JPH0639183B2 - Printed matter manufacturing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION “Object of the Invention” (Field of Industrial Application) The present invention relates to a method for producing a printed matter, in which a curable anchor coating agent is offset-printed on a substrate and offset ink is offset-printed thereon. Regarding

(Prior Art) Conventionally, silk screen or gravure printing has been performed on a printing material such as polypropylene or polyvinyl chloride, which is difficult to adhere with an active energy ray curable offset ink such as ultraviolet rays or electron beams. In recent years, a printing method has been performed in which an anchor coat is applied by a roll coater, silk screen, or gravure printing to cover the adhesiveness, and offset printing is performed on the anchor coat using an active energy ray curable offset ink such as ultraviolet rays or electron beams. This is aimed at improving productivity, cost, and print quality by offset printing using active energy ray-curable offset ink. However, roll coaters, silk screens, and gravure printing are still used as anchor coats, and their advantages have not been fully demonstrated. That is, the cost of anchor coat, the productivity, the difficulty of process control by using different printing methods,
There is a change over time in the anchor coat (deterioration of ink adhesion over time after printing the anchor coat). In addition, even if the anchor coat is applied only to the design part, the misalignment due to the use of a different printing method and the expansion and contraction of the printing object due to the heat during drying may cause the anchor coat to be the part where the color ink is printed due to the offset. The presence of the anchor coat is clearly visible as it has to be applied much larger.

Further, since the conventional anchor coating agent generally uses a petroleum solvent, when an antistatic agent, a plasticizer, etc. added to the printing material are raised on the anchor coating and cause uneven transfer of the offset ink or transfer failure. There is.

(Problems to be Solved by the Invention) The present inventors think that such problems can be solved by printing all of the anchor coating agent and printing by the offset printing method, and as a result of earnest research, active energy ray-curable offset The inventors have invented a method for producing a printed matter using ink as an anchor coating agent.

The present invention is described in JP-A-49-124133 and JP-A-55-124.
The present invention relates to a method for producing a printed material, which is used as an anchor coating agent for offset printing by making good use of the adhesiveness of a UV-curable coating composition to plastics disclosed in Japanese Patent 3431.

[Structure of the Invention] (Means for Solving Problems) That is, the present invention provides a printing medium selected from polypropylene moldings or polyvinyl chloride moldings, having the following general formula: (In the formula, R represents an organic residue having 1 to 3 carbon atoms, m and n each represent 0 or an integer, and m + n = 6.) A 5-membered ring compound having an unsaturated conjugated double bond, Or these Dies Alder compounds (A)
And a resin (I) having a hydroxyl group obtained by reacting a compound (B) having an unsaturated double bond and a hydroxyl group in the same molecule, and / or a resin having a hydroxyl group obtained by hydrogenating the resin (I) (II) as a polyol component in the production of an alkyd resin to produce an excess hydroxyl group alkyd resin (III), and the excess hydroxyl group alkyd resin (III)
In addition, an active energy ray anchor coating agent containing an active energy ray curable resin (IV) obtained by esterifying acrylic acid and / or methacrylic acid is applied by offset printing according to the area to be offset printed with offset ink, and then Offset printing on the anchor coat surface with an active energy ray-curable offset ink,
The present invention relates to a method for producing a printed matter in which active energy rays are irradiated before or after printing an offset ink, and further, an overprint varnish is applied if necessary, to a method for producing a printed matter.

The anchor coating agent used in the present invention contains the resin (IV) as a main component, and additionally uses a viscosity adjusting monomer, a sensitizer, a pigment, an additive and the like as required. The composition is 30 to 85 parts by weight of resin (IV), 5 to 25 sensitizer.
Parts by weight, pigment 5 to 30 parts by weight, viscosity adjusting monomer 5 to 4
0 parts by weight, and if necessary, other additives can be added. In the case of electron beam-curable anchor coating agent,
No sensitizer may be used. Next, the resin (IV) will be described in detail.

The resin (I) contains, as the component (A), cyclopentadiene, dicyclopentadiene, tricyclopentadiene,
Tetracyclopentadiene, etc. and their substitution products,
Preferably, one kind or two or more kinds of lower alkyl-substituted compounds having 1 to 3 carbon atoms (eg, methylcyclopentadiene) and the like are used.

Further, as the component (B), (meth) allyl alcohol, 2-hydroxyethyl (meth) acrylate, 1,
One or more of 4-butenediol, 1,3-butenediol, 2-hydroxypropyl (meth) acrylate and the like are used.

When the component (A) and the component (B) are reacted in the present invention, the molar ratio of component (A) / component (B) is 30 / 70-9.
5/5, preferably between 40/60 and 80/20,
In the presence of a radical catalyst at 150 ° C to 350 ° C, or
Uncatalyzed, if desired in the presence of a solvent, under pressure,
Polymerize for 3 to 10 hours. After completion of the polymerization reaction, a low molecular weight substance and unreacted substances are removed under reduced pressure at 180 to 230 ° C. to obtain a resin (I).
Has a melting point of 60 to 150 ° C. and consists of a mixture of several structures. In the reaction of both the components (A) and (B), cyclopentadiene and dicyclopentadiene are mainly used as the component (A), and allyl alcohol is mainly used as the component (B).

Further, the resin (II) may be a resin obtained by selectively hydrogenating only the double bond of the resin (I), and the resin (I) may be hydrogenated by a noble metal such as platinum or palladium, nickel, copper-chromium or the like. Hydrogenation can be carried out in the presence of a catalyst, if desired, in the presence of a solvent at room temperature to 250 ° C. and normal pressure to a pressure of 100 kg / cm ² without decreasing the amount of hydroxyl groups. is there. At this time, the degree of hydrogenation is not particularly limited, but is 40% or more, preferably 80% or more of the carbon-carbon double bond of the resin (I).

The hydrogenated resin (II) has less yellow coloring and lower odor than the resin (I) and is excellent.
(Hereinafter, the resin (I) and / or the resin (II) are collectively referred to as a DCPD polyol.) In the present invention, the above-mentioned DCPD poiol is used as a polyol component for producing a hydroxyl group-excess alkyd resin (III) described later. Used as part or all of.

Examples of the polyol component other than the DCPD polyol of the excess hydroxyl group alkyd resin include aliphatic polyols such as glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, and tripentaerythritol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, tripropylene. One or more kinds of glycols, glycols such as neopentyl glycol, trimethylol isocyanurate, trimethylol melamine, cyclic polyols such as hexamethylol melamine and the like are used.

The polybasic acid component of the hydroxyl group-excess alkyd resin is adipic acid, succinic acid, fumaric acid, maleic acid, maleic anhydride, isophthalic acid, phthalic anhydride, terephthalic acid, trimellitic acid, trimellitic anhydride, tetrahydro. One or more of phthalic anhydride, hexahydrophthalic anhydride and the like are used.

In addition, in order to produce the hydroxyl group-excess alkyd resin (III), flaxseed oil, rice bran oil, castor oil, dehydrated castor oil, coconut oil, tung oil or their fatty acids, caproic acid, caprylic acid, capric acid may be used as necessary. Saturated fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, etc., unsaturated fatty acids such as oleic acid, linoleic acid, linolenic acid, eleostearic acid, ricinolenic acid, rosin, water-added rosin, disproportionate Fluorinated rosin, polymerized rosin, etc. 1
At least 50 parts by weight can be used in combination with 100 or more parts by weight of polyol and polybasic acid.
If it exceeds 50 parts by weight, the molecular weight of the hydroxyl group-excess alkyd resin decreases, and further, the cured film becomes plastic and solvent resistance deteriorates.

In addition, if necessary, methanol, ethanol,
A monohydric alcohol such as propanol, butanol, hexanol, octanol, benzyl alcohol, cyclohexanol, ethylene glycol monoalkyl ether, or oxo alcohol can be used in combination.

In the present invention, the method for synthesizing the hydroxyl group excess alkyd resin (III) is as follows: DCPD polyol 20 to 80 parts by weight, D
5 to 50 parts by weight of a polyol other than the CPD polyol, 10 to 50 parts by weight of a polybasic acid, and if necessary, the above fatty oil,
Fatty acids, rosins, monohydric alcohols, etc. are added up to 50 parts by weight with respect to 100 parts by weight of polyol and polybasic acid in total, and these are charged in a four-necked flask equipped with a stirrer and a condenser and condensed at 150 ° C to 280 ° C. The reaction is carried out while removing water which is sometimes generated to obtain an alkyd resin (III) having an excess hydroxyl group with an acid value of 20 or less, preferably 10 or less.

During the above synthesis, the amount of DCPD polyol needs to be 20 to 80 parts by weight, and if it is less than 20 parts by weight, the polyester part due to the reaction of the polyol other than DCPD polyol and the polybasic acid increases, and as a result, The melting point rises and the solubility in mineral oil deteriorates. And
If an anchor coating agent is made using the finally obtained curable resin, the fluidity and gloss deteriorate. Also, DCPD
When the amount of the polyol is more than 80 parts by weight, the crosslinkable part is reduced, the molecular weight of the hydroxyl group-excess alkyd resin (III) is decreased, and the printability, setting property and drying property are deteriorated during the production of the anchor coating agent.

Further, in the above synthesis, when the polyester by-product is partially avoided by the reaction of the polybasic acid and the polyol other than the DCPD polyol, the DCPD polyol and the polybasic acid, if necessary, fatty oil, fatty acid, rosin, It is preferable to add the polyol other than the DCPD polyol after the esterification reaction with the polyhydric alcohol.

In the present invention, the hydroxyl group-excess alkyd resin (III) is produced as described above, and the hydroxyl group excess amount of the hydroxyl group-excess alkyd resin (III) is 120 to OH equivalent.
1260, preferably 150-300.

In the present invention, the hydroxyl group-excess alkyd resin (III) obtained as described above is esterified with acrylic acid and / or methacrylic acid to obtain a product curable resin (IV). When acrylic acid and / or methacrylic acid are used in an amount of 5 to 50 parts by weight, preferably 10 to 35 parts by weight, with respect to 95 to 50 parts by weight of the hydroxyl group excess alkyd resin (III), the resulting curable resin (IV) is obtained. The curability, molecular weight distribution, solubility, etc. of can be improved. The reaction of the hydroxyl group-excess alkyd resin (III) with acrylic acid and / or methacrylic acid is carried out by reacting 95 to 50 parts by weight of the hydroxyl group-excess alkyd resin (III), 10 parts by weight of a reflux solvent such as cyclohexane, and a thermal polymerization inhibitor such as hydroquinone. 1 part by weight was placed in a four-necked flask equipped with a stirrer and a condenser directly connected to a separation tube, and 5 to 50 parts by weight of acrylic acid and / or methacrylic acid was added at about 80 ° C., while blowing air to 1
When the acid value is 30 or less, preferably 20 or less, the reaction is carried out at 00 to 120 ° C. while removing water generated during the condensation,
The reflux solvent such as cyclohexane is removed and the curable resin according to the present invention is pumped out.

Examples of the sensitizer used in the production of the active energy ray-curable anchor coat composition include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin butyl ether, benzophenone, benzyl, xanthone, thioxanthone, methylbenzoylbenzoic acid, Ethylbenzoylbenzoic acid, acetophenone, 4-dimethylaminoacetophenone, p-dimethylaminobenzaldehyde, p-dimethylaminobenzoic acid, ethyl m-dimethylaminobenzoate, amyl p-dimethylaminobenzoate, m-dimethylaminobenzoic acid, o One or more of amyl dimethylaminobenzoate and 4,4-bisdiethylaminobenzophenone are used.

Further, as the viscosity adjusting monomer, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate,
One type of dipentaerythritol polyacrylate, dipentaerythritol polymethacrylate, triallyl isocyanurate, triallyl citrate, polyethylene glycol diacrylate, ethylene glycol dimethacrylate, polypropylene glycol diacrylate, phenylglycidyl acrylate, phenylene diglycol diacrylate, etc. Or 2 or more types are used.

Further, in the present invention, azo pigments (Hanser Yellow, Benzidine Yellow, Laked C, Carmine 6
B, Permanent Red 2B, etc.), phthalocyanine-based pigments (phthalocyanine blue, phthalocyanine green, etc.), quinacridone-based pigments, isoindolinone-based, quinophthalone-based organic pigments, titanium white, carbon black, red iron oxide, zinc white Inorganic pigments such as calcium carbonate can be used.

As the offset ink, an active energy ray curable ink is preferable, and a thermosetting ink can also be used if necessary.

The active energy ray curable ink is composed of a prepolymer, a monomer, a sensitizer, a pigment, an additive, etc. As the prepolymer, generally known epoxy acrylate, oil-modified alkyd acrylate, unsaturated polyester, etc. can be used. .

As the overprint varnish, active energy ray-curable varnish is desirable. Of course, any other over-punlitonis may be used.

UV curable offset ink to be printed on the anchor coat, general ink that is commercially available for over-punlitonis and over-punlitonis can be used. Wet-on-wet for anchor coat (printing without curing the anchor coat agent) ) And wet-on-dry (printing after curing the anchor coat).
However, in the case of wet-on-wet, the anchor coat agent may be insufficiently cured, and wet-on-dry is desirable.

The method for producing a printed matter of the present invention makes it possible to perform offset printing using all UV curable inks by using an anchor coating agent for UV curable offset printing, which has good adhesion to polypropylene, polyvinyl chloride and the like. Excel.

(B) The cost and productivity of the anchor coat are improved.

(B) Partial printing of the anchor coat is easy.

(C) It does not pollute the environment because it does not use volatile solvents. In addition, there is little adverse effect of the additive on the material to be printed.

(D) Since only accurate offset printing is used, the finishing effect is good and it is possible to apply an anchor coat only to the colored ink portion.

(E) There is no adverse effect of heat on the printing medium.

(F) There is no difficulty in process control by using different printing methods. Also, the change over time in the anchor coat is less than in the past.

Next, the present invention will be described in more detail with reference to synthesis examples, examples and comparative examples. In the examples, “part” means “part by weight”.

Synthesis Example 1 660 g of 96% pure dicyclopentadiene, 300 g of allyl alcohol and 500 g of commercially available mixed xylene were charged in an autoclave equipped with a stirrer and reacted at a temperature of 260 ° C. for 5 hours. After completion of the reaction, the autoclave was cooled, and the contents were distilled to remove unreacted monomer, low polymer and xylene to obtain 750 g of Resin (I). 100 g of this resin (I) was dissolved in 75 g of commercially available mixed xylene, 1 g of palladium carbon having a palladium concentration of 5% (5% Pd-C standard product made by Nippon Engelhardt) was added, and hydrogen pressure was 30 kg / cm ² , 150. A hydrogenation reaction was carried out at ℃ for about 1 hour and the solvent was distilled off to obtain a water-added resin (II). The properties of resin (I) and resin (II) are as follows.

Next, 45 parts of Resin (I), 29 parts of phthalic anhydride, and 26 parts of trimethylol punpan were placed in a four-necked flask equipped with a stirrer and a condenser directly connected to a separation tube, and charged under a nitrogen gas stream at 2
The reaction was carried out at 40 ° C. for 7.5 hours to obtain a hydroxyl group-excess alkyd resin (III) having an acid value of 7.8. 80 parts of this hydroxyl group-excess alkyd resin (III), 20 parts of acrylic acid, 1 part of paratoluene sulfonic acid, 0.1 part of hydroquinone are mixed with a stirrer,
A 4-necked flask equipped with a condenser directly connected to a separation tube was charged, and reacted under reflux of cyclohexane / methyl isobutyl ketone (2: 1) at 80 to 120 ° C for 15 hours to give an acid value of 20.5.
The reflux solvent (cyclohexane / methyl isobutyl ketone (MIBK)) was distilled off at 115 ° C. to obtain a curable resin (IV) acid value of 18.3.

Example 1 An anchor coating agent vehicle was manufactured using 65 parts of the curable resin (IV) obtained in Synthesis Example 1 and 35 parts of phenylenediglycol acrylate. 60 parts of vehicle, 15 parts of white luster O (exterior pigment manufactured by Shiraishi Industry Co., Ltd.), 10 parts of benzyl, and 15 parts of phenylene diglycol diacrylate were made into ink using a three-roll mill to obtain an anchor coating agent for offset printing.

Using this anchor coat agent, offset printing was performed on a 0.7 mm-thick polypropylene sheet (surface mat manufactured by Achilles Co., Ltd.) and 100 m / min with 5 lamps of 80 w / cm.
It was irradiated with ultraviolet rays and cured at a speed of. Immediately after printing the anchor coat agent, offset multicolor printing is performed on the anchor coat using FDO Yellow G, FDO Beni G, FDO Ai G, and FDO Black G (UV curable ink manufactured by Toyo Ink Mfg. Co., Ltd.). A printed matter was obtained by irradiation with ultraviolet rays, and the ink adhesion of this printed matter was good.

Further, the anchor coat was made thicker by 0.2 mm than the color ink part in order to cover the misregistration with the color ink, but the anchor coat on the printed matter was hardly discernible.

Example 2 60 parts of anchor coat vehicle obtained in Example 1, Fines Red F2B (red pigment manufactured by Toyo Ink Mfg. Co., Ltd.) 15
Part, 4,4-bis (diethylamino) benzophenone 5
Part, 3 parts of phenylene diglycol diacrylate 15 parts
This roll mill was used as an ink to obtain an anchor coating agent for offset printing.

Using this anchor coating agent, printing was performed in the same manner as in Example 1 to obtain a printed matter. The ink adhesion of this print was good.

Synthesis Example 2 An alkyd resin (II obtained in the same manner as in Synthesis Example 1 using the resin (II) obtained in Synthesis Example 1 as a polyol component
I) 78 parts, p-toluenesulfonic acid 1.0 part, hydroquinone 0.1 part, cyclohexane / MIBK (2:
1) Charge 15 parts of the mixed solvent into a 4-neck flask equipped with a stirrer and a condenser directly connected to a separation tube, and add acrylic acid 22 at 80 ° C.
Part, and reacted at 100 ° C. for 7.5 hours to give an acid value of 18.
Then, the cyclohexane / MIBK (2: 1) mixed solvent was distilled off over 3 hours at 115 ° C. to obtain a curable resin (IV) acid value of 15.4.

Example 3 The curable resin (IV) obtained in Synthesis Example 2 was converted into an ink in the same manner as in Example 1 to obtain an anchor coating agent.

Using this anchor coating agent, a 0.2 mm polyvinyl chloride sheet (manufactured by Sumitomo Bakelite Co., Ltd.) was printed in the same manner as in Example 1 to obtain a printed matter. The adhesiveness of this printed matter was good.

Example 4 Multicolor offset printing was performed in the same manner as in Example 1 one week after printing the anchor coating agent on Examples 1, 2 and 3 to obtain a printed matter, but the ink adhesion of the printed matter was good.

Synthetic Example 3 43 parts of the resin (II) obtained in Synthetic Example 1, 10 parts of rosin, 23.5 parts of adipic acid, and 24 parts of pentaerythritol were reacted in the same manner as in Synthetic Example 1 to give a hydroxyl group having an acid value of 10.6. An excess alkyd resin (III) acid value of 16.9 was obtained.

75 parts of this hydroxyl group-excess alkyd resin (III) and 25 parts of acrylic acid were reacted in the same manner as in Synthesis Example 1 to obtain a curable resin (IV).

Synthesis Example 4 27 parts of the resin (II) obtained in Synthesis Example 1, 11.2 parts of 2-ethylbutanol, 32.5 parts of RICACID HH (hexahydrophthalic anhydride manufactured by Shin Nippon Rika), and 29.2 parts of trimethylolpropane were prepared. The reaction was performed in the same manner as in Synthesis Example 2 to obtain a hydroxyl group-excess alkyd resin (III).

78 parts of the hydroxyl group-excess alkyd resin (III) and 22 parts of acrylic acid were reacted in the same manner as in Examples 1 and 2 to obtain a curable resin (IV) acid value of 16.3.

Examples 5 and 6 In the same manner as in Example 1, using the respective resins (IV) obtained in Synthesis Examples 3 and 4, respective anchor coating agents were obtained.

Anchor coat printing and offset multicolor printing were performed in the same manner as in Example 1 using this anchor coat agent, and the respective prints had good ink adhesion.

Example 7 In the same manner as in Example 2, the anchor coating agent was offset printed, irradiated with ultraviolet rays, and then offset multicolor printing was performed. Next, FDO multicolor OP varnish AL (manufactured by Toyo Ink Mfg. Co., Ltd.) was used as an ultraviolet-curable overprint varnish for offset printing and ultraviolet irradiation.

Synthesis example 4 Epicoat 828 (epoxy resin made by Shell Petrochemical) 7
5 parts, hydroquinone 0.1 part, ethylenediamine 0.
Charge 2 parts into a 4-necked flask equipped with a stirrer condenser,
Add 25 parts of acrylic acid at 80 ℃,
Curable resin (V) having an acid value of 3 was obtained by reacting for a time.

Comparative Example 1 Using the curable resin (V) obtained in Synthesis Example 3, an attempt was made to obtain a printed matter in the same manner as in Example 1, but the adhesiveness of the anchor coat was inferior, and when the offset multicolor printing was performed, Peeling occurred, and good printed matter was not obtained.

Comparative Example 2 The same sheet as in Example 1 was printed with an anchor coating agent by silk screen printing. As the anchor coat agent, matte SS26 mat 611 white (manufactured by Toyo Ink Mfg. Co., Ltd.) was used to match the gloss with the sheet, and 5 parts of the curing agent was added to 95 parts of the anchor coat agent. Curing was performed at 65 ° C. for 15 minutes.

The anchor coating agent was made thicker than the colored ink portion by about 5 mm due to the registerability of silk screen printing and the expansion and contraction of the sheet due to heat during curing.

Immediately after printing the anchor coat, offset multicolor printing was performed in the same manner as in Example 1 to obtain a printed matter. The ink adhesion of this print was good. However, the anchor coat part was considerably larger than the colored ink part, and there was swelling due to silk printing, and the existence of the anchor coat was clearly recognized.

Also, one week after the anchor coat printing, the ink printed on the same offset printing had poor ink adhesion.

Comparative Example 3 The same sheet as in Example 1 was anchor-coated with a roll coater. Ramicoat P (manufactured by Toyo Ink Mfg. Co., Ltd.) was used as the anchor coat agent for the roll coater. Immediately after applying the anchor coat, offset multicolor printing was performed in the same manner as in Example 1 to obtain a printed matter. The ink adhesion of this printed material was good, but the additive in the sheet was raised on the surface, causing uneven transfer of the colored ink.

In addition, by applying the anchor coat, the gloss of the sheet surface also increased, and the existence of the anchor coat was clearly recognized.

One week after applying the anchor coat, offset multicolor printing was similarly performed, but the ink adhesion of this print was poor.

Claims (2)

[Claims] 1. A printing material selected from polypropylene moldings and polyvinyl chloride moldings, having the following general formula: (In the formula, R represents an organic residue having 1 to 3 carbon atoms, m and n each represent 0 or an integer, and m + n = 6.) A 5-membered ring compound having an unsaturated conjugated double bond, Or these Dies Alder compounds (A)
And a compound (B) having an unsaturated double bond and a hydroxyl group in the same molecule, the resin (I) having a hydroxyl group, and / or the resin having a hydroxyl group obtained by hydrogenating the resin (I). (II) is contained as a polyol product in the production of an alkyd resin to produce a hydroxyl group-excess alkyd resin (III), and the hydroxyl group-excess alkyd resin (III) is produced.
The active energy ray anchor coating agent containing the active energy ray curable resin (IV) obtained by esterifying acrylic acid and methacrylic acid is applied by offset printing according to the area to be offset printed with the offset ink, and then, A method for producing a printed matter, which comprises performing offset printing on the anchor coat surface with an active energy ray-curable offset ink, and irradiating with an active energy ray before or after printing the offset ink. 2. The method for producing a printed matter according to claim 1, wherein the anchor coating agent and the offset ink are offset-printed on a printing medium, and an overprint varnish is further applied.