JPS60197779A - Vehicle composition for printing ink - Google Patents

Abstract

PURPOSE:To provide a vehicle compsn. for printing ink, which has excellent printability and adhesion to plastic moldings, containing a specified polyurethane resin and a low-molecular aliph. dicarboxylic acid. CONSTITUTION:A polyol component (A) (e.g. polypropylene glycol), an aliph. or alicyclic diisocyanate (B) wherein each isocyanate group is directly attached to a carbon atom to which two hydrogen atoms are attached (e.g. hydrogenated xylylene diisocyanate) and a chain extender (C) composed of a diol component and/or an amine component (e.g. isophoronediamine) are reacted together to prepare a polyurethane resin. The polyurethane resin is mixed with an aliph. dicarboxylic acid having an MW of 150 or below (e.g. adipic or succinic acid) to obtain the desired vehicle compsn. for printing ink.

Description

DETAILED DESCRIPTION OF THE INVENTION (Technical Field of the Invention) The present invention relates to a vehicle composition for printing ink. ,
The present invention also relates to a vehicle composition for printing ink having excellent printability.

(Prior Art) Conventionally, rosin-modified maleic acid resins, polyamide resins, chlorinated polypropylene resins, polyurethane resins, etc. have been used as vehicle components of printing ink compositions for plastic molded products, but polyolefins, polyesters, None of the molded products made of polyamide or the like had equally excellent adhesion. In addition, when printed, printing suitability such as 1 Oyogi”, -Fs, and # resolubility,
Blocking resistance and critical pigment volume concentration (opva
) etc., none of them satisfied all of the conditions. Therefore, there has been a demand for the development of a vehicle composition for printing ink that satisfies all of these conditions.

Furthermore, vehicle compositions for printing ink using -plane polyurethane resins are being applied to packaging materials for retort foods, which have been rapidly increasing in recent years.

In order to improve its boiling resistance, it is used throughout the polyester as a polyol component in polyurethane resins, but as a result, it has the disadvantage that its resolubility, which is suitable for printing, is greatly reduced.

(Objective of the Invention) An object of the present invention is to provide a vehicle composition for printing ink that satisfies all the conditions required by the above-mentioned printing ink.

(Structure of the Invention) To outline the present invention, vehicle composition 11 for printing ink of the present invention (A) (a) polyol component, (b)
) an aliphatic or alicyclic diisocyanate compound in which an incyanate group is directly bonded to a carbon atom bonded to two hydrogen atoms; and (0) a chain extender consisting of a diol component and/or an amine component. and (B) an aliphatic dicarboxylic acid having a molecular weight of 150 or less.

To explain the composition of the vehicle composition for printing ink of the present invention in more detail, the polyurethane resin (A) has the following (fL
) to (C) are reacted.

(a) Polyol component This polyol component has an average molecular weight of 600 to 5000, preferably 1500 to 250, regardless of molecular weight distribution.
Preferably, a value in the range 0 is used. This is because if the average molecular weight is less than 600, the solubility will be lowered, resulting in poor printability, while if it is more than 5,000, the drying properties will be lowered, resulting in poor blocking resistance, which is undesirable.

Polyol components include polyesters, polyethers, polyester ethers, etc. having hydroxyl groups, and polyesters include polyhydric alcohols such as ethylene glycol, propylene glycol, 1,6-
Condensates of hexanediol, trimethylolpropane, sorbitan, etc., and polyhydric carboxylic acids, such as cono-phosphoric acid, adipic acid, fumaric acid, glutaric acid, isophthalic acid, pyromellitic acid, etc.; hydroxycarboxylic acids and polyhydric alcohols; Examples include condensates and lactone polymers.

As the polyether, for example, polypropylene glycol, polytetramethylene glycol, etc. can be used.

Further, as the polyester-polyether, those obtained by adding an alkylene oxide to the above-mentioned polyester, those obtained by condensing polyether and polycarboxylic acid, and the like having a hydroxyl group can be used.

These polyol components can be used alone or in a mixture, but if polyether is used in a large amount as a polyol component, the boiling resistance tends to decrease. -The following blade types are appropriate.

(b) Aliphatic or alicyclic diisocyanate compounds in which the isocyanate group is directly bonded to the carbon atom bonded to two hydrogen atoms.

The diisocyanate compound used is one in which an isocyanate group is directly bonded to a carbon atom bonded to two hydrogen atoms. This is because if all incyanate compounds in which two or more other carbon atoms are bonded to the carbon atom to which an isocyanate group is bonded are used, the adhesion to polyolefin, polyester, and polyamide molded products will decrease. Therefore, aromatic diisocyanate compounds are not applicable to the present invention.

The diisocyanate compound in which the above-mentioned isocyanate group is directly bonded to a carbon atom bonded to two hydrogen atoms includes:
Hydrogenated compounds of hexamethylene diisocyanate, trimethylhexamethylene diisocyanate ($-), xylylene diisocyanate, and isocyanate compounds in which at least one incyanate group is directly bonded to a carbon atom bonded to two hydrogen atoms include: Lysine diisocyanate and inphorone diisocyanate can be used.

(C) Chain extender consisting of diol component and/or amine component The diol component used in the chain extender has 1 to 1 carbon atoms.
All diols in No. 6 are used. If a diol having 7 or more carbon atoms is used, it is not preferable because the popping resistance decreases. Specifically, the diol includes ethylene glycol, propylene glycol, trimethylene glycol, 1.4-butanediol, 1.5-bentanediol, 1.6-hexanediol, cyclopentane-1,2-diol,
Cyclohexane-1,2-diol, cyclohexane-
1,4-diol and the like are suitable.

On the other hand, diamines used in combination with the above diols or used alone include aliphatic diamines such as ethylenediamine, hexamethylenediamine, and trimethylhexamethylenediamine, isophoronediamine, piperazine, aminoethylpiperazine, 2,5-dimethylpiperazine, 3.
9-bis-(3-aminopropyl)-2,4,8,1
Alicyclic heterocyclic diamines such as 0-tetraxaspiro(5,5)undecane, as well as m-phenylene diamine, p-phenylene diamine, 2,4-tolylene diamine, m-xylylene ξbe p- Aromatic diamines such as xylylene diamine and 4.4''-diaminodiphenylmethane are used.

A polyurethane resin (A
) can be selected in any combination from those commonly used as solvents for polyurethane resins, such as dimethylformamide, diethylformamide, dimethylacetamide, acetone, methyl ethyl ketone, and dimethyl sulfoxide. Just use it.

As a reaction method, a conventionally known method for producing polyurethane resins can be used. For example, 1 mole of a polyol component and 2 moles of an incyanate compound are mixed at 50 to 100°C for 3
After reacting for ~12 hours, the urethane prepolymer with the terminal incyanate groups seen was diluted with an organic solvent and further treated with 7~1 mole of chain extender α at 40~100 °C for 2 ~
A method such as allowing the reaction to complete for 50 hours may be used.

The polyurethane resin used in the present invention has a number average molecular weight of 50,000 to 100,000. This is because those with a number average molecular weight of 50,000 or less have poor blocking resistance, while those with a number average molecular weight of 100,000 or more have poor solubility, resulting in decreased printability, which is undesirable. The number average molecular weight of the polyurethane resin is adjusted by the number average molecular weight of the polyol component and the molar amount of the chain extender used in polyurethane production.

(b) Aliphatic dicarboxylic acid with a molecular weight of 150 or less In the present invention, an aliphatic dicarboxylic acid with a molecular weight of 150 or less is used to improve the resolubility of printing ink.
0 or less aliphatic dicarboxylic acid is blended. molecular weight is 15
Even if a dicarboxylic acid larger than 0 is blended, the object of the present invention cannot be achieved. Dicarboxylic acids that can be used in the present invention include oxalic acid, malonic acid, conolic acid, glutaric acid,
Examples include adipic acid, maleic acid, and fumaric acid.

The vehicle composition for printing ink of the present invention comprises the above-mentioned (IL)
~ (b) To the polyurethane resin (mu) reacted with the component (
It is obtained by adding the aliphatic dicarboxylic acid 't-ti of component B), but the blending ratio is (A) polyurethane resin 100%
The ratio of (B) aliphatic dicarboxylic acid to 1 to 6 parts by weight is preferable. If the amount of dicarboxylic acid is outside this range, it is not preferable because the adhesion of the ink to the plastic molded product decreases. Specifically, a dicarboxylic acid is blended into a solution of a polyurethane resin obtained by the above reaction method, and this solution is used as it is or after further dilution as a vehicle for printing ink.

A printing ink can be prepared from this vehicle by kneading it with a pigment according to conventional methods.

The polyurethane resin that is the vehicle component for the ink of the present invention can increase the critical pigment volume concentration, and the pigment content is 50 to 500 parts by weight per 100 parts by weight of the solid content of the polyurethane resin.
By adding parts by weight, you can make a part.

The printing ink thus prepared exhibits excellent adhesion to polyolefin-based, polyester-based and polyamide-based molded products, and when printed,
Ink No. 1 has excellent printing properties such as smudgeability and resolubility, provides a clear print finish, and shows excellent properties such as no blocking on the printed surface.

(Examples of the Invention) Examples and synthesis examples of polyurethane resins used in the examples will be shown below to specifically explain the present invention.

Synthesis Example 1 540 parts of polyester (butanediol-inphthalic acid-adipic acid) having a molecular weight of 1800 was charged into a 3-ton four-bottle flask equipped with a thermometer, a reflux condenser, and a stirrer, and then 135 parts of isophorone diisocyanate, 1.
8 parts of 4-butanediol were added, and the reaction was carried out at 60°C for 1 hour.

Next, 1630 parts of methyl ethyl ketone were added, followed by 15 parts of isophorone diamine, and the mixture was reacted at 60°C for 5 hours to obtain a solution of a polyurethane resin having a number average molecular weight of 48.000'i.

Synthesis Example 2 In a reaction vessel similar to Synthesis Example 1, 400% polyester (ethylene glycol-adipic acid) with an average molecular weight of 1000 was added.
1 part and polypropylene glycol with an average molecular weight of 1000
Then, 146 parts of a hydrogenated compound of xylylene diisocyanate were added, and the reaction was carried out at 50°C for 1 hour.

Next, 1,650 parts of methyl ethyl ketone were added, followed by 42 parts of inphorondiamine, and the reaction was carried out at 50 to 60 DEG C. for 5 hours to obtain a solution of a polyurethane resin having a number average molecular weight of 72.000'i.

Synthesis Example 5 In a reaction vessel similar to Synthesis Example 1, 400% polyester (ethylene glycol-adipic acid) with an average molecular weight of 2000 was added.
1 part and average molecular weight of 2000 polypropylene glycol
Then, 125 parts of 4,4'-diphenylmethane diisocyanate were added, and the reaction was carried out at 40 to 50°C for 1 hour.

Next, 1,500 parts of methyl ethyl ketone was added, followed by 14 parts of ethylene glycol, and the reaction was carried out at 60 to 70 DEG C. for 5 hours to obtain a solution of a polyurethane resin having a number average molecular weight of 65,000'i.

Example 1 Using 800 parts of the polycrethane resin solution prepared in Synthesis Example 1, oxalic acid was added at 3% by weight based on the resin solid content, and red pigment (
Product name: 8anyo TintingRed (manufactured by Sanyo Shiki Co., Ltd.) 100% by weight and 640 parts of methyl ethyl ketone (MEK) and 160 parts of toluene as solvents were added and dispersed in a ball mill for 15 hours to obtain a non-volatile component of 20 parts by weight.
*A red ink was prepared.

Examples 2 to 3 and Comparative Examples 1 to 3 The same method as in Example 1 was carried out except that the amount of oxalic acid was varied as shown in Table 1,
Red inks were prepared for each.

Example 4 and Comparative Example 4 Red inks were prepared by following the same method as in Example 1 except that the dicarboxylic acids succinic acid and pimelic acid were used.

Example 5 A red ink was prepared by following the same method as in Example 1 except that the polyurethane resin solution prepared in Synthesis Example 2 was used.

Comparative Example 5 In the method of Example 1, in Synthesis Example 5 v! 411! A red ink was prepared by following the same procedure except that a solution of the polyurethane resin was used.

Preparation of specimen and test method Using each of the red inks prepared in Examples 1 to 5 and Comparative Examples 1 to 5, printing was performed on a nylon film with a gravure roll (500 lines) at a speed of 100 m and 7 minutes. was prepared.

In the re-dissolution test, the roll plate was checked to see if it was clogged 9 after 1100 m of printing had been carried out.

For the adhesion test, the printed specimen was dried at 80°C for 10 seconds,
Attach cellophane tape to the printing ink surface and carefully peel it off.

Next, Examples 1 to 5 and Comparative Examples 1 to 5 were evaluated as shown in the table below.

Re-solubility: Judgment was made by visually observing whether or not the gravure roll was clogged.

Adhesion: A cellophane tape (50) was pasted on the printing ink surface, one end of which was held and pulled off at once, and the peeling rate of the ink layer was evaluated.

However, ○...0-20%, Δ...20-70%,
X...70% or more (effect of the invention) As is clear from the above explanation, the vehicle composition for printing ink of the present invention exhibits excellent adhesion to any plastic product, and moreover, the printing ink is The required functions, namely printability, anti-blocking properties, anti-boil properties, re-dissolution properties, and critical pigment volume concentration alloy were satisfied.

Claims (1)

[Scope of Claims] t(A) (a) a polyol component, an aliphatic or alicyclic diisocyanate compound in which an isocyanate group is directly bonded to a carbon atom bonded to two hydrogen atoms, and (0) A polyurethane resin obtained by reacting a chain extender consisting of a diol component and/or an amine component, and (B) containing an aliphatic dicarboxylic acid having a molecular weight of 150 or less f:
4I vehicle composition for printing ink.