JP2002356529A - Polyurethane resin and binder for printing ink - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a binder for a printing ink, a coating composition and a coating agent comprising a chlorine-free resin, which have excellent adhesion to various plastic films such as a polyester(PET), nylon(NY), polyethylene(PE), polypropylene(PP). SOLUTION: A polyurethane resin is obtained by reacting a hydride of a petroleum resin having an active hydrogen (1), polymer polyol (2) and diisocyanate compound (3) as main components. The polyurethane resin is also obtained by reacting the hydride (1), the polyol (2), the diisocyanate compound (3), a chain extender (4) and if necessary a chain terminator (5) as main components. The binder using the resin; a composition for a printing ink containing the binder are provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a polyurethane resin. The polyurethane resin of the present invention has good adhesion to various plastics such as polyethylene (hereinafter abbreviated as PE), polypropylene (hereinafter abbreviated as PP), polyester (hereinafter abbreviated as PET), nylon (hereinafter abbreviated as NY). For example, it can be used as a binder for various coating agents such as printing inks and paints. In particular, the polyurethane resin of the present invention is useful as a binder for printing ink.

[0002]

2. Description of the Related Art In recent years, various plastic films as packaging materials have been developed in accordance with the complexity of packaging contents and the advancement of packaging technology, and as a result, films suitable for the contents have been appropriately selected and used. It was started.

Conventionally, rosin-modified maleic resin, nitrified cotton, polyurethane resin, chlorinated polyolefin, polyamide resin, vinyl chloride-vinyl acetate copolymer resin, polyester resin and the like have been used as binders for such printing inks for plastic films. It has been, but P
None of the E, PP, PET, and NY films exhibited excellent adhesiveness to any printed material. For example, a printing ink using a polyurethane resin as a binder has excellent adhesion to PET and NY alone, but does not have sufficient adhesion to polyolefin films such as general-purpose films such as PE and PP. In addition, chlorinated polyolefins show good adhesion to polyolefin films, but do not have sufficient adhesion to PET and NY films. As described above, since the conventional binders for printing inks are individually designed so as to match the characteristics of the film used, the types thereof have been various.

[0004] In order to improve the adhesiveness to any of the above various printing materials, there has been proposed a printing ink binder in which a polyurethane resin and a chlorinated polyolefin are mixed or reacted. However, since chlorinated polyolefin contains chlorine, there are problems such as stability over time due to the dehydrochlorination reaction over time, corrosion of the filling container due to the generated hydrogen chloride, and coloring of the resin. Furthermore, chlorinated polyolefins generate chlorine gas during the recycling process and during combustion, and may cause dioxin generation. Therefore, binders for printing inks that do not contain chlorine and have a low environmental impact have been desired.

[0005]

SUMMARY OF THE INVENTION The present invention relates to PET, N
An object of the present invention is to provide a polyurethane resin having excellent adhesiveness to various plastic films such as Y, PE, and PP, and further comprising a non-chlorine resin.

[0006]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems of the prior art, and as a result, have found that the following polyurethane resins can solve all of the problems of the above-mentioned prior art. Thus, the present invention has been completed.

That is, the present invention provides a polyurethane resin obtained by reacting a hydrogenated petroleum resin having active hydrogen (1), a polymer polyol (2) and a diisocyanate compound (3) as main components; Polyurethane resin obtained by reacting resin hydride (1), polymer polyol (2), diisocyanate compound (3), chain extender (4) and, if necessary, chain stopper (5) as main components A binder for printing ink using the polyurethane resin: a printing ink composition containing the binder for printing ink.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS First, a hydride (1) of a petroleum resin having active hydrogen, which is a component of the polyurethane resin of the present invention, will be described. The hydrogenated petroleum resin having active hydrogen (1) is a polymerizable monomer (C5 fraction such as isoprene and normal pentene contained in petroleum fraction, C9 fraction such as styrene, vinyltoluene, α-methylstyrene and indene). Fractions, cyclopentadiene-based fractions such as cyclopentadiene and dicyclopentadiene, and mixtures or purified products thereof, or the polymerizable monomers separately synthesized) and an active hydrogen-containing compound (isocyanate group). A compound having an active hydrogen-containing functional group such as an alcoholic hydroxyl group, a phenolic hydroxyl group, an amino group, and a carboxyl group (hereinafter, referred to as an “active hydrogen group”) which can react with Is a compound obtained by hydrogenating a petroleum resin having active hydrogen composed of

The polymerizable monomers include PE and PP.
Since it shows good adhesiveness to polyolefin films such as, for example, and can be easily hydrogenated, cyclopentadiene as the C5 fraction, aromatic hydrocarbon as the C9 fraction, and separately synthesized polymerization corresponding to these compounds Water-soluble monomers can be suitably used.

Examples of the active hydrogen-containing compound include an alcohol compound having a polymerizable unsaturated bond such as allyl alcohol, a hydroxyl group-containing compound such as a phenolic compound, and a carboxylic acid having a polymerizable unsaturated bond such as maleic acid or its anhydride. Examples thereof include an amine compound having a polymerizable unsaturated bond such as an acid compound, aniline, and allylamine. Among these, the phenolic compound is the amount of phenolic hydroxyl groups that can be introduced into the petroleum resin having the active hydrogen (hydroxyl value).
Tends to be restricted to some extent. In addition, a petroleum resin having an active hydrogen group provided with an active hydrogen group by a carboxylic acid compound having a polymerizable unsaturated bond such as maleic acid or its anhydride tends to be easily colored when hydrogenated. On the other hand, when an active hydrogen group is provided by an alcohol compound having a polymerizable unsaturated bond such as allyl alcohol, it is easy to control the amount of hydroxyl groups, and it is difficult to color when a petroleum resin having active hydrogen is hydrogenated. There are advantages.

The above-mentioned petroleum resin having active hydrogen is prepared by allowing the above-mentioned active hydrogen-containing compound to be present in the reaction system when polymerizing the above-mentioned polymerizable monomer, by using various known polymerization methods such as a cationic polymerization method or a thermal polymerization method. Can be manufactured

Further, as another method for producing a petroleum resin having an active hydrogen, a polymer comprising the polymerizable monomer and a compound containing a functional group such as an ester and a polymerizable unsaturated group in the molecule is hydrolyzed. There is a method of decomposing. Specifically, when polymerizing the polymerizable monomer, a monomer such as vinyl acetate is present, and a polymer in which an ester group is introduced by various known polymerization methods such as a cationic polymerization method or a thermal polymerization method is synthesized. To convert the ester group into a hydroxyl group.

Among the above-mentioned methods, the method of reacting an active hydrogen-containing compound when polymerizing the above-mentioned polymerizable monomer is preferable in view of its simplicity.

As the petroleum resin having active hydrogen,
As described above, it is possible to further modify the active hydrogen group introduced into the resin to increase the reactivity, and to use the resin. For example, when the active hydrogen group introduced into the resin is a hydroxyl group or a phenolic hydroxyl group, it can be used as an adduct obtained by adding an alkylene oxide or an epoxy compound to these functional groups. Is a carboxyl group, it can also be used as an amidated product with a hydroxyamine compound.

Since the thus obtained petroleum resin having active hydrogen has active hydrogen in the molecule, it can react with the diisocyanate compound. As the resin, when the polymerizable monomer is a C9 fraction, phenol or the like is preferable as the active hydrogen-containing compound to be reacted therewith, and the polymerizable monomer is a cyclopentadiene-based fraction such as cyclopentadiene or dicyclopentadiene. In this case, allyl alcohol or the like is preferable as the active hydrogen-containing compound to be reacted therewith. Particularly, alcohol-modified dicyclopentadiene-based compounds capable of increasing the average hydroxyl group content per molecule of a petroleum resin having active hydrogen obtained. Use of a resin is preferable in that the obtained polyurethane resin can be made to have a high molecular weight.

The amount of active hydrogen in a petroleum resin having active hydrogen is, for example, when the active hydrogen-containing group is a hydroxyl group, a hydroxyl value of about 70 to 250, preferably 100 to 250.
220 is preferable. When the hydroxyl value is smaller than 70,
The reactivity between the hydride (1) of the petroleum resin having the active hydrogen and the diisocyanate compound decreases, and the adhesiveness, heat resistance, and oil resistance of the obtained polyurethane resin tend to decrease. On the other hand, when the hydroxyl value is more than 250, the water resistance of the obtained polyurethane resin tends to deteriorate.

The hydride (1) of the petroleum resin having active hydrogen used in the present invention can be obtained by hydrogenating the above-mentioned petroleum resin having active hydrogen in a molten or dissolved state in a solvent under various known hydrogenation catalysts. The reaction is carried out and obtained.

As the reaction conditions for the hydrogenation reaction, the hydrogenation pressure is about 1 to 30 MPa, preferably 3 to 25 MPa.
a, and the reaction temperature is about 50 to 350 ° C, preferably 100 to 320 ° C. When the hydrogenation pressure is less than 1 MPa or the reaction temperature is less than 50 ° C., the hydrogenation reaction tends to be difficult to proceed. Hydrogenation pressure is 3
If it exceeds 0MPa, special equipment is required,
When the reaction temperature exceeds 350 ° C., the decomposition reaction of the resin tends to be remarkable. The hydrogenation reaction time is usually about 10 minutes to 10 hours, preferably 20 minutes to
7 hours. If the reaction time is less than 10 minutes,
Since the hydrogenation reaction hardly proceeds, it is necessary to use a large amount of a catalyst. If the reaction time exceeds 10 hours, the productivity tends to be poor. The range described above does not exclude hydrogenation conditions outside the range. For example, even if the hydrogenation pressure is less than 1 MPa, a hydrogenation reaction can be performed by using a catalyst that can react at the hydrogenation pressure. It can be performed.

As the hydrogenation catalyst, various catalysts such as metals such as nickel, palladium, platinum, cobalt, rhodium, ruthenium and rhenium and metal compounds such as oxides and sulfides thereof can be used. Such a hydrogenation catalyst may be used by being supported on a carrier such as alumina, silica, silica-alumina (diatomaceous earth), carbon, and titania having a large surface area and being porous. The amount of the catalyst used is usually 0.01 to 10% by weight based on the modified hydrocarbon resin (A) as the raw material resin.
It is about.

The reaction time of hydrogenation and the amount of catalyst used have been described in the case where a batch system is employed as the reaction system. However, other reaction systems such as a flow system (fixed bed system, fluidized bed system, etc.) are used. It is also possible to employ.

As the solvent used in the hydrogenation reaction, a petroleum resin which is inert during the reaction and has active hydrogen as a raw material resin or a hydride (1) of a petroleum resin having active hydrogen which is a product is used. Any solvent can be used as long as it is a soluble solvent. For example, tetrahydrofuran, dioxane, n-hexane, n-heptane, n-octane, 2-ethylhexane, cyclohexane, decalin, terpene, isopropyl alcohol, n-butanol, 2-methyl-2-propanol, cyclohexanol, n-hexanol , 2-ethylhexanol, non-aromatic hydrocarbon solvents (for example, trade name "Shellsol D-40" manufactured by Shell Japan KK), isoparaffinic hydrocarbon solvents (for example, "Shellsol D-7")
0 "Shell Japan Co., Ltd.), and various other known mineral spirits. These may be used alone or in combination of two or more. The amount of the solvent used is not particularly limited, but is usually 5% by weight or more, preferably 10 to 70% by weight, based on the modified hydrocarbon resin (A).
It may be used within the range.

The hydride of petroleum resin (1) having active hydrogen has a hydrogenation rate of 5 to 100%, and is excellent in color tone of 3 or less based on Gardner color number (JIS K5400).

The number average molecular weight of the hydride (1) of the petroleum resin having active hydrogen is not particularly limited, but is generally preferably about 200 to 3000 in consideration of workability.

The hydride (1) of a petroleum resin having active hydrogen can be used as a constituent of the polyurethane resin of the present invention because it contains an active hydrogen group which reacts with an isocyanate group in the molecule. As an active hydrogen group, an amino group,
A carboxyl group or the like is preferred in terms of reactivity with isocyanate, but a hydroxyl group is particularly preferred because it has no odor or coloration and is easy to produce. Further, when the active hydrogen group is a hydroxyl group, it is preferable in that the resolubility in a solvent of a printing ink using the obtained polyurethane resin as a binder for the printing ink is excellent.

Examples of the high molecular polyol (2) include polyether polyols such as polymers or copolymers such as ethylene oxide, propylene oxide and tetrahydrofuran; ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, pentanediol, 3-methyl-1,5-pentanediol, 1,6-
Various known saturated or unsaturated low molecular weight glycols such as hexanediol, octanediol, 1,4-butynediol, and dipropylene glycol; alkyl glycidyl ethers such as n-butyl glycidyl ether and 2-ethylhexyl glycidyl ether; Monocarboxylic acid glycidyl esters such as tic acid glycidyl ester, adipic acid, maleic acid, fumaric acid,
Dibasic acids such as phthalic anhydride, isophthalic acid, terephthalic acid, succinic acid, oxalic acid, malonic acid, glutaric acid, pimelic acid, azelaic acid, sebacic acid, suberic acid, and corresponding acid anhydrides and dimer acids And polyester polyols obtained by ring-opening polymerization of a cyclic ester compound; and other polycarbonate polyols, polybutadiene glycols, and bisphenol A obtained by adding ethylene oxide or propylene oxide. And various known high molecular polyols generally used in the production of polyurethane resins, such as glycols.

When the polymer polyol (2) is a polymer polyol obtained from a glycol and a dibasic acid, up to 5 mol% of the glycol is glycerin, trimethylolpropane or trimethylol. Methylolethane, 1,2,6-hexanetriol, 1,2,2
Polyol such as 4-butanetriol, sorbitol and pentaerythritol can be substituted.

The number average molecular weight of the high molecular polyol (2) is appropriately determined in consideration of the solubility, drying property, blocking resistance and the like of the obtained polyurethane resin.
It is in the range of about 0 to 10000, preferably 1000 to 6000. If the number average molecular weight is less than 700, the printability tends to decrease as the solubility decreases, and if it exceeds 10,000, the drying and blocking resistance tend to decrease.

As the diisocyanate compound (3), various known aromatic, aliphatic or alicyclic diisocyanates can be used. For example, 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl isocyanate, dialkyldiphenylmethane diisocyanate,
Tetraalkyldiphenylmethane diisocyanate,
1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2, 4,4-trimethylhexamethylene diisocyanate, cyclohexane-1,
4-diisocyanate, xylylene diisocyanate,
Carboxyl groups of hydrogenated xylylene diisocyanate, isophorone diisocyanate, lysine diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, methylcyclohexane diisocyanate, m-tetramethylxylylene diisocyanate and dimer acid A typical example is dimer isocyanate in which is converted to an isocyanate group.

The polyurethane resin of the present invention comprises a hydride of a petroleum resin having active hydrogen (1), a polymer polyol (2) and a diisocyanate compound (3). The usage ratio of the hydride (1) of the petroleum resin having the active hydrogen and the polymer polyol (2) ((1) /
(2)) is determined in consideration of the adhesiveness to olefin, PET, NY, and the like, and is usually (1) /
(2) is about 1/99 to 70/30, preferably 5/9
It is in the range of 5-50 / 50. If the ratio of the hydride (1) of the petroleum resin having active hydrogen is less than 1, the adhesiveness to a polyolefin film such as PE or PP is not sufficient, and if it exceeds 70, the adhesiveness to a film such as PET or NY. Tend to be insufficient. The amount of the diisocyanate compound (3) used is determined in consideration of the amount of active hydrogen groups that react with isocyanate groups in the hydride (1) of petroleum resin having active hydrogen and the polymer polyol (2). . Usually, (equivalent of isocyanate group of diisocyanate compound (3)) / (total equivalent of hydride of petroleum resin having active hydrogen (1) and active hydrogen group of polymer polyol (2)) is 0.8 / 1 to 0.8 / 1. 1.2
/ L is preferred.

The polyurethane resin of the present invention can be made high molecular weight by using various known chain extenders (4) shown below as constituents. As the chain extender (4),
For example, ethylenediamine, propylenediamine, hexamethylenediamine, triethylenetetramine, diethylenetriamine, isophoronediamine, dicyclohexylmethane-4,4'-diamine and the like can be mentioned. Others, such as 2-hydroxyethylethylenediamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine, and di-2-hydroxypropylethylenediamine Representative examples thereof include diamines having a hydroxyl group, low molecular weight glycols described in the above-mentioned section of the polyester diol, and dimer diamines obtained by converting carboxyl groups of dimer acid into amino groups. Further, as a constituent of the polyurethane resin of the present invention, a chain length terminator (5) can be used, if necessary.
As the chain terminator (5), for example, dialkylamines such as di-n-butylamine and alcohols such as ethanol and isopropyl alcohol can be used.

When the chain extender (4) and, if necessary, the chain terminator (5) are used, (equivalent of isocyanate group of diisocyanate compound (3)) / (petroleum resin having active hydrogen) (Total equivalent of active hydrogen groups contained in hydride (1), polymer polyol (2), chain extender (4), and chain length terminator) of 0.8 / 1 to 1.2 / 1
It is preferable to set it in the range.

The method for producing the polyurethane resin of the present invention includes a hydride of a petroleum resin having active hydrogen (1), a polymer polyol (2) and a diisocyanate compound (3), and a chain extender (4) if necessary. If necessary, a one-step method in which the chain length terminator (5) is reacted at once in a suitable solvent may be mentioned. Further, the hydride (1) of the petroleum resin having active hydrogen and the polymer polyol (2) are reacted with the diisocyanate compound (3) under the condition that the isocyanate group becomes excessive, and the hydride of the petroleum resin having active hydrogen is obtained. A prepolymer having an isocyanate group at the terminal of (1) and the high molecular polyol (2) is prepared, and then this is added to a chain extender (4)
In addition, a two-stage method of reacting with a chain terminator (5) may be employed if necessary. The two-stage method is preferred for obtaining a uniform polymer solution.

When the polyurethane resin is produced by a two-stage method, the conditions for reacting the prepolymer with the chain extender (4) and, if necessary, the chain terminator (5) are not particularly limited. When the equivalent of the free isocyanate groups contained in the prepolymer is 1 equivalent, the total equivalent of the active hydrogen capable of reacting with the isocyanate groups in the chain extender (4) and the chain terminator (5) is 0.5 to 5.0. The content is preferably in the range of 2 equivalents, and particularly preferably in the range of 0.5 to 1.3 equivalents when the active hydrogen-containing functional group is an amino group. If the total equivalent weight of the active hydrogen is less than 0.5, the resulting polyurethane resin has insufficient drying, blocking resistance and film strength, and if it is greater than 2, the chain extender remains unreacted in the reaction system. It tends to remain.

Solvents used in the above-mentioned process for producing a polyurethane resin include aromatic solvents such as benzene, toluene and xylene which are well known as solvents for printing inks; esters such as ethyl acetate and butyl acetate. System solvents: methanol, ethanol, isopropanol,
Alcohol solvents such as n-butanol; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone can be used alone or in combination.

The number average molecular weight of the polyurethane resin of the present invention may be determined, for example, when the polyurethane resin is used as a binder for printing ink, such as drying property, blocking resistance, film strength, oil resistance and viscosity of the obtained printing ink. Is determined appropriately in consideration of
00 range.

In the above applications, the polyurethane resin of the present invention is usually used as a resin solution. The resin solid content concentration is not particularly limited, and when used as a printing ink, may be appropriately determined in consideration of workability during printing and the like, and is usually about 15 to 60% by weight, and the viscosity is 50 to 100%.
It is practically preferable to adjust it to a range of about 000 mPa · s / 25 ° C.

The polyurethane resin of the present invention thus obtained can be suitably used as a binder for various coating agents such as printing inks and paints, or used as it is as a coating agent for various substrates. Useful as a binder for plastics. The polyurethane resin of the present invention is used as a binder for printing ink, and a conventional means can be employed for preparing a printing ink. That is, a colorant, a solvent, and a surfactant, a wax, and other additives for improving fluidity and a surface film as necessary are appropriately compounded, and a normal ink production apparatus such as a ball mill, an attritor, and a sand mill is used. By using and kneading, a printing ink is produced. When used as a printing ink, the amount of the polyurethane resin of the present invention is preferably such that the resin solid content is 3 to 20% by weight. Further, the printing ink of the present invention may be used in combination with a resin other than the present invention, such as a polyurethane resin, a nitrified cotton, and an ethylene / vinyl acetate copolymer, within a range not departing from the performance thereof.

[0038]

The polyurethane resin of the present invention has excellent adhesiveness to various plastic films because it comprises a hydride (1) of a petroleum resin having active hydrogen as a molecular component, and is used as a binder for printing ink. Particularly useful. PET, NY, PE, PP
It has excellent adhesion to any of a variety of plastics such as, for example, and can be suitably used as a binder for printing inks, paints, and various coating agents. Further, the printing ink containing the polyurethane resin of the present invention as a binder for a printing ink can be used for the anti-blocking property at the time of winding a printed material (such as various plastic films) and a sterilization process when the printed material is used for food filling. Excellent in various properties such as boil and retort resistance required in In addition, it is excellent in printability and lamination processability, and can be applied to PP direct lamination process, boil process, retort process, dry lamination process, extrusion lamination process, and the like. Further, since the polyurethane resin of the present invention does not use a chlorine-based resin, it is stable over time, and there is no problem of corrosion of containers and the like.

[0039]

EXAMPLES The present invention will be described more specifically with reference to Production Examples, Examples and Comparative Examples, but the present invention is not limited to these Examples. The parts and percentages are based on weight.

Production Example 1 (Production of hydride (1) of petroleum resin having active hydrogen) As a petroleum resin having active hydrogen in a 1-liter autoclave, alcohol-modified dicyclopentadiene-based petroleum resin (trade name "Quinton 1700"; Nippon Zeon Co., Ltd.
Softening point 102.0 ° C, number average molecular weight 360) 500
And 7 parts of a nickel / diatomaceous earth catalyst (50% by weight of nickel supported) were charged, the reaction temperature was maintained at 260 ° C., and hydrogenation was performed at a hydrogen pressure of 20 MPa for 5 hours. Then
The hydride of the obtained alcohol-modified dicyclopentadiene-based petroleum resin was taken out, dissolved in 500 parts of toluene, the catalyst was removed by filtration, and the solvent was removed under reduced pressure at 200 ° C. and 2.7 kPa for 30 minutes to give a softening point of 100. 450 parts of a hydride of an alcohol-modified dicyclopentadiene-based petroleum resin (hereinafter referred to as "resin A") at a temperature of ° C was obtained. Table 1 shows the color tone, hydroxyl value, hydrogenation rate of unsaturated bond, and number average molecular weight of the obtained resin A.

Production Example 2 (Production of hydride (1) of petroleum resin having active hydrogen) In Production Example 1, phenol-modified C9 petroleum resin ("Neopolymer E-10") was used as the petroleum resin having active hydrogen.
0 ", softening point 93.0 ° C, number average molecular weight 580, 500 parts of Nippon Petrochemical Co., Ltd.), 2 parts of nickel / diatomaceous earth catalyst (50% by weight of nickel supported), and reaction temperature of 28
The same operation was performed except that the temperature was changed to 0 ° C., to obtain 480 parts of a phenol-modified C9 petroleum resin hydride having a softening point of 92 ° C. (hereinafter, referred to as “resin B”). Table 1 shows the color tone, hydroxyl value, hydrogenation ratio of unsaturated bond, and number average molecular weight of the obtained resin B.

The softening point is determined by the ring and ball method (JIS K220).
7) is a measured value. The color tone conforms to Hazen Standard Color (H) (ASTM D1209).
The hydroxyl value is determined by potentiometric titration (JIS K007).
0). The hydrogenation rate of the unsaturated bonds was calculated by measuring the proton nuclear magnetic resonance spectra ^{(1 H-NMR).} That is, a deuterium-substituted chloroform (CDCl ₃ ) solution of the same concentration of the raw material resin and the obtained hydride is prepared, and ¹ H-NMR is measured, which is derived from an unsaturated double bond appearing around 5 to 6 ppm. H-spectrum and 7p
Calculated based on the following formula from the H-spectral area of the conjugated double bond of the aromatic ring appearing near pm (hydrogenation rate = ｛1
-(Spectral area of obtained hydride / spectral area of raw resin)｝ × 100 (%)). The number average molecular weight is determined by gel permeation chromatography (GPC) (manufactured by Tosoh Corporation, HLC8120, column used: TSKge)
1 SuperHM-L × 3, developing solvent: tetrahydrofuran).

[0043]

[Table 1]

Production Example 3 (Production of Polyurethane Resin) A round-bottomed flask equipped with a stirrer, a thermometer and a nitrogen gas inlet tube was charged with 200 parts of resin A and poly (3-methyl-1,5-pentylene having a number average molecular weight of 2,000). Adipate) glycol (Kuraray Co., Ltd., trade name "Kurapol P201
0 ") 800 parts and 280 parts of isophorone diisocyanate were charged and reacted at 100 ° C. for 6 hours under a nitrogen stream to obtain a prepolymer having a free isocyanate value of 4.13%, and 548 parts of methyl ethyl ketone was added thereto to homogenize the urethane prepolymer. The solution was used. Next, 1775 parts of the urethane prepolymer solution was added in the presence of a mixture consisting of 83.4 parts of isophoronediamine, 29.1 parts of di-n-butylamine, 1575 parts of methyl ethyl ketone and 1054 parts of isopropyl alcohol, and the mixture was added at 50 ° C. for 3 hours. Reacted. The polyurethane resin solution thus obtained has a resin solid content concentration of 30% and a viscosity of 400 mPa · s / 25.
The number average molecular weight by GPC at ℃ was 19000.

Production Example 4 (Production of Polyurethane Resin) A round-bottomed flask equipped with a stirrer, a thermometer and a nitrogen gas introducing tube was charged with 400 parts of resin A and poly (3-methyl-1,5-pentylene having a number average molecular weight of 2,000). Adipate) glycol (Kuraray Co., Ltd., trade name "Kurapol P201
0 ") 600 parts and 340 parts of isophorone diisocyanate were charged and reacted at 100 ° C. for 6 hours under a nitrogen stream to obtain a prepolymer having a free isocyanate value of 4.81%, and 574 parts of methyl ethyl ketone was added thereto to homogenize the urethane prepolymer. The solution was used. Next, 1860 parts of the urethane prepolymer solution was added in the presence of a mixture consisting of 106.1 parts of isophoronediamine, 30.9 parts of di-n-butylamine, 1680 parts of methyl ethyl ketone and 1119 parts of isopropyl alcohol, and the mixture was added at 50 ° C. for 3 hours. Reacted. The polyurethane resin solution thus obtained is
Resin solid content concentration is 30% and viscosity is 700 mPa · s / 2
The number average molecular weight by GPC at 5 ° C. was 25,000.

Production Example 5 (Production of Polyurethane Resin) In a round-bottomed flask equipped with a stirrer, a thermometer and a nitrogen gas inlet tube, 200 parts of resin A, poly (3-methyl-1,5-pentylene adipate) having a molecular weight of 2,000 were added. Glycol (Kuraray Co., Ltd., product name "Kurapol P2010")
800 parts and 128 parts of isophorone diisocyanate were charged and reacted at 100 ° C. for 6 hours under a nitrogen stream. 2632 parts of methyl ethyl ketone was added thereto to obtain a resin solution. The polyurethane resin solution thus obtained has a resin solid content concentration of 30% and a viscosity of 100 mPa · s / 25 ° C.
The number average molecular weight by GPC was 17000.

Production Example 6 (Production of Polyurethane Resin) In a round-bottomed flask equipped with a stirrer, a thermometer, and a nitrogen gas inlet tube, 200 parts of resin B and poly (3-methyl-1,5-pentylene adipate) having a molecular weight of 2000 were prepared. Glycol (Kuraray Co., Ltd., product name "Kurapol P2010")
800 parts and 235 parts of isophorone diisocyanate were charged and reacted at 100 ° C. for 6 hours under a nitrogen stream to obtain a prepolymer having a free isocyanate value of 3.61%. To this, 529 parts of methyl ethyl ketone was added to obtain a uniform urethane prepolymer solution. . Then, isophorone diamine 6
7.9 parts, di-n-butylamine 27.4 parts, methyl ethyl ketone 1477 parts and isopropyl alcohol 99
1685 parts of the urethane prepolymer solution was added in the presence of 1 part of the mixture, and reacted at 50 ° C. for 3 hours. The polyurethane resin solution thus obtained has a resin solid content concentration of 30% and a viscosity of 200 mPa · s / 25 ° C.
The number average molecular weight by GPC was 18,000.

Comparative Production Example 1 A round bottom flask equipped with a stirrer, a thermometer and a nitrogen gas introduction tube was charged with poly (3-methyl-1,5-pentylene adipate) glycol (trade name "Kurapol", manufactured by Kuraray Co., Ltd.). P2010 ") 1000 parts and isophorone diisocyanate 222 parts were charged and reacted at 100 ° C. for 6 hours under a nitrogen stream to obtain a prepolymer having a free isocyanate value of 3.44%. To this, 523 parts of methyl ethyl ketone was added to homogenize the urethane prepolymer. The solution was used. Then, 73.8 parts of isophorone diamine, di-n-butylamine 16.
In the presence of a mixture consisting of 9 parts, 1518 parts of methyl ethyl ketone and 1020 parts of isopropyl alcohol, 1745 parts of the above urethane prepolymer solution was added and reacted at 50 ° C. for 3 hours. The polyurethane resin solution thus obtained has a resin solid content concentration of 30% and a viscosity of 600 mPa.
S / 25 ° C., number average molecular weight by GPC is 21,000
Met.

(Preparation example 1 of printing ink) Titanium white (rutile type) 30 parts, toluene 10 parts, methyl ethyl ketone 1
0 parts, 10 parts of isopropyl alcohol, 4 parts of the polyurethane resin solution obtained in Production Examples 3 to 6 and Comparative Production Example 1.
0 parts of each were milled with a paint shaker to prepare a white printing ink. Printing inks using the polyurethane resins obtained in Production Examples 3 to 6 and Comparative Production Example 1 are referred to as Examples 1 to 4 and Comparative Example 1, respectively.

(Preparation Example 2 of Printing Ink) In Preparation Example 1 of printing ink, 32 parts of the polyurethane resin solution obtained in Comparative Production Example 1 was used as a polyurethane resin solution, and a raw material of resin A (trade name “Quinton 1700”) was used. A white printing ink was prepared in the same manner as in Preparation Example 1, except that 8 parts of a softening point of 102.0 ° C. and a number average molecular weight of 360 manufactured by Zeon Corporation were used. This is referred to as Comparative Example 2.

(Preparation Example 3 of Printing Ink) In Preparation Example 1, 32 parts of the polyurethane resin solution obtained in Comparative Production Example 1 was used as a polyurethane resin solution, and chlorinated polypropylene (trade name “Supercron 813A”, Japan) A white printing ink was prepared in the same manner as in Preparation Example 1, except that 8 parts of 30% toluene solution (manufactured by Paper Manufacturing Co., Ltd.) were used.
This is referred to as Comparative Example 3.

The white printing inks obtained in the above production examples and comparative production examples were subjected to a corona discharge treatment OPP having a thickness of 15 μm by a simple gravure printing machine equipped with a gravure plate having a depth of 30 μm. Printing was performed on one side of PET and on the discharge-treated surface of corona discharge treatment NY having a thickness of 15 μm, and dried at 40 to 50 ° C. to obtain a printed film.

Adhesion: After the printed matter was allowed to stand for one day, a cellophane tape was stuck to the printed surface, and the appearance of the printed film when this was rapidly peeled was observed and evaluated according to the following criteria. Table 2 shows the evaluation results. A: No peeling occurred. 〇: 80% or more of the printed film remained on the film. Δ: 50 to 80% or more of the printed film remained on the film. X: 50% or less of the printed film remained on the film.

Corrosion of Storage Container: The above-mentioned white printing ink was put in a petroleum can and stored at room temperature for 3 months, and then the presence or absence of a corrosion state inside the container was confirmed. Table 2 shows the evaluation results.

Resolubility: The above white printing ink was prepared using a bar coder No. 4 and then dried, then immersed in a mixed solvent of toluene / methyl ethyl ketone / isopropyl alcohol = 1/1/1 (weight ratio) to determine the degree of dissolution of the ink coating film according to the following criteria. Was visually evaluated. Table 3 shows the evaluation results. ：: The ink coating film began to dissolve immediately. Δ: The ink coating film was gradually dissolved. X: The ink coating film was hardly dissolved.

[Table 2]

 ──────────────────────────────────────────────────続 き Continued on front page F term (reference) 4J034 BA07 CA01 CA12 CA21 DB03 DC02 DF01 DF19 DF20 DF21 DF22 DG02 DG03 DG04 DG05 DN03 DP13 DP20 HA01 HA07 HC03 HC12 HC13 HC17 HC22 HC46 HC52 HC61 HC71 HC73 JA02 JA14 RA07 4J039 AE04 EA43 EA48 FA02

Claims (7)

[Claims] 1. A polyurethane resin obtained by reacting a hydride (1) of a petroleum resin having active hydrogen, a polymer polyol (2) and a diisocyanate compound (3) as main components. 2. A hydrogenated petroleum resin having active hydrogen (1), a polymer polyol (2), a diisocyanate compound (3), a chain extender (4) and, if necessary, a chain terminator (5). A polyurethane resin obtained by reacting as a main component. 3. The polyurethane resin according to claim 1, wherein the hydride (1) of the petroleum resin having active hydrogen is a hydride of an alcohol-modified dicyclopentadiene-based resin. 4. A use ratio of a hydride (1) of a petroleum resin having active hydrogen and a polymer polyol (2) (1) /
The polyurethane resin according to any one of claims 1 to 4, wherein (2) has a weight ratio of 1/99 to 70/30. 5. A number average molecular weight of 5,000 to 100,000
The polyurethane resin according to any one of claims 1 to 4, wherein 6. A binder for printing ink using the polyurethane resin according to claim 1. Description: 7. A printing ink composition comprising the printing ink binder according to claim 6.