JPH09255909A - Printing ink composition for decorative paper and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a printing ink composition for decorative paper production which has excellent adhesion to a decorative paper base even when used as a one-pack type ink and has tight adhesion to a topcoating based on a polyurethane or aminoalkyd resin and to provide a decorative paper and a decorative laminate made using the same. SOLUTION: The composition contains a binder consisting of a polyurethane resin obtained by reacting a dimer diol and (or) a polyester polyol of a polymerized fatty acid with an organic diisocyanate and at least either of a chain extender and a chain terminator, and a nitrocellulose resin having a nitrogen content of 10.7-12.2wt.% and an average degree of polymerization of 1-200. The decorative paper is obtained by printing a decorative paper base with the ink composition. The decorative laminate is obtained by laminating the decorative paper and a substrate with an adhesive.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a printing ink composition for decorative paper, a decorative paper using the same, and a decorative board.

[0002]

2. Description of the Related Art Conventionally, as printing inks for decorative paper, nitrified cotton-plasticizer ink containing nitrified cotton resin as a binder and containing a plasticizer, or nitrified cotton-alkyd ink containing nitrified cotton resin and alkyd resin as binders. Was using. Among these, the nitrified cotton-plasticizer type printing ink lacked flexibility of the printed matter and had poor adhesion to the resin-impregnated decorative paper base paper. Further, when a polyurethane resin or an aminoalkyd resin was used for the top coat layer, the adhesion was poor.

On the other hand, although the nitrified cotton-alkyd ink improves the flexibility of the printed matter, it does not adhere to the resin-impregnated decorative paper base paper, and when a polyurethane resin or aminoalkyd resin is used for the top coat layer. Had poor adhesion. In order to solve these problems, a two-component ink containing an isocyanate was used, but it had the drawbacks of lowering the printing speed and requiring aging. Further, in terms of work, there was a problem in handling the amount of isocyanate added.

[0004]

The object of the present invention is to have excellent adhesiveness to the base paper for decorative paper even when used as a single solution, and to be excellent in the topcoat processing using polyurethane resin or aminoalkyd resin. It is intended to provide a printing ink composition for decorative paper having adhesion, a decorative paper and a decorative board using the same.

[0005]

That is, the present invention provides:
Polyurethane resin obtained by reacting (A) dimer diol and / or (B) polymerized fatty acid polyester polyol, (C) organic diisocyanate, (D) chain extender and / or (E) end terminating agent, and nitrogen Minute 1
Provided is a printing ink composition for decorative paper, which comprises a nitrified cotton resin having a degree of polymerization of 0.7 to 12.2% and an average degree of polymerization of 1 to 200 as a binder. The present invention also provides the printing ink composition for decorative paper, wherein the weight ratio of the polyurethane resin and the nitrified cotton resin is 60/40 to 90/10.
Furthermore, the present invention provides a decorative paper obtained by printing the above printing ink composition on a decorative paper base paper. Furthermore, the present invention provides a decorative board obtained by laminating the above decorative paper on a base material via an adhesive.

The polyurethane resin of the present invention comprises (A) dimer diol and / or (B) polymerized fatty acid polyester polyol, optionally other polyols (A) and (B), (C) organic diisocyanate, (D). )
It is obtained by reacting a chain extender and / or (E) an end cap agent.

The (A) dimer diol is mainly composed of a diol obtained by reducing the carboxyl group of dimer acid. The (B) polymerized fatty acid polyester polyol is obtained by reacting a polymerized fatty acid, a polycarboxylic acid other than the polymerized fatty acid or an anhydride thereof, a diol, and, if necessary, a polyol other than the diol. As the polymerized fatty acids, C ₁₈ unsaturated fatty acids such as oleic acid and linoleic acid, dry fatty acids or semi-dry fatty acids, and lower monoalcohol esters of these fatty acids were bimolecularly polymerized in the presence or absence of a catalyst. There are things.

Examples of polycarboxylic acids other than polymerized fatty acids or their anhydrides include adibic acid, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, succinic acid,
Oxalic acid, malonic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and other dicarboxylic acids or their anhydrides, trimellitic acid, pyromellitic acid and other polycarboxylic acids or their anhydrides Things can be mentioned.

As the diol, ethylene glycol,
1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, pentanediol, hexanediol, octanediol, diethylene glycol, triethylene glycol, dipropylene glycol Examples thereof include saturated or unsaturated low molecular weight diols such as dimer diol, and diols obtained by reacting these low molecular weight diols with the above dicarboxylic acid or its anhydride.

As the polyol other than the diol, trifunctional or higher functional polyols such as glycerin, trimethylolpropane, trimethylolethane, 1,2,6-butanetriol, pentaerythritol and sorbitol,
Alternatively, polyols and diols obtained by reacting these polyols with dicarboxylic acids or their anhydrides and 3
Examples thereof include polyols obtained by a reaction with a polycarboxylic acid having a functionality or higher or an anhydride thereof.

As the polyol other than the above (A) and (B), in addition to the diols and polyols exemplified as the raw material of the (B) polymerized fatty acid polyester polyol, as the raw material of the diol or polyol and the (B) polymerized fatty acid polyester polyol. Polyester polyols obtained by dehydration condensation of the exemplified polycarboxylic acids or their anhydrides, polyester polyols obtained by ring-opening polymerization of cyclic ester compounds, polycarbonate polyols, polybutadiene glycols, ethylene oxide or oxidation to bisphenol A Examples thereof include polymer polyols usually used in the production of polyurethane resins, such as glycols obtained by adding propylene.

Examples of the organic diisocyanate (C) include conventionally known aromatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates. Examples of the chain extender (D) include ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine,
Amine such as triethylenetetramine, isophoronediamine, dicyclohexylmethane-4,4-diamine, 2-hydroxyethylethylenediamine, 2-hydroxyethylpropylenediamine, di-2hydroxyethylenediamine, di-2-hydroxypropylethylenediamine, di- Examples thereof include amines having a hydroxyl group such as 2-hydroxypropylethylenediamine. Also,
Examples of the (E) terminal stopper include dialkylamines such as di-n-butylamine.

The polyurethane resin of the present invention comprises (A) and / or (B) and, if necessary, (A) and (B).
After reacting a polyol other than (C) with (C) at a ratio such that an isocyanate group becomes excessive, a prepolymer having a terminal isocyanate group is obtained, and the obtained prepolymer is then mixed with (D) and / or () in a suitable solvent. A two-step method of reacting with E), or (A) and / or (B), if necessary, a polyol other than (A) and (B), (C),
It is produced by a one-step method in which (D) and / or (E) are reacted at once in a suitable solvent.

In order to obtain a uniform polyurethane resin, the two-step method is preferred. When the polyurethane resin is produced by the two-step method, the prepolymer and (D) and / or (E) are the number of isocyanate groups in the prepolymer / (D) and / or amino groups of (E). The total number of 1 / 0.90 to 1.30, preferably 1.01 to 1.
It is preferable to react at a ratio of 20.

Solvents used in the production of polyurethane resins include aromatic solvents such as benzene, toluene and xylene, ester solvents such as ethyl acetate and butyl acetate,
Methanol, ethanol, isopropyl alcohol, n
Examples include alcohol solvents such as butanol, and ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone.

The nitrified cotton resin used as a binder of the printing ink composition for decorative paper of the present invention together with the above polyurethane resin has a nitrogen content of 10.7 to 12.2% by weight and an average degree of polymerization of 1 to 200. . The nitrified cotton resin is a nitrate ester obtained by reacting natural cellulose with nitric acid to replace the three hydroxyl groups in the 6-membered ring of the anhydrous glucopyranose group in natural cellulose with nitrate groups. Glucopyranose residues and -C ₆ H ₇ O ₂ in the cellulose - (OH) glucopyranose residues nitrification Expressed in ₃ -C ₆ H ₇ O ₂ -
It is represented by (OH) ₃ -δ- (ONO ₂ ) δ. Δ at this time
Represents the degree of substitution, and the degree of substitution can also be expressed in% by weight of nitrogen atoms. The relationship between the degree of substitution and the nitrogen content is 6.76% by weight when the degree of substitution is 1, and 1 when the degree of substitution is 2.
When the substitution degree is 1.11% by weight, the nitrogen content is 14.14% by weight. The degree of substitution of the nitrified cotton resin used as the binder of the printing ink composition for decorative paper of the present invention depends on the balance with the solvent used for the ink, and the nitrogen content is 10.7-1.
Must be 2.2% by weight.

Further, a nitrified cotton resin having an average degree of polymerization of more than 200 has poor compatibility with the above-mentioned polyurethane resin.
The resulting printing ink composition has a high finish viscosity and is not suitable as a gravure ink. The polyurethane resin and the nitrified cotton resin are preferably used in a weight ratio of 60/40 to 90/10. When the proportion of the polyurethane resin is more than the above range, the heat resistance of the obtained printing ink composition is lowered, and the ink is taken up by the mirror-pressed plate during the production of the decorative plate. On the other hand, when the proportion of the polyurethane resin is less than the above range, the adhesion of the obtained printing ink composition to the resin-impregnated decorative paper base paper is poor.

The printing ink composition for decorative paper of the present invention comprises the above-mentioned polyurethane resin and nitrification cotton resin, an organic solvent, if necessary, a coloring agent such as a pigment, and an interfacial activity for improving the fluidity and film state of the ink. It is manufactured by appropriately mixing additives such as agents and waxes and dispersing them by a known method.

The printing ink composition for decorative paper of the present invention is printed on a decorative paper base paper by gravure printing to produce a decorative paper. A top coat layer may be provided on the printed layer for the purpose of imparting gloss and antifouling property. The top coat layer is a gravure coat or a roll coat and is printed in the same process as the ink or in a separate process. For the top coat layer, known resins such as phenol resin, urea resin, aminoalkyd resin, melamine resin, polyester resin, polyurethane resin, epoxy resin, silicone resin are used.

The decorative paper is adhered to the base material via an adhesive using a roll method or a mirror surface press plate to produce a decorative plate. Examples of the adhesive include vinyl acetate, ethylene-modified vinyl acetate, and acrylic resin. Examples of the base material include plywood, hard boards, iron plates, particle boats, calcium silicate plates, valve cement plates, gypsum boats, and other refractory materials.

[0021]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail based on embodiments. In the examples, “part” indicates “part by weight” and “%” indicates “% by weight”.

[Synthesis Example 1 of Polyurethane Resin] Polymerized fatty acid “Versadym 216” (manufactured by Henkel Hakusui Co.) and 1,4-butanediol having a weight molecular weight of 200.
100 parts of the polymerized fatty acid polyester polyol of 0 and 18 parts of isophorone diisocyanate were reacted at 100 ° C. for 6 hours to obtain a prepolymer of a terminal isocyanate. To this, 97 parts of toluene was added to obtain a solvent solution of a terminal isocyanate prepolymer. Next, isophorone diamine 6
Parts, 0.5 parts of di-n-butylamine, 97 parts of methyl ethyl ketone and 97 parts of isopropyl alcohol are added to 215 parts of a solvent solution of the obtained terminal isocyanate prepolymer and reacted at 50 ° C. for 3 hours,
A polyurethane resin solution a having a solid content of 30% and a viscosity at 25 ° C. of 400 cP was obtained.

[Synthesis Example 2 of Polyurethane Resin] In the same manner as in Synthesis Example 1 from the following raw materials, solid content 30%, 25 ° C.
A polyurethane resin solution b having a viscosity of 500 cP was obtained. Polymerized fatty acid "Versadym 216", adipic acid and 1,6-hexanediol obtained from a polymerized fatty acid polyester polyol having an average molecular weight of 2000 100 parts 1,3-bis (isocyanatomethyl) cyclohexane 18 parts toluene 97 parts isophorolone diamine 7 parts Di-n-butylamine 0.6 parts Methyl ethyl ketone 97 parts Isopropyl alcohol 97 parts

[Synthesis Example 3 of Polyurethane Resin] Synthesis Example 1 except that 30 parts of dimer diol (manufactured by Henkel Hakusui Co., Ltd.) was added to 100 parts of polymerized fatty acid polyester polyol.
Reaction is carried out in the same manner as in, solid content 30%, 500 cps
To obtain a polyurethane resin solution c.

Example 1 Titanium oxide in the following formulation, the polyurethane resin a obtained in Synthesis Example 1 and a solvent were mixed and dispersed by a sand mill to obtain a dispersion having a grindometer of 30 μm or less. Then, a nitrified cotton resin solution was added to obtain a printing ink composition d for decorative paper. Polyurethane resin solution a obtained in Synthesis Example 1 35 parts Titanium oxide "Taipeque R-780" (manufactured by Ishihara Sangyo Co., Ltd.) 50 parts Ethyl oxyacetate 5 parts Toluene 5 parts Nitrified cotton resin solution (Asahi Kasei Kogyo's "HIG1 / 16 , Nitrogen content 12%, polymerization degree 40, 30% solution) 5 parts

[Example 2] A printing ink composition e for decorative paper was obtained from the following raw materials in the same manner as in Example 1. Polyurethane resin solution b obtained in Synthesis Example 2 30 parts Titanium oxide "Taipeque R-780" (manufactured by Ishihara Sangyo Co., Ltd.) 50 parts Ethyl oxyacetate 3 parts Toluene 3 parts Isopropyl alcohol 4 parts Nitrified cotton resin solution (manufactured by Asahi Kasei Kogyo Co., Ltd. "HIG1 / 16", nitrogen content 12%, polymerization degree 40 30% resin solution) 10 parts

Example 3 A printing ink composition f for decorative paper was obtained from the following raw materials in the same manner as in Example 1. Polyurethane resin solution c obtained in Synthesis Example 3 30 parts Titanium oxide "Taipeque R-780" (manufactured by Ishihara Sangyo Co., Ltd.) 50 parts Ethyl oxyacetate 5 parts Toluene 5 parts Nitrified cotton resin solution (Asahi Kasei Kogyo's "HIG1 / 16 ] Nitrogen content 12%, polymerization degree 40 30% resin solution) 10 parts

Example 4 For decorative paper in the same manner as in Example 1 except that 35 parts of the polyurethane resin solution a obtained in Synthesis Example 1 was changed to 22 parts and 5 parts of the nitrified cotton resin solution was changed to 18 parts. A printing ink composition g was obtained.

Comparative Example 1 A printing ink composition h for decorative paper was obtained in the same manner as in Example 1 except that 35 parts of the polyurethane resin solution a obtained in Synthesis Example 1 was changed to 5 parts of a plasticizer. [Comparative Example 2] A nitrified cotton resin solution was mixed with "HI" manufactured by Asahi Kasei Kogyo Co., Ltd.
A printing ink composition i for decorative paper was obtained in the same manner as in Example 1 except that a 30% resin solution of "G20" (nitrogen content 20%, polymerization degree 270) was used.

The finished viscosities of the printing ink compositions for decorative paper obtained in the examples and comparative examples were measured at a liquid temperature of 25 ° C.
The measurement was performed using "Zahn Cup No. 4" manufactured by Riaisha.
The results are shown in Table 1. A printing ink composition having a finish viscosity of more than 50 seconds needs to use a large amount of a diluting solvent at the time of printing, resulting in uneven printing or insufficient concentration of the obtained printed matter, which is a practical problem. In addition, the printing ink composition for decorative paper obtained in Examples and Comparative Examples was applied to a resin-impregnated decorative paper base paper “HPN-29UB” (manufactured by Tenma Paper Co., Ltd.) and a gravure plate (conventional 60 μ, 100 μm).
Line) was used for gravure printing, and the obtained printed matter was evaluated for ink adhesion by the following method. The results are shown in Table 1.

Further, a top coat prepared by adding an acid catalyst in an amount of 2% of the resin solution to an aminoalkyd resin solution "Marblack ALNS" (manufactured by China Paint Co., Ltd.) was added to the above-mentioned printed matter, and a polyurethane resin solution "Orestar Q169".
(Mitsui Toatsu Chemical Co., Ltd.), a top coat prepared by adding an isocyanate-based curing agent in an amount corresponding to 30% of the resin solution was roll-coated and dried at 150 ° C. for 30 seconds. The adhesion of the top coat was evaluated by the following method. The results are shown in Table 1.

Next, the adhesive "Sebian A" (manufactured by Daicel Chemical Industries, Ltd.) was applied over the entire surface of the obtained decorative paper on which the printing layer and the top coat layer were not formed, and then plywood "Particle board" (Takehara Kogyo) (Manufactured by the same company) was attached and laminated with a mirror surface press plate to obtain a decorative plate. The heat resistance of the ink was evaluated by the following method since the ink was taken up by the mirror-pressed plate when the decorative plate was manufactured by the mirror-pressed method. The results are shown in Table 1.

The evaluation method and evaluation criteria are as follows. [Adhesion] A 12 mm wide cellophane tape manufactured by Nichiban Co., Ltd. is attached to the printing ink layer or the top coat layer,
The ink removal at the time of peeling was visually evaluated on a scale of five. 5: Ink removal is 0% and good 3: Ink removal is 50% 1: Ink removal is 100% and poor [heat resistance] When manufacturing a decorative plate by the mirror surface pressing method Heat is applied to bond under the conditions of pressure 150 kg / cm ² and time 30 seconds, and the ink removal to the mirror surface press plate at that time is 5
It was visually evaluated in stages. 5: Ink removal was 0% and good 3: Ink removal was 50% 1: Ink removal was 100% and poor

[0034]

[Table 1]

[0035]

INDUSTRIAL APPLICABILITY According to the present invention, it has excellent adhesiveness to resin-impregnated decorative paper base paper, and also has excellent adhesiveness when a top coat containing a polyurethane resin and an aminoalkyd resin is used. A liquid type printing ink composition for decorative paper has come to be obtained.

Claims (4)

[Claims] 1. A dimer diol (A) and / or
(B) Polymerized fatty acid polyester polyol, (C) Organic diisocyanate, (D) Chain extender and / or
(E) Polyurethane resin obtained by reacting a terminal stopper, nitrogen content 10.7 to 12.2% by weight, average degree of polymerization 1
A printing ink composition for decorative paper, which comprises a nitrified cotton resin of 200 to 200 as a binder. 2. The printing ink composition for decorative paper according to claim 1, wherein the weight ratio of the polyurethane resin and the nitrified cotton resin is 60/40 to 90/10. 3. A decorative paper obtained by printing the printing ink composition according to claim 1 on a decorative paper base paper. 4. A decorative board obtained by laminating the decorative paper according to claim 3 on a base material via an adhesive.