amino group) in the molecular terminal can be obtained especially For example, a known method such as a one-shot method can be used.

  Moreover, the main ingredient should just contain the said polyurethane resin at least, and can contain another main ingredient component.

  Specific examples of the other main component include the active hydrogen group-containing compound component described above.

  In the case where the other main agent component is contained, the blending ratio of the polyurethane resin and the other main agent component is, for example, 10 to 95 parts by mass, preferably 10 to 95 parts by mass with respect to the total amount of 100 parts by mass. It is 30-80 mass parts, and other main ingredient components are 5-90 mass parts, for example, Preferably, it is 20-70 mass parts.

  The main agent thus obtained can be used as it is, that is, after removing the organic solvent from the polyurethane resin produced as described above (and other main component if necessary), and the organic solvent is removed. It can also be used as a solution without. Furthermore, the polyurethane resin produced as described above (and other main component if necessary) can be diluted with the above organic solvent and used as a solution.

  When the main agent is used as a solution, the solid content concentration is, for example, 20 to 80% by mass, and preferably 30 to 70% by mass.

  Moreover, the viscosity (25 degreeC) of a main ingredient is 50-20000 mPa * s, for example, Preferably, it is 100-10000 mPa * s.

  The curing agent is prepared as a polyisocyanate composition containing pentamethylene diisocyanate and / or a derivative thereof.

  Examples of pentamethylene diisocyanate include 1,5-pentamethylene diisocyanate, 1,4-pentamethylene diisocyanate, 1,3-pentamethylene diisocyanate, or a mixture thereof, and preferably 1,5-pentamethylene. Diisocyanate is mentioned.

  In addition, although pentamethylene diisocyanate can be obtained as a commercial product, for example, pentamethylenediamine or a salt thereof is produced by a known method, for example, a biochemical method, and the pentamethylenediamine or a salt thereof is obtained. It can manufacture by making it react by methods, such as a phosgenation method and a carbamate method.

  The derivative of pentamethylene diisocyanate can be obtained, for example, by modifying pentamethylene diisocyanate, and examples thereof include the same derivatives as the polyisocyanate derivative described above.

Moreover, as a derivative | guide_body of pentamethylene diisocyanate, Preferably it contains at least 1 type of the functional group of the following (a)-(e).
(A) isocyanurate group (b) allophanate group (c) biuret group (d) urethane group (e) urea group The derivative of pentamethylene diisocyanate containing the functional group (isocyanurate group) of (a) is pentamethylene Diisocyanate trimer (trimer), for example, pentamethylene diisocyanate, monool or low molecular weight diol is converted into a known isocyanurate catalyst (trimerization catalyst such as N- (2-hydroxypropyl)- N, N, N-trimethylammonium-2-ethylhexanoate etc.) and the reaction can be obtained by trimerization.

  The trimer of pentamethylene diisocyanate can contain, in addition to the isocyanurate group, a polyisocyanate having an iminooxadiazinedione group.

  The derivative of pentamethylene diisocyanate containing the functional group (allophanate group) of (b) is an allophanate modified product of pentamethylene diisocyanate, and, for example, pentamethylene diisocyanate and monoalcohol are converted into a known allophanate catalyst (for example, Can be obtained by the reaction in the presence of the above isocyanurate-forming catalyst).

  The derivative of pentamethylene diisocyanate containing the functional group (biuret group) of (c) above is a biuret-modified product of pentamethylene diisocyanate, for example, pentamethylene diisocyanate and, for example, water, tertiary alcohol (for example, t-butyl alcohol, etc.), secondary amines (eg, dimethylamine, diethylamine, etc.) and the like can be obtained by reacting in the presence of a known biuretization catalyst (eg, trimethylphosphoric acid, etc.). .

  The derivative of pentamethylene diisocyanate containing the functional group (urethane group) of (d) above is a polyol modified form of pentamethylene diisocyanate, for example, pentamethylene diisocyanate and a polyol component (for example, trimethylolpropane). It can be obtained by reaction.

  The derivative of pentamethylene diisocyanate containing the functional group (urea group) of (e) above is a polyamine modified product of pentamethylene diisocyanate, and can be obtained, for example, by reaction of pentamethylene diisocyanate with water, a polyamine component, etc. Can do.

  In each of the above reactions, if necessary, for example, an additive such as a hindered phenol antioxidant (for example, 2,6-di (tert-butyl) -4-methylphenol), for example, organic phosphorus A co-catalyst such as an acid ester (eg, tris (tridecyl) phosphite) can be added to the reaction system.

  Furthermore, each said component can be made to react in presence of the above-mentioned organic solvent, Furthermore, an organic solvent can also be removed by a well-known method after reaction.

  The derivative of pentamethylene diisocyanate contains at least one kind of the functional groups (a) to (e), or can contain two or more kinds. Such a derivative of pentamethylene diisocyanate is produced by appropriately combining the above reactions.

  In the derivative of pentamethylene diisocyanate, the free pentamethylene diisocyanate may be removed by a known method after the modification of pentamethylene diisocyanate as described above, and the concentration is determined based on the total amount of pentamethylene diisocyanate and its derivatives. On the other hand, it is, for example, 5% by mass or less, preferably 1% by mass or less, usually exceeding 0% by mass.

  These pentamethylene diisocyanates and / or derivatives thereof can be used alone or in combination of two or more.

  As the pentamethylene diisocyanate and / or a derivative thereof, a derivative of pentamethylene diisocyanate is preferably used.

  The derivative of pentamethylene diisocyanate preferably has an isocyanurate group and / or an allophanate group.

  When the derivative of pentamethylene diisocyanate has an isocyanurate group and / or allophanate group, ink curing obtained by curing an ink prepared from a polyurethane resin, pentamethylene diisocyanate and / or its derivative, and a pigment It is possible to improve physical properties such as surface tackiness, weather resistance, and moisture resistance.

  When the derivative of pentamethylene diisocyanate has an isocyanurate group and an allophanate group, the molar ratio of isocyanurate group / allophanate group is, for example, 0.2 to 2000, preferably 0.5 to 400, more preferably 1 to 300, most preferably 1.5 to 200.

The molar ratio of isocyanurate group / allophanate group is calculated, for example, by determining the ratio (area ratio) between the signal corresponding to the allophanate group and the signal corresponding to the isocyanurate group by ¹ H-NMR. be able to.

  The isocyanate group concentration of pentamethylene diisocyanate and / or a derivative thereof is, for example, 10 to 28% by mass, preferably 18 to 28% by mass, more preferably 20 to 26% by mass, and most preferably 23 to 26% by mass. It is.

  The isocyanate group concentration of pentamethylene diisocyanate and / or its derivative can be measured by the n-dibutylamine method (based on JIS K-1556 (2006)).

  Moreover, the viscosity (25 degreeC) of pentamethylene diisocyanate and / or its derivative (s) is 100-8000 mPa * s, for example, Preferably, it is 200-5000 mPa * s.

  In addition, pentamethylene diisocyanate and / or derivatives thereof include, for example, a compound containing a sulfonamide group, specifically, aromatic sulfonamides (for example, o- and p-toluenesulfonamide), aliphatic Sulfonamides can also be contained.

  The compounding ratio of the compound containing a sulfonamide group is, for example, 10 to 5000 ppm, preferably 50 to 4000 ppm, more preferably 100 to 3000 ppm with respect to pentamethylene diisocyanate and / or a derivative thereof.

  Moreover, the hardening | curing agent should just contain the said pentamethylene diisocyanate and / or its derivative at least, and can contain another hardening | curing agent component.

  Specific examples of other curing agent components include the isocyanate components described above.

  In the case where the other curing agent component is contained, the blending ratio of pentamethylene diisocyanate and / or its derivative and the other curing agent component is pentamethylene diisocyanate and / or its content with respect to 100 parts by mass of the total amount thereof. The derivative is, for example, 5 parts by mass or more, preferably 50 parts by mass or more, more preferably 80 parts by mass or more, usually less than 100 parts by mass, and the other curing agent component is, for example, 95 parts by mass or less. Preferably, it is 50 parts by mass or less, more preferably 20 parts by mass or less, and usually exceeds 0 part by mass.

  The isocyanate group concentration of the curing agent is, for example, 7 to 30% by mass, preferably 15 to 28% by mass, more preferably 17 to 28% by mass, and most preferably 23 to 28% by mass.

  If the isocyanate group concentration of the curing agent is within the above range, the surface tackiness and weather resistance of an ink cured product obtained by curing an ink prepared from a polyurethane resin, pentamethylene diisocyanate and / or a derivative thereof, and a pigment. It is possible to improve physical properties such as heat resistance and moisture resistance.

  The isocyanate group concentration of the curing agent can be measured by the n-dibutylamine method (based on JIS K-1556 (2006)).

  Further, the curing agent can be used as it is, that is, by removing the organic solvent from the pentamethylene diisocyanate and / or its derivative (and other curing component if necessary) produced as described above. It can also be used as a solution without removing the solvent. Furthermore, the pentamethylene diisocyanate and / or its derivative (and other curing agent component if necessary) produced as described above can be diluted with the above organic solvent and used as a solution.

  When a hardening | curing agent is used as a solution, the solid content concentration is 50-95 mass%, for example, Preferably, it is 75-95 mass%.

  Moreover, the viscosity (25 degreeC) of a hardening | curing agent is 50-7000 mPa * s, for example, Preferably, it is 100-4000 mPa * s.

  The ink binder is prepared from the main agent described above and the curing agent described above.

  In the ink binder, the mass ratio of the main agent to the curing agent is 100 parts by mass of the main agent (including the organic solvent when the main agent is used as a solution). The curing agent (the curing agent is used as the solution). In the case, the organic solvent is included.) Is, for example, 0.05 to 20 parts by mass, preferably 0.1 to 5 parts by mass, and is cured with respect to 100 parts by mass of the solid content in the main agent. The solid content in the agent is, for example, 0.1 to 60 parts by mass, or preferably 0.2 to 20 parts by mass.

  Further, the mixing ratio of the main agent and the curing agent is such that the equivalent ratio R (NCO / active hydrogen group) of the isocyanate group in the curing agent to the active hydrogen group in the main agent is, for example, 1.1 to 2.4, preferably Is adjusted to be 1.2 to 1.9.

  In addition, for the ink binder, if necessary, known additives such as heat stabilizers, lubricants, plasticizers, antiblocking agents, antioxidants, ultraviolet absorbers, light stabilizers, mold release agents, fillers. , Hydrolysis inhibitors, flame retardants and the like can be blended.

  In addition, the mixture ratio of an additive is suitably set according to the objective and use.

  Such an additive can be added in advance to either or both of the main agent and the curing agent, or can be added separately when the main agent and the curing agent are blended.

  In addition, when an additive is added to the main agent and / or curing agent, the preparation of each component, specifically, the preparation of a polyurethane resin in the main agent, pentamethylene diisocyanate and / or a derivative thereof in the curing agent, etc. Further, it can be added to each reaction raw material, and can also be added to a polyurethane resin after reaction, pentamethylene diisocyanate and / or a derivative thereof, and the like.

  And the ink of this invention contains the above-mentioned ink binder and a pigment.

  The pigment is not particularly limited, and a known pigment can be used. Specific examples of the pigment include organic pigments such as phthalocyanine, azo, condensed azo, anthraquinone, quinacridone, indigo, and perylene, such as titanium oxide, carbon black, petal, ultramarine. And inorganic pigments.

  These pigments can be used alone or in combination of two or more.

  The blending ratio of the binder for ink and the pigment is such that the pigment is, for example, 1 to 500 parts by mass with respect to 100 parts by mass of the main agent in the ink binder (including the organic solvent when the main agent is used as a solution). The pigment is, for example, 2 to 1500 parts by mass, preferably 4 to 500 parts by mass with respect to 100 parts by mass of the solid content in the main agent.

  Moreover, the above-mentioned organic solvent can be mix | blended with ink as needed, and the resin solid content in ink is 2-40 mass%, for example, Preferably, it is 5-20 mass%.

  Moreover, the above-mentioned well-known additive etc. can be mix | blended with ink in an appropriate ratio as needed. As described above, the additive can be added to the ink binder in advance, or can be added separately when the ink binder and the pigment are blended.

  The obtained ink is subjected to coating / printing using a known coating / printing method such as brush coating, roll coater coating, bar coater coating, dispenser coating, screen printing coating, or the like. It can apply | coat to a base material (for example, a board | substrate, a support body, etc.).

  And the ink hardened | cured material of this invention can be obtained by hardening ink.

  Although it does not restrict | limit especially as a method of hardening ink, For example, it apply | coats to a base material as mentioned above, for example, 25-80 degreeC, Preferably, 30-60 degreeC, for example, 0.5-30 Dry for 1 minute, preferably 1 to 10 minutes. Thereafter, if necessary, the relative humidity (RH) is, for example, 30 to 80%, preferably 45 to 55%, for example, 23 to 60 ° C, preferably 23 to 40 ° C. Curing (aging treatment) for -14 days, preferably 1-7 days.

  Thereby, an ink cured product can be obtained.

  The above-mentioned ink binder is prepared from a main agent containing a polyurethane resin having an active hydrogen group and a curing agent containing pentamethylene diisocyanate and / or a derivative thereof, and thus obtained using this ink binder. According to the ink, the surface tackiness is reduced, and an ink cured product having excellent durability and adhesion can be obtained.

  In addition, pentamethylenediamine or a salt thereof used in such a method is suitable as a raw material for production (polymerization monomer raw material) such as polyimide, polyamide, and polyamideimide, and as a curing agent such as polyurethane and epoxy resin, for example. Can be used.

  Further, pentamethylene diisocyanate and / or a derivative thereof used in such a method can be suitably used as a raw material for, for example, a carbodiimide derivative, a uretonimine derivative, a uretdione derivative, a urea derivative, a biuret derivative, or an allophanate derivative.

  Also, pentamethylene diisocyanate and / or its derivatives can be used, for example, paints, overprint varnishes (OP varnishes), industrial or packaging adhesives, thermoplastic and thermosetting or millable elastomers, sealants, aqueous resins, thermosetting resins, Binder resin (specifically, used in various materials such as rubber chips, granular natural stone, paper, wood, various plastic chips, various metals, toners, magnetic recording materials, for example, in applications such as ink, screen printing, concrete) Binder resin), lens resin, active energy curable resin, liquid crystalline resin, flexible foam, rigid foam, etc., when used in the manufacture of their heat resistance, water resistance, chemical resistance, mechanical properties and electrical properties Can be improved.

  Furthermore, such pentamethylene diisocyanate and / or derivatives thereof, pentamethylenediamine or salts thereof include, for example, the above-mentioned active hydrogen group-containing compound components, especially sugars, amino acids, fatty acids and the like derived from the above-mentioned natural products. It can also be used as a crosslinking agent or modifier.

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In the following description, “part” and “%” are based on mass unless otherwise specified. Moreover, the measuring method used for a manufacture example etc. is shown below.
<Concentration of hydrolyzable chlorine (unit:%)>
The concentration (HC) of hydrolyzable chlorine contained in the isocyanate was measured in accordance with the test method for hydrolyzable chlorine described in Annex 3 of JIS K-1556 (2000).
<Pentamethylene diisocyanate concentration (unit: mass%)>
Using the pentamethylene diisocyanate obtained in Preparation Example 1 described later, the concentration of pentamethylene diisocyanate in the polyisocyanate composition was calculated using a calibration curve created from the area values of the chromatogram obtained under the following HPLC analysis conditions. did.

Equipment; Prominence (manufactured by Shimadzu Corporation)
1) Pump LC-20AT
2) Degasser DGU-20A3
3) Autosampler SIL-20A
4) Column thermostat COT-20A
5) Detector SPD-20A
Column; SHISEIDO SILICA SG-120
Column temperature: 40 ° C
Eluent: n-hexane / methanol / 1,2-dichloroethane = 90/5/5 (volume ratio)
Flow rate: 0.2 mL / min
Detection method: UV 225 nm
<Conversion rate of isocyanate group (unit:%)>
The conversion rate of the isocyanate group is the ratio of the area of the peak on the high molecular weight side of the peak of pentamethylene diisocyanate to the total peak area, based on the chromatogram obtained under the following GPC measurement conditions, as the conversion rate of the isocyanate group. .

Apparatus; HLC-8020 (manufactured by Tosoh Corporation)
Column; G1000HXL, G2000HXL and G3000HXL (trade name, manufactured by Tosoh Corporation) connected in series Column temperature: 40 ° C
Eluent: Tetrahydrofuran Flow rate: 0.8 mL / min
Detection method: Differential refractive index Standard material: Polyethylene oxide (manufactured by Tosoh Corporation, trade name: TSK standard polyethylene oxide)
<Isocyanate group concentration (unit: mass%)>
The isocyanate group concentration of the polyisocyanate composition was measured by an n-dibutylamine method based on JIS K-1556 (2006) using a potentiometric titrator.
<Viscosity (unit: mPa · s)>
The viscosity at 25 ° C. of the polyisocyanate composition was measured using an E-type viscometer TV-30 manufactured by Toki Sangyo Co., Ltd.
<Amine value (unit: mgKOH / g)>
The amine value of the polyurethane resin was calculated by the following equation by dissolving the sample in 20 mL of ethanol and titrating with a 0.2N ethanolic hydrochloric acid solution.
Amine number = (A × f × 0.2 × 56.1) / M
M: sample weight f: titer of ethanolic hydrochloric acid solution of 0.2N A: titration <molar ratio of isocyanurate group / allophanate group>
The molar ratio of isocyanurate group / allophanate group was measured by ¹ H-NMR, and the molar ratio of isocyanurate group / allophanate group was calculated from the area ratio of signals.
Apparatus: AL-400 (manufactured by JEOL, 399.65 MHz, probe: TH5ATFG2, 30 degree pulse, pulse repetition time: 15 seconds, resolution: 0.06 Hz, number of integrations 64 times, shift value standard: TMS (d ₆ DMSO Solvent), sample concentration: 0.2 wt%, test tube: 5 mmΦ)
Urethane bond peak: 6.7 to 7.5 ppm
Allophanate group peak: 8.5 ppm
Isocyanurate group peak: 3.7 ppm
Preparation Example 1 (Production of pentamethylene diisocyanate)
2000 parts by mass of o-dichlorobenzene was charged into a jacketed pressurized reactor equipped with an electromagnetic induction stirrer, an automatic pressure control valve, a thermometer, a nitrogen introduction line, a phosgene introduction line, a condenser, and a raw material feed pump. Subsequently, 2300 mass parts of phosgene was added from the phosgene introduction line, and stirring was started. Cold water was passed through the reactor jacket to maintain the internal temperature at about 10 ° C. A solution obtained by dissolving 400 parts by mass of pentamethylenediamine (purity 99.9% by mass) in 2600 parts by mass of o-dichlorobenzene was fed over 60 minutes with a feed pump, and was cooled at 30 ° C. or less at normal pressure. Phosgenation was started. After the feed was completed, the inside of the pressurized reactor became a pale brown white slurry.

  Next, the internal liquid of the reactor was pressurized to 0.25 MPa while gradually raising the temperature to 160 ° C., and further subjected to thermal phosgenation at a pressure of 0.25 MPa and a reaction temperature of 160 ° C. for 90 minutes. During the thermal phosgenation, 1100 parts by mass of phosgene was further added. During the thermal phosgenation, the liquid in the pressurized reactor became a light brown clear solution. After the completion of the thermal phosgenation, nitrogen gas was aerated at 100 to 140 ° C. and degassed.

  Subsequently, after o-dichlorobenzene was distilled off under reduced pressure, pentamethylene diisocyanate was also distilled off under reduced pressure. Subsequently, pentamethylene diisocyanate was charged into a four-necked flask equipped with a stirrer, a thermometer, a reflux tube, and a nitrogen introduction tube, and was heated at 190 ° C. for 3 hours under normal pressure while introducing nitrogen. Next, the heat-treated pentamethylene diisocyanate was charged into a glass flask, and a distillation tube filled with 4 elements of a packing (manufactured by Sumitomo Heavy Industries, Ltd., trade name: Sumitomo / Sulzer Lab Packing EX type), reflux ratio Further reflux under conditions of 127 to 132 ° C. and 2.7 KPa using a distillation tower equipped with a control timer (manufactured by Shibata Kagaku Co., Ltd., trade name: distillation head K type) and a rectifier equipped with a condenser. While rectifying, pentamethylene diisocyanate having a purity of 99.9% by mass was obtained. The concentration of hydrolyzable chlorine in pentamethylene diisocyanate was 0.004%.

Synthesis Example 1 (Production of polyisocyanate composition (a))
In a four-necked flask equipped with a stirrer, thermometer, reflux tube, and nitrogen introduction tube, 500 parts by mass of pentamethylene diisocyanate, 7 parts by mass of 1,3-butanediol, 2,6-di (tert-butyl) ) -4-methylphenol 0.3 parts by mass and tris (tridecyl) phosphite 0.3 parts by mass were charged and reacted at 82 ° C. for 3 hours.

  Next, the mixture was cooled to 50 ° C., and 0.025 parts by mass of N- (2-hydroxypropyl) -N, N, N-trimethylammonium-2-ethylhexanoate was added as a trimerization catalyst. The refractive index and the purity of the isocyanate were measured, the reaction was continued until a predetermined reaction rate was reached, and 0.01 parts by mass of a trimerization catalyst was further added. Since a predetermined reaction rate was reached after 90 minutes, 0.1 part by mass of o-toluenesulfonamide was added (conversion rate of isocyanate group: 15% by mass). The obtained reaction liquid was passed through a thin-film distillation apparatus (vacuum degree 0.093 KPa, temperature 150 ° C.) to remove unreacted pentamethylene diisocyanate, and further, o-based on 100 parts by mass of the obtained composition. 0.02 parts by mass of toluenesulfonamide was added to obtain a polyisocyanate composition (a).

  In this polyisocyanate composition (a), the concentration of pentamethylene diisocyanate is 0.2% by mass, the concentration of isocyanate groups is 23.2% by mass, the viscosity at 25 ° C. is 2500 mPa · s, and the molar ratio of isocyanurate groups / allophanate groups is 2.1.

Synthesis Example 2 (Production of polyisocyanate composition (b))
In a four-necked flask equipped with a stirrer, thermometer, reflux tube, and nitrogen introduction tube, 500 parts by mass of pentamethylene diisocyanate, 0.2 parts by mass of tris (tridecyl) phosphite, and 8 parts by mass of trimethyl phosphoric acid Then, 4 parts by mass of water was charged, the temperature was raised to 130 ° C., and the reaction was continued until the isocyanate group concentration reached the calculated value (48.7% by mass). The obtained reaction liquid was passed through a thin film distillation apparatus (vacuum degree 0.093 KPa, temperature 150 ° C.) to remove unreacted pentamethylene diisocyanate, thereby obtaining a polyisocyanate composition (b).

  In this polyisocyanate composition (b), the concentration of pentamethylene diisocyanate is 0.6% by mass, the concentration of isocyanate groups is 24.9% by mass, the viscosity at 25 ° C. is 2800 mPa · s, and the molar ratio of isocyanurate groups / allophanate groups is 0.

Synthesis Example 3 (Production of polyisocyanate composition (c))
500 parts by mass of pentamethylene diisocyanate was charged into a four-necked flask equipped with a stirrer, a thermometer, a reflux tube, a dropping funnel, and a nitrogen introduction tube, and the temperature was raised to 75 ° C. in a nitrogen atmosphere. Next, 48.4 parts by mass of dissolved trimethylolpropane (hereinafter sometimes abbreviated as TMP) was charged into a dropping funnel heated with a ribbon heater and dropped over 1 hour. After dropping, the temperature was raised to 80 ° C., and the reaction was continued until a predetermined isocyanate group concentration (41.4% by mass) was reached, to obtain a polyisocyanate reaction liquid (c). The obtained reaction liquid was passed through a thin film distillation apparatus (vacuum degree: 0.093 KPa, temperature: 150 ° C.) to remove unreacted pentamethylene diisocyanate to obtain a polyisocyanate composition (c).

  The concentration of pentamethylene diisocyanate in this polyisocyanate composition (c) is 0.3% by mass, the concentration of isocyanate groups is 18.1% by mass, the viscosity at 25 ° C. is 2100 mPa · s, and the molar ratio of isocyanurate groups / allophanate groups is 0.

Synthesis Example 4 (Production of polyol A)
The molar ratio of terephthalic acid, adipic acid, neopentyl glycol and 3-methyl-1,5-pentanediol is terephthalic acid / adipic acid / neopentyl glycol / 3-methyl-1,5-pentanediol = 1. It mix | blended so that it might become / 1/1/2, and it was made to esterify at 180-220 degreeC under nitrogen stream. After distilling a predetermined amount of water, the system was gradually depressurized and subjected to a condensation reaction at 13.3 kPa or less and 220 ° C. to obtain a polyester polyol having a number average molecular weight of 2000 (hereinafter, polyol A).

Synthesis example 5
Adipic acid, 1,4-butanediol and 3-methyl-1,5-pentanediol have a molar ratio of adipic acid / 1,4-butanediol / 3-methyl-1,5-pentanediol = 1. The mixture was blended so as to be 1/1/1 and subjected to an esterification reaction at 180 to 220 ° C. under a nitrogen stream. After distilling a predetermined amount of water, the system was gradually depressurized and subjected to a condensation reaction at 13.3 kPa or less and 220 ° C. to obtain a polyester polyol having a number average molecular weight of 2000 (hereinafter, polyol B).

Synthesis Example 6 (Production of polyurethane resin A)
In a four-necked flask equipped with a stirrer, thermometer, reflux tube, and nitrogen introduction tube, 91.7 parts by mass of polyol A, 137.6 parts by mass of polyol B, neopentyl glycol (hereinafter abbreviated as NPG). 8.3 parts by mass, N-methyldiethanolamine (hereinafter sometimes abbreviated as MDEA) 3.7 parts by mass, and methyl ethyl ketone (hereinafter sometimes abbreviated as MEK) 300. The mass part was charged and stirred uniformly. Subsequently, after adding 45.2 mass parts of pentamethylene diisocyanate, it heated at 70 degreeC and added 0.002 mass part of dibutyltin (IV) dilaurate (made by Wako Pure Chemical Industries). After reaching a predetermined isocyanate group concentration (0.98% by mass), it was cooled to 25 ° C. Next, 182.1 parts by mass of MEK was added, and further 213.8 parts by mass of isopropanol (hereinafter sometimes abbreviated as IPA) and isophoronediamine (manufactured by Evonik Degussa Japan, trade name: VESTANAT IPD, hereinafter) , And may be abbreviated as IPDA. Polyurethane resin A was obtained by reacting until an isocyanate group peak was not detected by FT-IR. Polyurethane resin A had a solid content of 30%, a viscosity at 25 ° C. of 750 mPa · s, and an amine value of 4 mgKOH / g.

Synthesis Example 7 (Production of polyurethane resin B)
In a four-necked flask equipped with a stirrer, a thermometer, a reflux tube, and a nitrogen introduction tube, 90.5 parts by mass of polyol A, 135.7 parts by mass of polyol B, 8.1 parts by mass of NPG, and MDEA 3.6 parts by mass and 300 parts by mass of MEK were charged and stirred uniformly. Next, 48.7 parts by mass of hexamethylene diisocyanate (Mitsui Chemicals, trade name: Takenate 700, hereinafter abbreviated as HDI) was added, and then heated to 70 ° C. to dibutyltin (IV) dilaurate. Was added in an amount of 0.002 parts by mass. After reaching a predetermined isocyanate group concentration (0.98% by mass), it was cooled to 25 ° C. Next, 184.9 parts by mass of MEK was added, and further, an amine solution in which 210.8 parts by mass of IPA and 17.7 parts by mass of IPDA were mixed was added. Polyurethane resin B was obtained by reacting until an isocyanate group peak was not detected by FT-IR. Polyurethane resin B had a solid content of 30%, a viscosity at 25 ° C. of 520 mPa · s, and an amine value of 4 mgKOH / g.

Synthesis Example 8 (Production of polyurethane resin C)
In a four-necked flask equipped with a stirrer, a thermometer, a reflux tube, and a nitrogen introduction tube, 85.5 parts by mass of polyol A, 128.3 parts by mass of polyol B, 7.7 parts by mass of NPG, and MDEA 3.4 parts by mass and 300 parts by mass of MEK were charged and stirred uniformly. Next, 61.7 parts by mass of isophorone diisocyanate (manufactured by Evonik Degussa Japan, trade name: VESTANAT IPDI, hereinafter sometimes abbreviated as IPDI) was added, followed by heating to 70 ° C. to dibutyltin (IV) dilaurate. Was added in an amount of 0.002 parts by mass. After reaching a predetermined isocyanate group concentration (0.98% by mass), it was cooled to 25 ° C. Next, 196.4 parts by mass of MEK was added, and further, an amine solution in which 199.3 parts by mass of IPA and 17.7 parts by mass of IPDA were mixed was added. Polyurethane resin C was obtained by reaction until an isocyanate group peak was not detected by FT-IR. Polyurethane resin C had a solid content of 30%, a viscosity at 25 ° C. of 800 mPa · s, and an amine value of 4 mgKOH / g.

Synthesis Example 9 (Production of polyurethane resin D)
In a four-necked flask equipped with a stirrer, thermometer, reflux tube, and nitrogen introduction tube, 91.7 parts by mass of polyol A, 137.6 parts by mass of polyol B, 8.3 parts by mass of NPG, and MDEA 3.7 parts by mass and 300 parts by mass of MEK were charged and stirred uniformly. Subsequently, after adding 45.2 mass parts of pentamethylene diisocyanate, it heated at 70 degreeC and added 0.002 mass part of dibutyltin (IV) dilaurate. After reaching a predetermined isocyanate group concentration (0.98% by mass), it was cooled to 25 ° C. Next, 172.7 parts by mass of MEK was added, and further, 213.8 parts by mass of IPA, 4.7 parts by mass of 1,4-butanediol, and 4.7 parts by mass of 1,3-butanediol were mixed. Then, the mixture was heated to 70 ° C., and 0.002 parts by mass of dibutyltin (IV) dilaurate was added. Polyurethane resin D was obtained by reacting until an isocyanate group peak was not detected by FT-IR. Polyurethane resin D had a solid content of 30% and a viscosity at 25 ° C. of 700 mPa · s.

Example 1
Prepare 100 parts by mass of polyurethane resin A as the main agent, 100 parts by mass of titanium dioxide (TiO ₂ , manufactured by Wako Pure Chemical Industries) as the pigment, and 50 parts by mass of MEK as the organic solvent. The mixture was stirred and mixed to obtain a dispersion solution.

  Next, a polyisocyanate composition (a) is prepared as a curing agent, and the curing agent and the dispersion solution are mixed so that the formulation of each component is as shown in Table 1, and an ink binder and its An ink containing an ink binder was obtained.

  Thereafter, the obtained ink was applied to the discharge-treated surface of a 15 μm-thick stretched polyethylene terephthalate film subjected to a corona discharge treatment with a bar coater so that the thickness after drying was 1 μm, and at 60 ° C. for 1 minute. It was dried and then aged in a room at 23 ° C. and 50% relative humidity for 24 hours. Thereby, an ink cured product (coating film) was obtained.

Examples 2-6
In the same manner as in Example 1 except that the type and blending amount of the main agent, the blending amount of the pigment, the blending amount of the organic solvent, the type and blending amount of the curing agent are as shown in Table 1, the binder for ink, the ink and An ink cured product was obtained.

Comparative Example 1
As a main agent, 100 parts by mass of polyurethane resin A, 100 parts by mass of titanium dioxide as a pigment, and 50 parts by mass of MEK as an organic solvent were prepared and stirred together with a glass bead in a paint shaker to obtain a dispersion solution. .

  Next, Takenate D-170N (hexamethylene diisocyanate trimer, isocyanate group content 20.7%, manufactured by Mitsui Chemicals Co., Ltd.) was prepared as a curing agent, and the curing agent and the dispersion solution were combined with each component. Mixing was performed so that the formulation was as shown in Table 1 to obtain an ink binder and an ink containing the ink binder.

  Thereafter, an ink cured product was obtained in the same manner as in Example 1.

Comparative Example 2
The binder for ink, the ink and the same as in Comparative Example 1 except that the type and blending amount of the main agent, the blending amount of the pigment, the blending amount of the organic solvent, the type and blending amount of the curing agent were as shown in Table 1. An ink cured product was obtained.

Evaluation The ink cured product obtained in each Example and each Comparative Example was evaluated by the following method. The results are shown in Table 1.
<Surface tackiness (blocking resistance)>
Prepare two samples (polyethylene terephthalate film with an ink cured product formed on the surface) obtained in each example and each comparative example, and the back of the polyethylene terephthalate film of one sample (an ink cured product is formed). The non-coated surface) and the ink cured product of the other sample were bonded together to form a laminated film.

Next, the obtained laminated film was sandwiched between glass plates, and a 5 kg weight was placed thereon, and the plate was allowed to stand in a constant temperature bath at 60 ° C. and 90% RH for 24 hours. After the lapse of the specified time, the film was taken out from the thermostatic chamber, the film was removed from the glass plate, and allowed to stand for 1 hour in a room at 23 ° C. and 50% RH. Next, after carefully peeling off the sample, the peeled state of the ink cured product was evaluated according to the following criteria.
○ There is no peeling of the cured ink.
Δ: Partial peeling of the ink cured product is observed.
X Peeling of the ink cured product is seen in the majority.
<Adhesion>
Adhesiveness was tested by the cross-cut method (cut interval 1 mm) according to JIS K5600-5-6 (1999), and evaluated according to the following criteria.
◎ The ink cured product was not removed at all.
○ Less than 20% of the ink cured product was peeled off.
Δ: 20% or more and less than 50% of the ink cured product was peeled off.
X 50% or more of the ink cured product was peeled off.
<Weather resistance>
After performing the QUV test under the following conditions, the sample was allowed to stand in a room at 23 ° C. and 50% RH for 1 hour. Next, adhesion was tested by a cross-cut method (cut interval 1 mm) according to JIS K5600-5-6 (1999), and evaluated according to the following criteria.
QUV test condition equipment: Dew panel light control weather meter (model FDP, manufactured by Suga Test Instruments)
Cycle conditions: 60 ° C. × 10% RH × 4 hours, 50 ° C. × 95% RH × 4 hours Number of cycles: 15 cycles Irradiance: 28 W / m ²
◎ The ink cured product was not removed at all.
○ Less than 20% of the ink cured product was peeled off.
Δ: 20% or more and less than 50% of the ink cured product was peeled off.
X 50% or more of the ink cured product was peeled off.
<Humidity resistance (warm water resistance)>
After being immersed in warm water at 80 ° C. for 1 week, it was left to stand in a room at 23 ° C. and 50% RH for 1 hour. Next, adhesion was tested by a cross-cut method (cut interval 1 mm) according to JIS K5600-5-6 (1999), and evaluated according to the following criteria.
◎ The ink cured product was not removed at all.
○ Less than 20% of the ink cured product was peeled off.
Δ: 20% or more and less than 50% of the ink cured product was peeled off.
X 50% or more of the ink cured product was peeled off.

  The details of the abbreviations in the table are as follows.

  Takenate D-170N: hexamethylene diisocyanate trimer, isocyanate group content 20.7%, viscosity at 25 ° C. 2700 mPa · s, isocyanurate group / allophanate group molar ratio 2.4 (Mitsui Chemicals)

Claims (7)

A main agent containing a polyurethane resin having an active hydrogen group;
Prepared from a curing agent containing pentamethylene diisocyanate and / or a derivative thereof ,
The ink binder, wherein the polyurethane resin has an amine value of 0.2 to 15 mgKOH / g .   The binder for ink according to claim 1, wherein the polyurethane resin is obtained by a reaction of a resin raw material containing pentamethylene diisocyanate.   The ink binder according to claim 1 or 2, wherein the pentamethylene diisocyanate derivative has an isocyanurate group and / or an allophanate group.   The ink binder according to claim 1, wherein the active hydrogen group includes an amino group. The ink binder according to any one of claims 1 to 4 , wherein the isocyanate group concentration of the curing agent is 15 to 28% by mass. An ink comprising the ink binder according to any one of claims 1 to 5 and a pigment. An ink cured product obtained by curing the ink according to claim 6 .