JP2896995B2 - Binder for printing ink and printing ink - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a binder for printing ink and a printing ink. More specifically, a binder for a printing ink having good adhesion to a plastic film and having direct lamination suitability; and
It relates to a printing ink using these.

[0002]

2. Description of the Related Art Conventionally, in the production of a packaging material called a flexible package based on a plastic film such as a polyester (PET) film, a nylon (NY) film, and an oriented polypropylene (OPP) film, a gravure film is used as a film substrate. After printing using a method such as printing or flexographic printing, a polyethylene film is used to improve the functionality of the packaging material such as heat sealability and airtightness.
Lamination of an unstretched polypropylene film by dry lamination or extrusion lamination is usually performed.

[0003] In the extrusion lamination processing for coating with molten polyethylene or polypropylene, an anchor coating agent (AC agent) mainly composed of polyethyleneimine or polyisocyanate is usually used for the purpose of imparting adhesive strength to an ink layer. But AC
A method of directly laminating with a molten polypropylene or the like without using an agent (direct lamination) is also performed.
Although the direct lamination method is economically advantageous,
Its suitability is mainly determined by the binder resin used in the printing ink.

[0004] Conventionally, solvent-based printing inks have been widely used, and PET, NY, OP
Urethane resins having wide adhesiveness to films using various substrates such as P are generally used. Also,
Chlorinated polyolefins such as chlorinated polypropylene are used as those having direct lamination suitability. On the other hand, as a binder resin for aqueous printing ink aimed at removing solvent in the future, urethane resin emulsions having good adhesion properties (JP-A-63-37160, JP-A-2-238015, etc.) have been proposed. As a material having direct laminating suitability, a product obtained by emulsifying a chlorinated polyolefin such as chlorinated polypropylene (Japanese Patent Laid-Open No. 5-209006) has been proposed.

[0005]

However, conventional printing inks using a polyurethane resin as a binder are inadequate in lamination processing suitability, particularly in direct lamination suitability, in both solvent-based and water-based printing inks. On the other hand,
Ink using chlorinated polyolefin as binder is O
It adheres well to PP, but has insufficient adhesion to PET, NY, etc., which limits the usable base film.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies on printing ink binders and printing inks which have good lamination suitability and have sufficient adhesion to various plastic films. It has been found that the above problems can be solved in any of organic solvent-containing printing inks and water-based printing inks by using a polyurethane resin containing a high molecular polyol having a structure as a polyol component as a binder, and reached the present invention. That is, the present invention relates to the following <1> and <2> binders and the following <3> and <4> printing inks.

<1> Consisting of a polyurethane resin (U) having a polyol component (A) as a structural unit, (A) contains an aliphatic hydrocarbon group having 3 to 40 carbon atoms as a side chain, and has a number average molecular weight of A binder for printing ink, which is a polyol component comprising at least one of 500 to 10,000 high molecular polyols (A1). <2> The polyurethane resin (U) is a polyurethane resin (Uaq) having an acid group neutralized with ammonia and / or an organic amine, and a component comprising the resin (Uaq) is diluted in an aqueous medium. <1> The binder according to <1>. <3> A solvent-based printing ink containing the binder according to <1> as a main binder component. <4> An aqueous printing ink comprising the binder according to <2> as a main binder component.

The aliphatic hydrocarbon group having 3 to 40 carbon atoms in the polymer polyol (A1) in each of the binders <1> and <2> is a linear, branched or alicyclic, saturated or unsaturated hydrocarbon group. A saturated hydrocarbon group is mentioned, and a preferable one is a linear or branched saturated hydrocarbon group. The carbon number of the aliphatic hydrocarbon group is usually 3 to 40, preferably 5 to
30, more preferably 8 to 20. If the number of carbon atoms is less than 3, the direct lamination adhesiveness is insufficient, and 40
If the ratio exceeds the above, the blocking resistance of the ink coating film decreases.

The content of the aliphatic hydrocarbon group having 3 to 40 carbon atoms in the polyol component (A) is usually 5 to 80% by weight, preferably 10 to 70% by weight, respectively. In particular, it is 15 to 60% by weight. If it is less than 5% by weight, the direct laminating adhesiveness will be reduced, and if it exceeds 80% by weight, the blocking resistance of the ink coating film will be reduced.

<1> and <2> Examples of the compound which gives a side chain of an aliphatic hydrocarbon group in the polyol for obtaining (A1) include the following (a1) to (a5). . (A1) a 1,2-alkanediol having 5 to 42 carbon atoms:
1,2-hexanediol, 1,2-octanediol, 1,2-decanediol, 1,2-dodecanediol, 1,2-octadecanediol, etc. (a2) Glycerin monoalkyl ether having 6 to 43 carbon atoms: glycerin Monohexyl ether, glycerin monooctyl ether, glycerin mono-2-ethylhexyl ether, glycerin monodecyl ether, glycerin monododecyl ether, glycerin monooctadecyl ether, etc. (a3) Glycerin fatty acid monoester having 7 to 44 carbon atoms: glycerin hexanoate mono Esters, glycerin octanoic acid monoester, glycerin-2-ethylhexanoic acid monoester, glycerin decanoic acid monoester,
(A4) Alkylamine having 3 to 40 carbon atoms: butylamine, hexylamine, 2-ethylhexylamine, octylamine, dodecylamine, stearylamine, etc. (a5) C5 to 5 carbon atoms 42 α-olefin oxides:
α-decene oxide, α-dodecene oxide, α-
Octadecene oxide, etc.

The 1,2-alkanediol (a1) and the α-olefin oxide (a5) can be produced by a known method such as a method of reacting α-olefin with acetic acid and hydrogen peroxide in the presence of an acid catalyst. Glycerin alkanol monoether (a2) can be produced by, for example, a method of reacting a long-chain alkyl alcohol with epichlorohydrin and then hydrolyzing it; a method of reacting glycerin with an alkyl halide. Glycerin fatty acid monoester (a3) can be produced by a method of esterifying glycerin and a fatty acid in the presence of an alkali catalyst.

<1> and <2> are the above (a1) to
Examples of (A1) obtained by using (a5) include the following (A11) to (A15). (A11) A 1,2-alkanediol having 5 to 42 carbon atoms (a1), a glycerin monoalkyl ether having 6 to 43 carbon atoms (a2) or a glycerin fatty acid monoester having 7 to 44 carbon atoms (a3), A polyether diol obtained by adding 2 to 4 alkylene oxides (b). (A12) A polyether diol obtained by adding 2 mol or more of an alkylamine oxide (b) having 2 to 4 carbon atoms to an alkylamine having 3 to 40 carbon atoms (a4). (A13) A polyether diol derived from an alkylene oxide composed of an α-olefin oxide (a5) having 5 to 42 carbon atoms. (A14) (a1), (a2), (a3), (A1
1) A polyester diol comprising a diol component comprising at least one diol selected from the group consisting of (A12) and (A13), and a dicarboxylic acid (c). (A15) (a1), (a2), (a3), (A1
1) A polylactone diol obtained by adding a lactone monomer (d) to a diol component comprising at least one diol selected from the group consisting of (A12) and (A13). Of these, (A14) and (A15) are preferred because they have excellent oil resistance.

The alkylene oxide (b) having 2 to 4 carbon atoms used in (A11) and (A12) is ethylene oxide (hereinafter referred to as EO), propylene oxide (hereinafter referred to as PO), butylene oxide, or a mixture thereof. Combination is mentioned. (A11) and (A12) can be produced by a conventionally known alkylene oxide addition reaction. When two or more alkylene oxides are used, the addition form may be either block or random.

(A13) can be obtained by adding α-olefin oxide (a5) alone or in combination with (a5) and the above-mentioned alkylene oxide (b) to two active hydrogen atom-containing compounds. Examples of the compound containing two active hydrogen atoms include lower diols having 9 or less carbon atoms (ethylene glycol, propylene glycol, neopentyl glycol, etc.) and monoamines having 10 or less carbon atoms (methylamine, ethylamine, butylamine, 2-ethylhexyl) Liquid substances such as amines) can be suitably used. The method of adding (a5) alone or (a5) and (b) to these may be a known method, and the addition form when adding two or more kinds may be either block or random.

As the diol component in (A14),
Other diols may be used. Other diols include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol having a number average molecular weight of less than 500, 1,4-
Butanediol, 1,3-butanediol, 3-methyl-1,5 pentanediol, 1,6-hexanediol, neopentyl glycol, 2-methyl-1,8 octanediol, 2,2,4-trimethyl-1 , 6 hexanediol, 3,3,5-trimethyl-1,6 hexanediol, 1,9-nonanediol, cyclohexyldimethanol, bis (hydroxyethoxy) benzene, a low molar adduct of bisphenols with EO or PO, Those having a number average molecular weight of less than 500 and combinations of two or more of them are mentioned.

When another diol is used, (a1)
(A2), (a3), (A11), (A12) and (A
13) The ratio of one or more diols selected from the group consisting of the other diols to the other diols is consequently 3 carbon atoms in (A).
As described above, the content of the aliphatic hydrocarbon group of from 40 to 40 is usually 5 to 80% by weight, preferably 10 to 70%, particularly 15
The ratio may be up to 60%.

The dicarboxylic acids (c) in (A14)
Examples thereof include the following (c1) and (c2) and a combination of two or more of them. (C1) an aliphatic dicarboxylic acid having 4 to 10 carbon atoms (adipic acid, succinic acid, sebacic acid, azelaic acid, fumaric acid, maleic acid, etc.) or an ester-forming derivative thereof (anhydride, lower alkyl ester, etc.) (c2) A) Aromatic dicarboxylic acids (phthalic acid, terephthalic acid, isophthalic acid, etc.) or ester-forming derivatives thereof Among these, preferred are aliphatic or aromatic dicarboxylic acids having 6 to 10 carbon atoms, especially adipic acid, sebacic acid , Azelaic acid, terephthalic acid, isophthalic acid and their ester-forming derivatives. (A14) can be produced by a conventionally known method. For example, a method in which an excess molar amount of a diol component and a dicarboxylic acid (c) are subjected to dehydration condensation polymerization or transesterification to obtain a polyester having a terminal hydroxyl group ( A14) is obtained.

The lactone monomer (d) used in (A15) includes ε-caprolactone, δ-valerolactone and the like. (A15) can be produced by a conventionally known method of adding a lactone monomer to a diol component.

The number average molecular weight of each of <1> and <2> is generally 500 to 10,000.
0, preferably 700 to 6,000. Molecular weight 50
If it is less than 0, the resulting polyurethane resin film becomes hard, and when used as an ink, the adhesiveness to a plastic film decreases. If it exceeds 10,000, the coating of the polyurethane resin becomes soft, and when used as an ink, the blocking resistance of the coating decreases.

<1> and <2> Each of the polyol component (A) may be used together with (A1), if necessary, with another polymer polyol (A2). Examples of (A2) include the following <A21>, <A22>, and a combination of two or more of them. (A21) Polyether polyol: polyoxyethylene polyol, polyoxypropylene polyol, polyoxyethylene propylene polyol, EO and / or PO adduct of bisphenol, etc. (A22) Polyester polyol: polyethylene adipate diol, polybutylene adipate diol,
Polyethylene butylene adipate diol, polyneopentyl adipate diol, poly 3-methylpentylene adipate diol, polycaprolactone diol, polyvalerolactone diol, polyhexamethylene carbonate diol, etc.

The resin (U) in <1> has (A) as a structural unit. Examples thereof include (A) and (A).
Polyurethane resin (Us) from organic polyisocyanate (B) and, if necessary, chain extender (C). The resin (Uaq) in <2> has (A) as a structural unit and has an acid group neutralized with ammonia and / or an organic amine, and (Uaq) is a water-based product of (U). It can be said. Examples of (Uaq) include (A),
Acid of the organic polyisocyanate (B), the compound (D) having an acidic group and at least two active hydrogen-containing groups in the molecule and, if necessary, the polyurethane resin (Ua) having an acid group from a chain extender (C). Those obtained by neutralizing a group with ammonia and / or an organic amine are exemplified.

Examples of the organic polyisocyanate (B) (Us) and (Ua) include, for example, the following (B1) to (B1)
5) and mixtures of two or more of these. (B1) 6 to 16 aromatic diisocyanates [2,4- and / or 2,6-tolylene diisocyanate (TDI), 4,4 ′ (B2) aliphatic diisocyanate having 6 to 10 carbon atoms [hexamethylene diisocyanate (HDI), lysine diisocyanate, etc.]; (B3) alicyclic diisocyanate having 6 to 16 carbon atoms [isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4'-diisocyanate (hydrogenated MD
(B4) araliphatic diisocyanate having 8 to 12 carbon atoms [xylylene diisocyanate (XDI), α, α,
(B5) Modified products of these organic diisocyanates (for example, modified products of isocyanurate, buret, carbodiimide, etc.) Preferred among these are ink re-dissolution (B3) and (B4) which are less problematic in the properties and yellowing, especially IPDI,
Hydrogenated MDI, TMXDI and XDI.

(Us) and (Ua) Each of the chain extenders (C) to be used if necessary includes, for example, the following (C1) to (C1)
(C3) and a combination of two or more of these. (C1) Low molecular polyol having an average molecular weight of less than 500: compounds exemplified as other glycols constituting the above (A14), alkylene oxide adducts of bisphenols, dimethylolpropionic acid, etc. (C2) Polyamine compound: aliphatic diamine (Ethylenediamine, hexamethylenediamine, etc.), alicyclic diamine (isophoronediamine, 4,4'-dicyclohexylmethanediamine, norbornanediamine, etc.), aromatic diamine (4,4'-diaminodiphenylmethane, etc.), araliphatic diamine (Xylylenediamine, etc.), pyridine, or derivatives thereof (C3) Alkanoldiamine: hydroxylethylethylenediamine, N, N'-dihydroxyethylethylenediamine, etc.

The compound (D) having an acid group and at least two active hydrogen groups in the molecule in (Ua) includes:
For example, the following (D1) to (D3) are exemplified. (D1) Hydroxy acid: glycolic acid, tartaric acid, 4,6
-Dihydroxyisophthalic acid, α, α-dimethylolpropionic acid, α, α-dimethylolbutyric acid, α, α-dimethylolnonanoic acid, and carboxyl group-containing polycaprolactone diol obtained by addition polymerization of caprolactone monomer with these ( D2) Hydroxysulfonic acid: 1,7-dihydroxynaphthalenesulfonic acid, etc. (D3) Aminosulfonic acid: 2,4-diaminobenzenesulfonic acid, etc. Of these, preferred are two hydroxyl groups and one carboxyl in the molecule. Compounds having a group: α, α-dimethylolpropionic acid, α, α-dimethylolbutyric acid, and carboxyl group-containing polycaprolactone diol obtained by addition-polymerizing a caprolactone monomer to these compounds.

When the acid group of (D) is a carboxyl group, the content of carboxyl group based on the weight of (Ua) is usually 1.0 to 7.0% by weight, preferably 1.5 to 6.0% by weight. , Especially 2.0 to 5.0% by weight. If the content of the carboxyl group is less than 1.0%, a stable aqueous binder cannot be obtained, and if it exceeds 7.0%, the water resistance of the film when used as an ink decreases.

In producing (Us) and (Ua), a terminating agent (E) can be used if necessary. (E)
Examples thereof include monoalcohols (such as methanol and butanol), monoamines (such as butylamine and dibutylamine), and alkanolamines (such as monoethanolamine and diethanolamine).

The resin (Us) may have a primary and / or secondary amine value not exceeding 20, and the amine value is more preferably from 0.5 to 15, particularly preferably from 1 to 10. is there. The functional group having an amine value may be any of a primary amino group and a secondary amino group, as long as these groups are introduced into the urethane molecular chain. In the production of the resin (Us), the equivalent ratio of the isocyanate group of (B) to the total of the active hydrogen groups (A) and (C), which are active hydrogen components, and the active hydrogen group (E) used if necessary is usually 1 : (1.00 to 1.5), preferably 1: (1.
05 to 1.3).

The method for producing the resin (Us) is not particularly limited, and the resin (Us) may be produced by a one-shot method in which the components are reacted at once or a multi-step method. The multi-stage method is a multi-stage method in which the reaction is carried out stepwise. For example, after reacting (B) with a part of the active hydrogen compound to form an isocyanate group-terminated prepolymer, the remaining active hydrogen compound is added and further reacted. Manufacturing method. Also (U
In the production of s), the reaction temperature is usually 20 to 140 ° C,
Preferably, it is performed at a temperature of 40 to 120 ° C. However, when an amine compound is reacted as the chain extender (C) or the like, the reaction is usually performed at a temperature of 100 ° C or lower, preferably 0 to 80 ° C.

In order to accelerate the reaction if necessary, catalysts used in ordinary urethane reactions [amine catalysts (triethylamine, N-ethylmorpholine, triethylenediamine, etc.), tin catalysts (dibutyltin dilaurate, dioctyltin dilaurate, octyl) Tin oxide, etc.), titanium-based catalysts (tetrabutyl titanate, etc.)]
May be used.

If necessary, the reaction may be carried out with an organic solvent, such as ketones [acetone, methyl ethyl ketone (hereinafter referred to as MEK), methyl isobutyl ketone, etc.], esters (ethyl acetate, butyl acetate, ethyl cellosolve acetate, etc.), ethers (dioxane, Tetrahydrofuran, etc.), hydrocarbons (n-hexane, n-heptane, cyclohexane, tetralin, toluene, xylene, etc.), alcohols [methanol, ethanol, isopropyl alcohol (hereinafter referred to as IPA), n-propyl ether, Butanol), amides (dimethylformamide, dimethylacetamide, etc.), N-methylpyrrolidone, etc., or an organic solvent may be added during or after the reaction.

The number average molecular weight of (U) is usually 5,000
~ 200,000, preferably 8,000-100,0
00. When the number average molecular weight is less than 5,000, the blocking resistance of the coating film becomes poor when used as an ink,
If it exceeds 000, the re-solubility of the ink will decrease.
The binder of the present invention <1> is generally used as a solution obtained by dissolving the resin (U) in the organic solvent exemplified above, for a solvent-based printing ink. The resin concentration of the solution is usually 10
It is 80% by weight, preferably 20 to 60% by weight. The viscosity (Brookfield viscometer) is usually 50
１００100,000 cP / 25 ° C., preferably 100-1
It is 0.000 cP / 25 degreeC.

It is preferable that the terminal isocyanate group of the resin (Ua) does not have to be present, and the concentration thereof is preferably 0.1 to 3.0% by weight, particularly 0.2 to 2.0%, more preferably 0.2 to 2.0%. 0.3 to 1.0%. If it is less than 0.1%, the molecular weight of the obtained resin is increased, and the solubility in an aqueous medium is reduced. If the content exceeds 3.0% by weight, the molecular weight of the obtained resin becomes small, and when it is used as an ink, the adhesive strength and oil resistance are reduced.

(A) and (D), which are active hydrogen components in the production of the resin (Ua), and (C) which is used if necessary.
The equivalent ratio of the total of the active hydrogen groups of (E) to the isocyanate groups of (B) is usually 1: (1.02-2), preferably 1: (1.05-1.5). The method for producing (Ua) is not particularly limited, and it may be produced by a one-shot method in which the components are reacted at the same time as in (Us) or a multi-step method. The reaction temperature in the production of (Ua) is also (U
Same as s).

In order to accelerate the reaction if necessary, a catalyst used in a usual urethane reaction may be used, and the usable catalyst is also the same as (Us). Also (U
As in the case of s), the reaction may be carried out in an organic solvent, if necessary, or the organic solvent may be added during or after the reaction.
The solvent that can be used is the same as (Us). Resin (Ua)
Has the same number average molecular weight as that of the polyurethane resin (U). The resin concentration of the binder of <2> is usually 10 to 80% by weight, preferably 20 to 60% by weight. The viscosity (Brookfield viscometer) is usually 50-100,00
0 cP / 25 ° C., preferably 100 to 10,000 cP
/ 25 ° C.

The resin (Uaq) has a structure in which an acid group is neutralized, and is obtained, for example, by neutralizing the resin (Ua) with ammonia and / or an organic amine. Specific examples of the organic amine used for neutralization include those having preferably 6 or less carbon atoms, such as trimethylamine, triethylamine, and triethanolamine, and mixtures of two or more thereof. The carbon number of the organic amine is preferably 6 or less from the viewpoint of volatility from the printed coating film. However, for neutralization, ammonia having good volatility and having little residual odor after printing is more preferable.

The aqueous medium in the present invention <2> includes water or a combination of water and a water-soluble organic solvent.
Examples of the water-soluble organic solvent include methanol, ethanol, I
PA, methyl cellosolve, ethyl cellosolve, cellosolve acetate, acetone, MEK, dioxane, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like. When water and a water-soluble organic solvent are used in combination, water is usually at least 50% by weight, preferably 70% by weight.
Above, especially 80% or more.

As an example of the method for producing the aqueous binder of <2>, the above-mentioned (A) can be prepared in the presence or absence of an organic solvent.
(B), (D), and if necessary, (C) and (E) are reacted to synthesize a polyurethane resin having an isocyanate group at the molecular terminal, and ammonia is added to the resin to block the isocyanate group at the molecular terminal. A method of obtaining an aqueous binder by dissolving or dispersing and diluting in an aqueous medium after neutralizing an acid group (such as a carboxyl group) and removing an organic solvent as necessary; adding an organic amine to (Ua), After neutralizing the group, a method of dissolving or dispersing the group in an aqueous medium, elongating the chain with water and / or the polyamine compound (c2), and removing an organic solvent as necessary to obtain an aqueous binder may be mentioned. Among these methods, the method is preferable because the volatility of ammonia from the printed coating film is good and the re-solubility of the ink is good.

The binder of <2> may contain, as optional components, the following additives such as an antifoaming agent, a preservative and an antifreezing agent. Antifoaming agent: Silicone-based or alcohol-based antifoaming agent Preservative: Organic nitrogen sulfur compound-based or organic sulfur halide-based antiseptic, etc. Antifreeze: Ethylene glycol, propylene glycol, etc.

The solvent-based printing ink of <3> is an organic solvent dispersion containing the binder and pigment of <1> as main components. The pigment is not particularly limited, and ordinary inorganic and organic pigments can be used. If necessary, additives such as resins, solvents and stabilizers for other ink binders, and pigment dispersants may be added. Other resins include polyamide resins, nitrocellulose, acrylic resins, vinyl acetate resins, vinyl chloride resins, styrene-maleic acid copolymer resins, chlorinated polyolefins, epoxy resins and rosin resins. Examples of the stabilizer include hindered phenol-based, hydrazine-based, benzophenone-based, benzotriazole-based, oxalic acid anilide-based, and hindered amine-based stabilizers. Examples of the pigment dispersant include sorbitan fatty acid esters, partial fatty acid esters of polyacrylic acid, alkylamine fatty acid salts, and alkyldiamines. The mixing method of each component is not particularly limited, and <3> can be manufactured using a usual ink manufacturing apparatus such as a three-roll, ball mill, and sand grinder mill.

The formulation examples of the printing ink of <3> are as follows (% is% by weight). Binder of the present invention <1> (amount of solid content) 10 to 30% Pigment 5 to 40% Optional component Other resins (amount of solid content) 0 to 10% Additive (amount of solid content) 0 to 3 % Solvent (including solvent in resin component) 40-70%

The printing ink of <3> may be used as a one-pack type printing ink, but can also be used as a two-pack type ink in combination with a polyisocyanate-based curing agent.
In this case, as the polyisocyanate-based curing agent, for example, an adduct synthesized from 1 to 4 mol of trimethylolpropane and 3 to 4 mol of 1,6-hexamethylene diisoisocyanate, tolylene diisocyanate or isophorone diisocyanate; Trimers containing isocyanurate groups synthesized by cyclotrimerization of isocyanate groups of hexamethylene diisoisocyanate or isophorone diisocyanate; partial burette synthesized from 1 mol of water and 3 mol of 1,6-hexamethylene diisocyanate Reactants and mixtures of two or more of these are preferred. When used as a two-part printing ink, the amount of the polyisocyanate-based curing agent added is usually 0.5 to 10% by weight based on the ink. The printing with the printing ink of <3> may be the same as the case of the conventional gravure ink or flexographic ink.

The aqueous printing ink of <4> is, for example, <2>
> A pigment, water as an aqueous medium and / or
Alternatively, a mixture of alcohols (ethyl alcohol, isopropyl alcohol, etc.) and other optional additives such as an aqueous resin and a stabilizer, a pigment dispersant, a thickener, etc., as described below, is added to a three-roll, sand grinder. It is obtained by kneading using a usual ink production apparatus such as a mill or a ball mill.

Other aqueous resins: acrylic resin, vinyl acetate resin, vinyl chloride resin, styrene maleic acid copolymer resin, chlorinated polyolefin, epoxy resin, rosin resin, etc. Stabilizer: used in the above <3> As well as stabilizers that can be. Pigment dispersant: Nonionic surfactant such as nonylphenol ethylene oxide adduct, anionic surfactant such as sodium alkyl sulfate, etc. Thickener: Cellulose derivative, starch derivative, polyacrylate, polyethylene oxide, polyvinyl Alcohol etc.

An example of the formulation of the printing ink of <4> is as follows (% is% by weight). Binder of the present invention (amount of solid content) 10 to 30% Pigment 5 to 40% Optional component Other aqueous resin (amount of solid content) 0 to 10% Additive (amount of solid content) 0 to 3% Aqueous medium ( (Including the aqueous medium in the resin component) 40 to 70%

The aqueous printing ink <4> comprising the binder <2> may be used as a one-part ink, but may also be used as a two-part ink in combination with a curing agent. As the curing agent, for example, an aqueous polyepoxy compound [aqueous emulsion of bisphenol A type glycidyl ether and hydrogenated bisphenol A type glycidyl ether; glycidyl ether of ethylene glycol or polyethylene glycol;
Glycidyl ethers of polyhydric alcohols such as glycerin, polyglycerin, trimethylolpropane, and sorbitol; glycidyl ethers obtained by adding alkylene oxides (2 to 3 carbon atoms) to glycerin, trimethylolpropane, sorbitol, and the like] Aqueous amino resin [methylolated and / or alkoxymethylated urea or melamine resin], polyisocyanate compound [IPDI and HDI 3
Aqueous emulsion of polyisocyanate obtained by blocking a quantified product with methyl ethyl ketoxime or ε-caprolactam], and an aqueous oxazoline compound. Of these, aqueous polyepoxy compounds are preferred. The amount of the curing agent to be added is generally 0 to 30% by weight, preferably 0 to 20% by weight, based on the weight of the aqueous polyurethane resin.

The printing inks <3> and <4> are particularly suitable as special gravure inks and flexographic inks. Applicable objects include polyester films, nylon films, polypropylene films, polyethylene films, polyvinyl chloride films, cellophane films, and the like.

[0047]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto. In the following, “part” indicates “part by weight” and “%” indicates “% by weight”. [Synthesis of Polymer Polyol (A1)] Synthesis Example 1 "Linearene 12" [molecular weight 168, 1-dodecene; Idemitsu Petrochemical Co., Ltd. in a four-necked flask equipped with a reflux condenser, a thermometer, a nitrogen inlet tube, and a stirrer. 254 parts, acetic acid 159
And 3 parts of sulfuric acid, and a 60% aqueous hydrogen peroxide solution was gradually added dropwise while maintaining the temperature at 85 ° C. Thereafter, 271 parts of toluene, 90 parts of sodium hydroxide, and 200 parts of water were added, and neutralization and hydrolysis were performed. Further, 11 parts of hydrochloric acid was added, and then liquid separation was performed using a separating funnel, and 520 parts of a supernatant toluene solution was added. I got This was transferred to another four-necked flask, toluene was removed, and then purified by distillation under reduced pressure.
220 parts of dodecanediol were obtained. In a separate four-necked flask, 200 parts of the above 1,2-dodecanediol and 140 parts of adipic acid were charged, and nitrogen gas was passed through under normal pressure to give 1 part.
Esterification was carried out at 90 to 210 ° C. while distilling off water. When the acid value of the produced polyester became 1 or less, the degree of pressure reduction was increased to complete the reaction. The obtained polyester [hereinafter referred to as polyester diol [1]] had a hydroxyl value of 55.2, an acid value of 0.3 and a molecular weight of 2020.

Synthesis Example 2 In a four-necked flask equipped with a reflux condenser, a thermometer, a nitrogen introducing tube, and a stirrer, 381 parts of “Linearene 18” (molecular weight: 252, 1-octadecene; manufactured by Idemitsu Petrochemical Co., Ltd.) Acetic acid 1
59 parts and 3 parts of sulfuric acid were charged, and a 60% aqueous hydrogen peroxide solution was gradually added dropwise while maintaining the temperature at 85 ° C. afterwards,
Toluene 271 parts, sodium hydroxide 90 parts, water 200
The mixture was neutralized and hydrolyzed, and 11 parts of hydrochloric acid was further added. Then, liquid separation was performed using a separating funnel to obtain 520 parts of a supernatant toluene solution. This was transferred to another four-necked flask, toluene was removed, and then purified by distillation under reduced pressure.
340 parts of octadecanediol were obtained. In another four-necked flask, 200 parts of the above-mentioned 1,2-octadecanediol and 94 parts of adipic acid were charged, and esterification was carried out at 190 to 210 ° C. while passing nitrogen gas under normal pressure while distilling off water. When the acid value of the produced polyester became 1 or less, the degree of pressure reduction was increased to complete the reaction. The obtained polyester [hereinafter referred to as polyester diol [2]] had a hydroxyl value of 56.5, an acid value of 0.3 and a molecular weight of 1975.

Synthesis Example 3 A four-necked flask equipped with a reflux condenser, a thermometer, a nitrogen introducing tube, and a stirrer was charged with 186 parts of 1-dodecanol, 138 parts of epichloropidrine and 200 parts of toluene, and the temperature was 35 ° C. , And 60 parts of sodium hydroxide was gradually added to carry out the reaction. Thereafter, 200 parts of water was added, and liquid separation was performed with a liquid separating funnel to obtain a supernatant toluene solution. This was transferred to another four-necked flask, 1 part of sulfuric acid was added, and the temperature was 85 ° C.
For 5 hours. After cooling to 40 ° C., 1 part of sodium hydroxide was added for neutralization, and the mixture was separated with a separating funnel to obtain 500 parts of a supernatant toluene solution. This was transferred to another four-necked flask, toluene was removed, and then purified by distillation under reduced pressure to obtain glycerindodecanol monoether 220.
Got a part. In a separate four-necked flask, 200 parts of the above-mentioned glycerin dodecanol monoether and 92 parts of adipic acid were charged, and nitrogen gas was passed under normal pressure, and the temperature was lowered to 190 to 210 ° C.
The esterification was carried out while distilling off water with. When the acid value of the produced polyester became 1 or less, the degree of pressure reduction was increased to complete the reaction. The obtained polyester [hereinafter referred to as polyester diol [3]] had a hydroxyl value of 57.0, an acid value of 0.2 and a molecular weight of 1970.

Synthesis Example 4 In a separate four-necked flask, 286 parts of 1,2-octadecanediol obtained in Synthesis Example 2, 1714 parts of ε-caprolactone monomer, and 0.02 part of tetrabutyl titanate were charged. Through nitrogen gas, reaction temperature 160 ~
The reaction was performed at 180 ° C. for 6 hours. The obtained polylactone diol [hereinafter referred to as polylactone diol [4]] had a hydroxyl value of 56.0, an acid value of 0.1 and a molecular weight of 2002.

Synthesis Example 5 In an autoclave, 3 parts of potassium hydroxide were added to 286 parts of 1,2-octadecanediol obtained in Synthesis Example 2, and the mixture was alcoholated by dehydration at 130 ° C. under reduced pressure.
At a reaction temperature of 110 ° C., 1714 parts of PO was injected to cause a reaction, and aging was performed at 130 ° C. Polyetherdiol [hereinafter referred to as polyetherdiol [5]] obtained by dehydration at 130 ° C. after neutralization and activated clay treatment had a hydroxyl value of 55.0 and a molecular weight of 2,040.

Synthesis Example 6 An autoclave was charged with 185 parts of dodecylamine.
At a temperature of 110 ° C., 88 parts of EO were injected and reacted to obtain 1
Aging was performed at 30 ° C. to obtain N-dodecyl-diethanolamine. In another flask, 200 parts of N-dodecyl-diethanolamine obtained and 87.5 parts of adipic acid were charged, and esterification was carried out at 190 to 210 ° C. while distilling water at 190 to 210 ° C. under a normal pressure through nitrogen gas. When the acid value of the produced polyester became 1 or less, the degree of pressure reduction was increased to complete the reaction. The obtained polyester [hereinafter referred to as polyester diol [6]] had a hydroxyl value of 55.5 and a molecular weight of 2020.

Synthesis Example 7 An autoclave was charged with 269 parts of octadecylamine, and 88 parts of EO was injected at a temperature of 110 ° C. to cause a reaction, followed by aging at 130 ° C. to obtain N-octadecyl diethanolamine. To this, 1643 parts of ε-caprolactone monomer and 0.02 of tetrabutyl titanate were added.
The reaction temperature was 160
The reaction was carried out at ℃ 180 ° C. for 6 hours. The obtained polylactone diol [hereinafter referred to as polylactone diol [7]] had a hydroxyl value of 56.1, an acid value of 0.1 and a molecular weight of 1996.

Synthesis Example 8 An autoclave was charged with 269 parts of octadecylamine and 3 parts of triethylamine.
1731 parts were press-fitted and reacted, and aged at 130 ° C. After neutralization and activated clay treatment, the polyether [hereinafter referred to as polyether diol [8]] obtained by dehydration had a hydroxyl value of 56.0 and a molecular weight of 2004.

Synthesis Example 9 In an autoclave, 24 parts of ethylene glycol and 3 parts of potassium hydroxide were added, followed by dehydration at 130 ° C. under reduced pressure to carry out alcoholation. Next, α-dodecene epoxide 800
Part at a reaction temperature of 130-140 ° C., followed by PO
And pressurized at a reaction temperature of 100 to 110 ° C., and aged at 130 ° C. Polyetherdiol [hereinafter referred to as polyetherdiol [9]] obtained by dehydration at 130 ° C. after neutralization and activated clay treatment had a hydroxyl value of 55.0 and a molecular weight of 2020.

[Binder <1> and Printing Ink <3
Example 1] In a four-necked flask equipped with a thermometer and a stirrer, 238 parts of polyesterdiol [1] and 47.6 parts of IPDI were charged and reacted at 120 ° C for 5 hours with stirring, and then at 40 ° C. Then, 500 parts of MEK was added and dissolved to obtain a MEK solution of an NCO-terminated polyurethane resin having an NCO content of 1.00%. To the obtained MEK solution, 200 parts of IPA and 14.2 parts of isophoronediamine were added to perform chain extension, and the solid content was 30.0%, the viscosity was 660 cP / 25 ° C., and the amine value (1
1.3 and / or secondary amine value; the same applies to the following examples) to obtain a polyurethane resin solution of 1.3. The number average molecular weight (hereinafter the same) of the resin measured by gel permeation chromatography (GPC) was 25,000. Using the obtained polyurethane resin solution as a binder, a raw material mixture having the following formulation was put into a steel can having an inner volume of 500 ml, and kneaded with a paint conditioner (manufactured by Red Devil Co., Ltd.) for 1 hour to form a printing ink. [1] was obtained. Polyurethane resin solution 100 parts Pigment (rutile type titanium oxide) 80 parts IPA 30 parts MEK 90 parts Ceramic ball 150 parts

Example 2 A four-necked flask equipped with a thermometer and a stirrer was charged with 238 parts of polyester diol [2] and 47.6 parts of IPDI, reacted at 120 ° C. for 5 hours with stirring, and then reacted at 40 ° C.
Then, 500 parts of MEK was added and dissolved to obtain a MEK solution of an NCO-terminated polyurethane resin having an NCO content of 1.02%. To the obtained MEK solution, 200 parts of IPA and 14.2 parts of isophoronediamine were added to carry out chain extension to obtain a polyurethane resin solution having a solid content of 30.0%, a viscosity of 300 cP / 25 ° C., and an amine value of 1.4. Was. The number average molecular weight of this resin was 22,000. A printing ink [2] was obtained in the same manner as in Example 1 except that the obtained resin solution was used as a binder.

Example 3 In a four-necked flask equipped with a thermometer and a stirrer, 246 parts of polylactone diol [4] and 47.6 parts of IPDI were added.
After reacting at 120 ° C for 5 hours with stirring, 40 ° C
Then, 500 parts of MEK was added and dissolved to obtain a MEK solution of an NCO-terminated polyurethane resin having an NCO content of 1.00%. 200 parts of IPA and 14.2 parts of isophoronediamine were added to the obtained MEK solution to extend the chain, and the solid content was 30.0%, the viscosity was 260 cP / 25 ° C., and the amine value was 1.3.
Was obtained. The number average molecular weight of this resin was 27,000. A printing ink [3] was obtained in the same manner as in Example 1 except that the obtained resin solution was used as a binder.

Example 4 A four-necked flask equipped with a thermometer and a stirrer was charged with 246 parts of polyether diol [5] and 47.6 parts of IPDI, and reacted at 120 ° C. for 5 hours with stirring.
Then, 500 parts of MEK was added and dissolved to obtain a MEK solution of an NCO-terminated polyurethane resin having an NCO content of 1.00%. 200 parts of IPA and 14.2 parts of isophoronediamine were added to the obtained MEK solution to perform chain extension, and the solid content was 30.0%, the viscosity was 200 cP / 25 ° C., and the amine value was 1.4.
Was obtained. The number average molecular weight of this resin was 22,000. A printing ink [4] was obtained in the same manner as in Example 1 except that the obtained resin solution was used as a binder.

Example 5 A four-necked flask equipped with a thermometer and a stirrer was charged with 246 parts of polyester diol [6] and 47.6 parts of IPDI, reacted at 120 ° C. for 5 hours with stirring, and then reacted at 40 ° C.
Then, 500 parts of MEK was added and dissolved to obtain a MEK solution of an NCO-terminated polyurethane resin having an NCO content of 1.03%. To the obtained MEK solution, 200 parts of IPA and 14.2 parts of isophoronediamine were added to perform chain extension, and the solid content was 30.0%, the viscosity was 400 cP / 25 ° C., and the amine value was 1.4.
Was obtained. The number average molecular weight of this resin was 20,000. A printing ink [5] was obtained in the same manner as in Example 1 except that the obtained resin solution was used as a binder.

Example 6 A four-necked flask equipped with a thermometer and a stirrer was charged with 246 parts of polylactone diol [7] and 47.6 parts of IPDI, and reacted at 120 ° C. for 5 hours with stirring. ° C
Then, 500 parts of MEK was added and dissolved to obtain a MEK solution of an NCO-terminated polyurethane resin having an NCO content of 1.00%. 200 parts of IPA and 14.2 parts of isophoronediamine were added to the obtained MEK solution to perform chain extension, and the solid content was 30.0%, the viscosity was 600 cP / 25 ° C., and the amine value was 1.4.
Was obtained. The number average molecular weight of this resin was 23,000. A printing ink [6] was obtained in the same manner as in Example 1 except that the obtained resin solution was used as a binder.

Example 7 A four-necked flask equipped with a thermometer and a stirrer was charged with 246 parts of polyether diol [8] and 47.6 parts of IPDI, and reacted at 120 ° C. for 5 hours with stirring. ° C
Then, 500 parts of MEK was added and dissolved to obtain a MEK solution of an NCO-terminated polyurethane resin having an NCO content of 1.05%. To the obtained MEK solution, 200 parts of IPA and 14.2 parts of isophoronediamine were added to perform chain extension, and the solid content was 30.0%, the viscosity was 560 cP / 25 ° C., and the amine value was 1.4.
Was obtained. The number average molecular weight of this resin was 23,000. A printing ink [7] was obtained in the same manner as in Example 1 except that the obtained resin solution was used as a binder.

Example 8 A four-necked flask equipped with a thermometer and a stirrer was charged with 246 parts of polyether diol [9] and 47.6 parts of IPDI, and reacted at 120 ° C. for 5 hours with stirring. ° C
Then, 500 parts of MEK was added and dissolved to obtain a MEK solution of an NCO-terminated polyurethane resin having an NCO content of 1.03%. 200 parts of IPA and 14.2 parts of isophorone diamine were added to the obtained MEK solution to perform chain extension, and the solid content was 30.0%, the viscosity was 660 cP / 25 ° C., and the amine value was 1.4.
Was obtained. The number average molecular weight of this resin was 23,000. A printing ink [8] was obtained in the same manner as in Example 1 except that the obtained resin solution was used as a binder.

[Production of Comparative Binder and Comparative Organic Solvent-Containing Printing Ink] Comparative Example 1 In a four-necked flask equipped with a thermometer and a stirrer, 2 polybutylene adipatediol having a number average molecular weight of 2,000 was added.
46 parts, 47.6 parts of IPDI were charged, and the mixture was stirred at 120 ° C.
After cooling to 40 ° C., 500 parts of MEK was added and dissolved to obtain a MEK solution of an NCO-terminated polyurethane resin having an NCO content of 1.02%. MEK obtained
200 parts of IPA and 14.2 of isophoronediamine were added to the solution.
Part of the mixture, the chain was extended, the solid content was 30.0%, and the viscosity was 900.
A polyurethane resin solution having a cP / 25 ° C. and an amine value of 1.4 was obtained. A comparative printing ink was obtained in the same manner as in Example 1 except that the obtained resin solution was used as a binder.

Comparative Example 2 In a four-necked flask equipped with a thermometer and a stirrer, 246 parts of polypropylene diol having a number average molecular weight of 2,000 were added.
47.6 parts of IPDI was charged and reacted at 120 ° C. for 5 hours with stirring, then cooled to 40 ° C., and 672 parts of MEK were added and dissolved to obtain a MEK solution of an NCO-terminated polyurethane resin having an NCO content of 1.00%. . IP to the obtained MEK solution
A200 parts, 14.2 parts of isophoronediamine and 1.8 parts of di-n-butylamine were added to extend the chain, and a polyurethane resin solution having a solid content of 30.0%, a viscosity of 12,000 cP / 25 ° C. and an amine value of 0 was prepared. Obtained. A comparative printing ink was obtained in the same manner as in Example 1 except that the obtained resin solution was used as a binder.

Comparative Example 3 A comparative printing ink was obtained in the same manner as in Example 1 except that "Hardlen 15L" (a chlorinated polypropylene resin solution, manufactured by Toyo Kasei Co., Ltd.) was used as a binder. [Production of Binder <2> and Aqueous Printing Ink <4>] Example 9 A pressure polymerization reactor equipped with a thermometer and a stirrer was used to prepare 618 parts of polyester diol [1] and 1 part of 1,4-butanediol.
9 parts, 102 parts of dimethylolpropionic acid, IPDI
290 parts and acetone 670 parts, and stirred at 80 ° C.
For 10 hours to obtain an acetone solution of an NCO-terminated polyurethane resin having an NCO content of 0.20%. The acetone solution was cooled to 30 ° C., and 42 parts of 28% ammonia water was added. Next, 1515 parts of water was added to the acetone solution, acetone was removed at 50 to 60 ° C. under reduced pressure, and the solid content was 40.0 parts.
%, And a polyurethane resin aqueous solution having a viscosity of 660 cP / 25 ° C. was obtained. Number average molecular weight of this resin measured by gel permeation chromatography (GPC) (the same applies hereinafter)
Was 15,000. Using the obtained polyurethane resin solution as a binder, a raw material mixture having the following formulation was put into a steel can having an inner volume of 500 ml, and kneaded for 1 hour with a paint conditioner (manufactured by Red Devil Co.) to obtain an aqueous printing ink. [9] was obtained. Aqueous polyurethane resin solution 100 parts Pigment (rutile type titanium oxide) 80 parts IPA 30 parts Water 90 parts Ceramic balls 150 parts

Example 10 A pressure polymerization reactor equipped with a thermometer and a stirrer was charged with 618 parts of polyester diol [2] and 1,4-butanediol 2
0 parts, dimethylolpropionic acid 102 parts, IPDI2
90 parts and 670 parts of acetone were charged and stirred at 80 ° C.
For 10 hours to obtain an acetone solution of an NCO-terminated polyurethane resin having an NCO content of 0.20%. The obtained acetone solution was cooled to 30 ° C., and 28% aqueous ammonia 4
Two parts were added. Next, 1515 parts of water was added to the acetone solution, and acetone was removed under reduced pressure at 50 to 60 ° C.
A 0.0% polyurethane resin aqueous solution having a viscosity of 360 cP / 25 ° C. was obtained. The number average molecular weight of this resin is 13,000
Met. A printing ink [10] was obtained in the same manner as in Example 9 except that the obtained resin liquid was used as a binder.

Example 11 A pressure polymerization reactor equipped with a thermometer and a stirrer was charged with 618 parts of polyester diol [3] and 1,4-butanediol 2
0 parts, dimethylolpropionic acid 102 parts, IPDI2
90 parts and 670 parts of acetone were charged and stirred at 80 ° C.
For 10 hours to obtain an acetone solution of an NCO-terminated polyurethane resin having an NCO content of 0.20%. The acetone solution was cooled to 30 ° C., and 42 parts of 28% ammonia water was added. Next, 1515 parts of water is added to the acetone solution,
The acetone was removed at 50-60 ° C under reduced pressure to give a solid content of 40.
A 0% polyurethane resin aqueous solution having a viscosity of 530 cP / 25 ° C. was obtained. The number average molecular weight of this resin was 15,000. A printing ink [11] was obtained in the same manner as in Example 9 except that the obtained resin liquid was used as a binder.

Example 12 A pressure polymerization reactor equipped with a thermometer and a stirrer was charged with 618 parts of polylactone diol [4] and 1,4-butanediol 2
0 parts, dimethylolpropionic acid 102 parts, IPDI2
90 parts and 670 parts of acetone were charged and stirred at 80 ° C.
For 10 hours to obtain an acetone solution of an NCO-terminated polyurethane resin having an NCO content of 0.20%. The acetone solution was cooled to 30 ° C., and 42 parts of 28% ammonia water was added. Next, 1515 parts of water is added to the acetone solution,
The acetone was removed at 50-60 ° C under reduced pressure to give a solid content of 40.
A polyurethane resin aqueous solution having a viscosity of 0% and a viscosity of 600 cP / 25 ° C. was obtained. The number average molecular weight of this resin was 14,000. A printing ink [12] was obtained in the same manner as in Example 9 except that the obtained resin liquid was used as a binder.

Example 13 A pressure polymerization reactor equipped with a thermometer and a stirrer was charged with 618 parts of polyether diol [5] and 1,4-butanediol 2
0 parts, 102 parts of dimethylolpropionic acid, 290 parts of IPDI and 670 parts of acetone were charged, and stirred.
C. for 10 hours at an NCO content of 0.20%
An acetone solution of the base-terminated polyurethane resin was obtained. The acetone solution was cooled to 30 ° C.
Parts were added. Next, 1515 parts of water was added to the acetone solution, and acetone was removed under reduced pressure at 50 to 60 ° C.
A 0.0% polyurethane resin aqueous solution having a viscosity of 500 cP / 25 ° C. was obtained. The number average molecular weight of this resin is 15,000
Met. A printing ink [13] was obtained in the same manner as in Example 9 except that the obtained resin liquid was used as a binder.

Example 14 A pressure polymerization reactor equipped with a thermometer and a stirrer was charged with 618 parts of polyester diol [6] and 1,4-butanediol 2
0 parts, 102 parts of dimethylolpropionic acid, 290 parts of IPDI and 670 parts of acetone were charged, and stirred.
C. for 10 hours at an NCO content of 0.20%
An acetone solution of the base-terminated polyurethane resin was obtained. The acetone solution was cooled to 30 ° C.
Parts were added. Next, 1515 parts of water was added to the acetone solution, and acetone was removed under reduced pressure at 50 to 60 ° C.
A 0.0% polyurethane resin aqueous solution having a viscosity of 360 cP / 25 ° C. was obtained. The number average molecular weight of this resin is 12,000
Met. A printing ink [14] was obtained in the same manner as in Example 9 except that the obtained resin liquid was used as a binder.

Example 15 A pressure polymerization reactor equipped with a thermometer and a stirrer was charged with 618 parts of polylactone diol [7] and 1,4-butanediol 2
0 parts, dimethylolpropionic acid 102 parts, IPDI2
90 parts and 670 parts of acetone were charged and stirred at 80 ° C.
For 10 hours to obtain an acetone solution of an NCO-terminated polyurethane resin having an NCO content of 0.20%. The acetone solution was cooled to 30 ° C., and 42 parts of 28% ammonia water was added. Next, 1515 parts of water is added to the acetone solution,
The acetone was removed at 50-60 ° C under reduced pressure to give a solid content of 40.
A 0% polyurethane resin aqueous solution having a viscosity of 560 cP / 25 ° C. was obtained. The number average molecular weight of this resin was 17,000. A printing ink [15] was obtained in the same manner as in Example 9 except that the obtained resin liquid was used as a binder.

Example 16 A pressure polymerization reactor equipped with a thermometer and a stirrer was charged with 618 parts of polyether diol [8] and 1,4-butanediol 2
0 parts, dimethylolpropionic acid 102 parts, IPDI2
90 parts and 670 parts of acetone were charged and stirred at 80 ° C.
For 10 hours to obtain an acetone solution of an NCO-terminated polyurethane resin having an NCO content of 0.20%. The acetone solution was cooled to 30 ° C., and 42 parts of 28% ammonia water was added. Next, 1515 parts of water is added to the acetone solution,
The acetone was removed at 50-60 ° C under reduced pressure to give a solid content of 40.
A polyurethane resin aqueous solution having 0% viscosity and 780 cP / 25 ° C. was obtained. The number average molecular weight of this resin was 16,000. A printing ink [16] was obtained in the same manner as in Example 9 except that the obtained resin liquid was used as a binder.

Example 17 A pressure polymerization reactor equipped with a thermometer and a stirrer was charged with 618 parts of polyether diol [9] and 1,4-butanediol 2
0 parts, dimethylolpropionic acid 102 parts, IPDI2
90 parts and 670 parts of acetone were charged and stirred at 80 ° C.
For 10 hours to obtain an acetone solution of an NCO-terminated polyurethane resin having an NCO content of 0.20%. The acetone solution was cooled to 30 ° C., and 42 parts of 28% ammonia water was added. Next, 1515 parts of water is added to the acetone solution,
The acetone was removed at 50-60 ° C under reduced pressure to give a solid content of 40.
A polyurethane resin aqueous solution having 0% and a viscosity of 300 cP / 25 ° C. was obtained. The number average molecular weight of this resin was 13,000. A printing ink [17] was obtained in the same manner as in Example 9 except that the obtained resin liquid was used as a binder.

[Production of Comparative Aqueous Binder and Comparative Aqueous Printing Ink] Comparative Example 4 Polybutylene adipate glycol 618 having a number average molecular weight of 2000 was placed in a pressure polymerization vessel equipped with a thermometer and a stirrer.
, 27 parts of 1,4-butanediol, 102 parts of dimethylolpropionic acid, 290 parts of IPDI and 690 parts of acetone, and reacted under stirring at 80 ° C. for 20 hours.
An acetone solution of a polyurethane resin having an NCO content of 0.02% was obtained. This acetone solution is cooled to 30 ° C. and
42 parts of aqueous ammonia were added. Next, 1523 parts of water was added to the acetone solution, and acetone was removed at 50 to 60 ° C. under reduced pressure to obtain a polyurethane resin aqueous solution having a solid content of 40.0% and a viscosity of 2,000 cP / 25 ° C. The number average molecular weight of this resin was 250,000. A comparative printing ink was obtained in the same manner as in Example 9 except that the obtained resin liquid was used as a binder.

Comparative Example 5 618 parts of a polypropylene glycol having a number average molecular weight of 2,000,
27 parts of 4-butanediol, 102 parts of dimethylolpropionic acid, 290 parts of IPDI and 690 parts of acetone were charged and reacted at 80 ° C. for 20 hours with stirring to obtain an acetone solution of a polyurethane resin having an NCO content of 0.02%.
The acetone solution was cooled to 30 ° C., and 42 parts of 28% ammonia water was added. Next, 1523 parts of water was added to the acetone solution, and acetone was removed at 50 to 60 ° C. under reduced pressure to obtain a polyurethane resin aqueous solution having a solid content of 40.0% and a viscosity of 1600 cP / 25 ° C. The number average molecular weight of this resin is 20
It was 0000. A comparative printing ink was obtained in the same manner as in Example 9 except that the obtained resin solution was used as a binder.

Comparative Example 6 A comparative printing ink was obtained in the same manner as in Example 9 except that "Hardlen EA-11" (chlorinated polypropylene resin emulsion, manufactured by Toyo Kasei Co., Ltd.) was used as a binder.

[Performance Test of Printing Ink Containing Organic Solvent] Test Examples and Comparative Test Examples (Part 1) Printing Inks [1] to [8] and Comparative Printing Inks
The following performance tests were performed using each of them. The results are shown in Tables 1 and 2. Redissolvability: 2～3Myu the printing ink to the glass plate at a solids
m with a bar coater to obtain a thickness of 1 m at room temperature.
After leaving the ink surface semi-dry by leaving it for 0 seconds, the solvent (ME
The glass plate was immersed in K / IPA = 2/1), and the resolubility of the ink film was observed. Evaluation criteria ○: The coating film is re-dissolved ×: The coating film is left undissolved

Cellotape Adhesion : A printing ink is coated on a surface-treated polypropylene film (surface-treated OPP), a surface-treated polyester film (surface-treated PET) and a surface-treated nylon film so as to have a solid content of 2 to 3 μm. And dried at 60 ° C. for 1 minute and left at room temperature for 1 day. A cellophane (Nichiban, 12 mm width) was stuck on the coating surface, and the state of the coating surface when one end of the cellophane was rapidly peeled off in a direction perpendicular to the coating surface was observed. Evaluation criteria ◎: The coating film is not peeled off 塗膜: The coating film remains at 80 to 100% Δ: The coating film remains at 50 to 80% ×: The remaining of the coating film is less than 50%

Blocking resistance : The coated surface of the coated test piece (coated on a PET film) obtained by the same method as the cellophage adhesiveness test was overlaid on the non-coated surface, and the test was performed at 40 ° C. and 60% RH at 60% RH. A load of 0 kgf / cm ² was applied, and after 24 hours, it was peeled off and the state of the surface was observed.

Oil resistance : A coated test piece (coated on a PET film) obtained by the same method as in the cellophane adhesive test was used at 25 ° C.
After immersion in rapeseed oil for 24 hours, the surface condition was observed. Evaluation criteria A: No change in the surface of the coating film. ：: The gloss of the coating film was slightly reduced. Δ: The coating film has blisters. X: The coating film peeled from the substrate.

Water resistance : A coated test piece (coated on a PET film) obtained by the same method as the cellophane adhesive test was used at 25 ° C.
After immersion in water for 24 hours, a cellophane tape was stuck on the coated surface, and the state of the coated surface when one end of the cellophane tape was rapidly peeled off in a direction perpendicular to the coated surface was observed. Evaluation criteria A: No change in the surface of the coating film. ：: The gloss of the coating film was slightly reduced. Δ: The coating film has blisters. X: The coating film peeled from the substrate.

Laminating adhesiveness : A printing ink is applied to a surface-treated OPP film by a bar coater so as to have a thickness of 2 to 3 μm in solid content, dried at 60 ° C. for 1 minute, and then left at room temperature for 1 day. did. An untreated polypropylene film (CPP) was superimposed on the coated surface, and was hot-melt-bonded with a heat sealer (manufactured by Toyo Seiki Co., Ltd.) under the conditions of 180 ° C. × 2 kgf / cm ² × 1 second, and then cooled to form a laminate film. From this, a test piece having a width of 15 mm was collected, and the T peel strength (g) was measured by an autograph.

[0084]

[Table 1]

[0085]

[Table 2]

[Performance Test of Aqueous Printing Ink] Test Examples and Comparative Test Examples (Part 2) Using each of the aqueous printing inks [9] to [17] and the comparative aqueous printing ink, resolubility, cellophane tape adhesion , Blocking resistance, oil resistance, water resistance and laminate adhesion performance test. The resolubility was tested in the following manner, and other test items were tested in the same manner as in the test examples and comparative test examples (part 2). The results are shown in Tables 3 and 4.
The nylon film used for the cellophane tape adhesion test was a vinylidene chloride resin-coated nylon film (K
NY) was used.

[0087] redissolvability: so that the thickness of 2~3μm aqueous printing ink in solids to a glass plate bar - co - data - and applied in, and the ink surface in the semi-dry and left at room temperature for 2 minutes Thereafter, the resultant was immersed in a mixed solution of 5% aqueous ammonia / IPA = 5/1, and the solutions were mixed with a glass rod to observe the re-solubility of the ink coating film. Evaluation criteria ○: The coating film is re-dissolved ×: The coating film is left undissolved

[0088]

[Table 3]

[0089]

[Table 4]

[0090]

According to the present invention, the binder for printing inks can be used as a binder for both organic solvent-containing printing inks and aqueous printing inks. Regardless of the type of the OPP or other base film, suitability for laminating, particularly, direct laminating adhesiveness can be improved. Because of these effects, the printing ink binder of the present invention and the printing ink of the present invention using the same are not only useful for the existing organic solvent-containing printing ink applications, but also aimed at solvent removal. It is useful for aqueous printing ink applications in the future, especially as a special gravure printing ink binder for plastic films used for packaging materials and the like. Further, the binder of the present invention
Is excellent in adhesiveness to various base materials, not only for the above applications, but also for paint binders, adhesives,
It is also useful as a coating agent for paper and the like.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-7-3199 (JP, A) JP-A-6-100817 (JP, A) JP-A-6-100816 (JP, A) JP-A 5- 222330 (JP, A) JP-A-63-317562 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C09D 11/10 C09D 175/00-175/16 C08G 18/66

Claims (11)

(57) [Claims] 1. A polyurethane resin (U) having a polyol component (A) as a constitutional unit, wherein (A) has 3 to 3 carbon atoms.
Polymer polyol (A) containing 40 aliphatic hydrocarbon groups as side chains and having a number average molecular weight of 500 to 10,000
1) A binder for printing ink, which is a polyol component comprising at least one kind. 2. The binder according to claim 1, wherein the content of the aliphatic hydrocarbon group having 3 to 40 carbon atoms in (A) is 5 to 80% by weight. 3. (A1) is the following (A11) to (A1)
3. The binder according to claim 1, wherein the binder is at least one polymer polyol selected from 5). (A11) A 1,2-alkanediol having 5 to 42 carbon atoms (a1), a glycerin monoalkyl ether having 6 to 43 carbon atoms (a2) or a glycerin fatty acid monoester having 7 to 44 carbon atoms (a3), A polyether diol obtained by adding 2 to 4 alkylene oxides (b). (A12) A polyether diol obtained by adding 2 mol or more of an alkylamine oxide (b) having 2 to 4 carbon atoms to an alkylamine having 3 to 40 carbon atoms (a4). (A13) A polyether diol derived from an alkylene oxide composed of an α-olefin oxide (a5) having 5 to 42 carbon atoms. (A14) (a1), (a2), (a3), (A1
1) A polyester diol comprising a diol component comprising at least one diol selected from the group consisting of (A12) and (A13), and a dicarboxylic acid (c). (A15) (a1), (a2), (a3), (A1
1) A polylactone diol obtained by adding a lactone monomer (d) to a diol component comprising at least one diol selected from the group consisting of (A12) and (A13). 4. The binder according to claim 1, wherein (U) is a polyurethane resin from the polyol component (A), the organic polyisocyanate (B) and, if necessary, the chain extender (C). 5. The binder according to claim 1, which is used for printing ink for a plastic film. 6. The polyurethane resin (U) is a polyurethane resin (Uaq) having an acid group neutralized with ammonia and / or an organic amine, and the resin (Uaq).
The component (q) is diluted in an aqueous medium.
6. The binder according to any one of items 5 to 5. 7. (Uaq) is a polyol component (A),
Acid groups of a polyurethane resin (Ua) having an organic group from an organic polyisocyanate (B), a compound (D) having an acid group and at least two active hydrogen-containing groups in a molecule and, if necessary, a chain extender (C) Is a binder neutralized with ammonia and / or an organic amine. 8. The binder according to claim 6, wherein the acid group of (D) is a carboxyl group. 9. The binder according to claim 6, wherein (Uaq) contains an isocyanate group at a molecular terminal, and the isocyanate group is sealed with ammonia. 10. A solvent-based printing ink comprising the binder according to claim 1 as a main binder component. 11. An aqueous printing ink comprising the binder according to claim 6 as a main binder component.