JPS6178815A - Photocurable resin - Google Patents

Abstract

PURPOSE:The titled resin excellent in curability, adhesion to an oil-base ink as an undercoat, gloss, etc., and suitable as, e.g., a base for photocurable paints, obtained by reacting polymerized rosin with a polyisocyanate, a polyfunctional alcohol and/or an epoxy compound. CONSTITUTION:100pts.wt. polymerized rosin (A) (e.g., gum rosin or wood rosin) is reacted with 5-70pts.wt. polyisocyanate (B) (e.g., tolylene diisocyanate) and 20-120pts.wt. polyfunctional alcohol (e.g., 2-hydroxyethyl acrylate) and/or epoxy compound (e.g., butyl glycidyl ether) (C). In this way, an ester is formed by reaction of component A with component C and urethane bonds are formed by reaction of component B with active hydrogen atoms to obtain the purpose photocurable resin comprising a polymerized rosin-modified urethanized unsaturated resin having at least one photosensitive polymerizable unsaturated group in the molecule.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of industrial application;
This invention relates to photocurable resins used for paint pastes (abbreviated as varnishes), paint pastes for photocurable printing inks, pasteboards for photocurable paints, etc.

Conventional technology: Conventional sheet-fed offset ink (hereinafter referred to as oil-based ink).

) requires nine steps of evaporation of a high-boiling-point liquefier, oxidative polymerization, and then drying, so it takes a long time to dry and there is a risk of pollution from the solvent. Sheet-fed printing, such as printing with Calton printing, is printed at high speed and the printed matter is piled up in the delivery department, so set-off may cause a blocking phenomenon.
In order to prevent this, Bakugou is sprayed on the printing surface, but Bakugou scatters and adheres to the printing rubber roll, causing a decrease in ink migration, damage to the rubber roll itself, contamination of the working environment, and powder. Its use itself is a factor in increasing costs.

As a way to solve the shortcomings of these conventional oil-based inks, radiation-curable inks, especially ultraviolet-curable inks, have begun to be used, and EVC has become possible to stack without blocking without spraying, and furthermore, it can be stacked immediately after printing. It is now possible to process However, conventional ultraviolet curable inks are expensive and have the disadvantage of being difficult to commercialize.

As a compromise measure to reduce prices, oil-based ink is used as the base color ink, and an ultraviolet-curing OP varnish (hereinafter referred to as UV0P varnish) is simultaneously overprinted (coutte coat), which is treated with ultraviolet irradiation. Attempts have been made to find a way to obtain prints that dry instantly and can be stacked without blocking. However, when conventional photocurable resin is used as UV 0P varnish, the adhesion to the underlying oil-based ink is poor. There is a drawback that the gloss of the printed matter is not sufficient.

Problems to be solved by the present invention: In the present invention, the problems are the problems of the above-mentioned folding type ink. We aim to improve the imperfect mQ properties with oil-based inks and the rain m point of poor gloss, and to provide a complete photocurable resin.

Means for solving all problems: The photocurable resin of the present invention contains (a) 100 parts by weight of polymerized rosin, (5 to 70 parts by weight of Hakatahydric incyanate, and (c) polyfunctional alcohol (polyhydric alcohol). , work,
Acryloyloxy is a general term for monohydric alcohols having metabroyloxy type acyloxyl groups. ), machining/mafcVi, epoxy compound 20-120 g
1ri? It is a polymerized rosin-modified phretanized unsaturated side fat contained as a bound fraction.

It goes without saying that the resin having the above composition must further have one or more photopolymerizable unsaturated bonds per polymer molecule.

In the present invention, polymerized rosin means, for example, gum rosin, cladomidine, tall rosin, etc., 0°-200°C.
This refers to a rosin modified product in which the abietic acids contained therein are trimerized using an acid catalyst such as sulfuric acid. The reason for containing polymerized rosin in the photocurable resin of the present invention is that the rosin double body Compared to the monomer, it has a larger polycyclic structure and is a dibasic acid, so this polycyclic structure is present in the main chain of the photocurable resin molecule. Due to its presence, oil-based inks (usually containing rosin-modified phenolic resins) were introduced.

), adhesion is the same as above, and gloss is increased.Especially when used in offset inks, the gloss is further improved due to its greater affinity for pigments (C increased, hydrophobic It is the first type that exhibits excellent effects such as increased emulsification resistance because of its large size.In this case, it does not have up to G5 or completely loses the photocurability of 1T4 fat, but rather has a polycyclic structure in the main chain. In addition, the photocurability from the viewpoint of surface dryness is the same as above.

Examples of the polyvalent incyanates used herein include tolylene diisocyanate, diphenylmethane isocyanate, hexamethylene diisocyanate, inophorone diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, polymers of various incyanates, and the above polyvalent inocyanates. Polyvalent incyanates such as adducts of cyanates and active water injection compounds.

The reason for using 5 to 70 parts of poly-11 [5 isocyanate is that the flex bond is intact, the photocurability is the same as above,
In addition, highly hydrophilic hydroxyl groups are reduced and 7t are eliminated, resulting in better compatibility with oil-based inks, increased adhesion and gloss, and improved emulsion resistance. If the amount of polyvalent incyanate is less than 5 parts by weight, the yield of phletane decreases, the hydroxyl value increases, and the photocurability improves.B! The film strength, gloss, dark blue property, il resistance, and curing property are all reduced, and on the other hand, if the coating is increased by 70% by weight, high rotting and gelation occur, which is not preferable.

Examples of polyfunctional alcohols used for large-scale use include 2-hydroxyethyl (meth)acrylate ((meth)acrylate is a general term for acrylate and methacrylate), 2-hydroxypropyl (
meth)acrylate, allyl alcohol, ethylene glycol, propylene glycol, diethylene glycol, 1,3-gutylene gelicol, 1,6-hexanediol, neopentyl glycol, chrycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, and many more Ethylene oxide of alcohol is a propylene oxide adduct, ethylene oxide of bisphenol A is a propylene oxide adduct, etc., which contain an alcoholic hydroxyl group with a VC of 1 or more in one molecule, and when the alcoholic hydroxyl group is 1, (meth) ) It has an acryloyloxy type acyloxyl group.

Next (in the present invention, epoxy compound is referred to as 1,000 yen per minute.
Refers to substances having the above epoxy groups that can be ring-opened to provide alcoholic hydroxyl groups, such as ξ, butyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether, di-coated polyhydric polyols of polyhydric alcohols, etc. glycidyl ether, bisphenol A diglycidyl ether and combinations thereof, 0-cresol novolac polyglycidyl ether, glycidyl (meth)acrylate, heptacuric acid diglycidyl ester, trimellitic acid glycidyl ester, triglycidyl in cyanurate,
These include diglycidyl ester of Guyaric acid (a polymer of animal and vegetable oil fatty acids), epoxidized parts, and epoxidized polygetadiene.

The above-mentioned polyfunctional alcohols and epoxy compounds have a common point in that their raw materials after reaction have an alcoholic hydroxyl group, and can be considered as the same group. Since there is no problem even if a mixture is used, this is expressed using Table A21- of (OLBI/MANOHA). Its use for polymerization logs 2100 weight units (iI is 2
0 to 120 parts by weight is desirable; if the content is less than 20M parts, the content of alcoholic hydroxyl groups will not be sufficient to form a desirable level of urethane bonds; 1) photopolymerizable unsaturated bonds will decrease; 3) photocuring Sexuality decreases.

In addition, if 12071i (Miyako or higher) is used, the content of hydroxyl groups in the photocurable resin will increase, compatibility with oil-based ink will deteriorate, and adhesiveness and gloss will decrease.In addition, in offset printing,
Emulsification resistance decreases due to increased water resistance O A part of the photocurable N resin V′i polymerized rosin of the present invention is added to other carboxylic acids 17j.1 For example, non-polymerized rosin, benzoic acid,
p-tert-glutylbenzoic acid, O-benzoylbenzoic acid, 1
Fragrant acid, (meth)acrylic acid, various cut vegetable oils and fats Δ2, and their polymers, guimaric acid, succinic anhydride, maleic anhydride, 7-maric acid, icconic acid, adipic acid, cepatic acid, 7-talic anhydride, Monosalt springs such as isophthalic acid, trimellitic anhydride, and pyromellitic anhydride can be used even if all dibasic acids or higher polybasic acids are used. Carvone tR other than the polymerized rosin of Koori et al. can also cause an esterification reaction, and in particular, polybasic acids of two or more basic acids have the effect of linking molecules together rather than ester bond traps. It is chemically similar to polymerized rosin and can be used as a complete substitute for polymerized rosin. However, and 1 et al.
It is inferior to polymerized rosin in terms of gloss, pigment dispersibility, photocuring/curving, fL resistance, etc., and is actually not as good as polymerized rosin. However, by adding 7-talic anhydride, maleic anhydride, 7-malic acid, etc., which are available at a relatively low cost, to the polymerized rosin, the price of the photocurable resin produced can be reduced.

Polymerized rosin, polyvalent isocyanate, and polyfunctional alcohol-coated/coated epoxy compound mutually create a chemical moiety and bond. It reacts with an epoxy compound to form an ester, and the polyvalent isoneanate reacts with active hydrogen (particularly the hydrogen of the hydroxyl group) to form a urethane bond. You can also react to all three at the same time.

It goes without saying that in order to cause photocuring, each molecule of the polymer produced by the above reaction must have at least one photopolymerizable unsaturated bond.

Naturally, it is desirable to adjust the working viscosity, curability, properties of the cured film, etc. of the photocurable resin of the present invention depending on the intended use. , polyfunctional alcohol preparation/ma7tF
The type and mixing ratio of the i-technical poxy compound may be varied.

For example, in order to completely reduce the viscosity, the content of polyvalent incyanate is completely reduced, the molecular weight of the photocurable resin is lowered, and polyfunctional alcohols and/or epoxy compounds with low functionality or aliphatic compounds are added. You can use something like that.

In order to increase the curability, the total concentration of Vi photopolymerizable unsaturated groups was increased, and the aromatic If? If the molecular weight of the photocurable resin is increased and the molecular weight of the photocurable resin is increased. In order to increase the strength of the cured film, the amount of urethane bond gold is increased, and the photopolymerizable unsaturated group concentration is increased. For example, a (meth)acroyl group-containing compound or a vinyl group-containing compound can be added.

The above-mentioned difference between the collected fraction of the present invention and the reactive diluent is that the collected fraction of the present invention is in the state of a relatively high molecular weight resin,
It exhibits consistent performance when used in formulations for applications such as OP varnish and ink. On the other hand, reactive diluents are compounds with relatively low molecular weights, e.g., less than 1000, and low viscosity, and are used in formulations for various purposes to impart a specific working viscosity and adjust performance. It is. Therefore, the pre-release resin of the present invention serves as a paste resin when processed into photocurable OP varnish, ink, paint, etc. in the final use.

Examples of reactive diluents include (meth) such as methyl, ethyl, butyl, offyl, tetrahydrofurfuryl, sifenoquiethyl, butoxyethyl, glycidyl, 2-hytomyxethyl, hydroxypropyl, dimethylaminoethyl, etc. ) acrylate, ethylene glycol, neobentyl glyco-7L/, di(meth)acrylic acid ester such as 1-5 hexipundiol, diethylene glycol, polyethylene glycol, bisphenol di(oxyethyl) diether di(meth)acrylate, trimethylolpropane, penta Examples include tri(meth)acrylic acid esters such as erythritol, and hekiza(meth)acrylic esters such as dipentaylythritol and hekiza(meth)acrylate.

In addition, when using ultraviolet light as light,
It goes without saying that it is advantageous to use known initiators such as carbonyl compounds, ioc compounds, and azobis compounds.

Example 1 Thermometer, cooler, stirrer included, internal volume 11! Tolylene diisocyanate (TDI-80) in a four-necked flask.
300 parts (the same applies below), 1 part of dibutyltin silacrate was charged, heated to 60°C, then dissolved in 1 part of hydroquinone, and 200 parts of 92-hydroxyethyl acrylate was added dropwise over 3 hours. Keep the temperature at the same time, N
Acrylated incyanate with 14.0% CO groups (D total yield 7j.

Next, a thermometer, gas blowing pipe, stirrer, water separator, and cooler were installed, and a polymerized rosin with an acid value of 142 and a softening point of 140°C (People's Republic of China 1 (manufactured by) 2
84 J tetrapropanol ethylene diamine (average molecular weight 300, product name AE-300, manufactured by Nihon σtatsu@J) 1
100% of the mixture was charged and reacted for 10 hours at 270°C under a stream of nitrogen gas to reach an acid value of 8. After that, the mixture was cooled for 120°C, 200 parts of butyl acetate was added, and the temperature was raised to 60°C.

The above-mentioned acrylated incyanate (I) 1
06 parts were added in a total of 1 hour, and after being kept at 60°C for 2 hours, the reaction was carried out for 2 hours under the flow of butyl #acid, and the infrared spectrum showed 22
After the absorption of 60c+i+-' (NCO group) had disappeared and the residue was confirmed, butyl acetate was distilled off under reduced pressure to obtain a photocurable M resin (A) with a softening point of 80°C.

Example 2 300 parts of TDI-80 and 1 part of diptyltin laflate were charged into 1 ton of the same apparatus used to obtain acrylated isocyanate (I) in Example 1, and heated to 60°C. Next, a mixture of 21 parts of hydroquino dissolved, 133 parts of 2-hydroxyethyl acrylate, and polypropylene glyco was added dropwise over 3 hours, and the temperature was kept at the same temperature for 3 hours.
5% of acrylated isocyanate 01 -O obtained Next, among the materials used in Example 1, 106 parts of acrylated incyanate (I) ([) 211 parts of the above acrylated incyanate) except for t, using
A photocurable resin (B) with a softening point of 72° C. was obtained by substantially the same treatment.

Example 3 Polymerized rosin 283 was added to the esterification apparatus used in Example 1.
1 part, 64 parts of asymmetric rosin (manufactured by Harima Kasei Kogyo ■, part name: Pandis G-100F), 51 parts of stearic acid, 18 parts of succinic anhydride, AE-300165. After the same treatment, the softening point was 7.
Obtain photocurable resin (C) at 7°C.

Example 4 χ Acrylated in Example 1) (In'fc
? TD-80300ill in the same equipment as G fc,
Charge 1 part of dibutyl roughrate and heat to 60°C.

Next, hydroquinone I Fl's k r8 dissolved nigecilone-cabrolactone addition and droxyethyl acrylate (Gycel Chemical Industry Co., Ltd. Same product name Glaxel FA-1
, hydroxyl value 244) 397 gis was added dropwise over 3 hours and kept at the same temperature for 2 hours to obtain acrylated incyanate (IID) with 10% NCO groups. 100 parts of the above acrylated isocyanate (Ill) 148 parts of the above acrylated isocyanate (Ill) The same treatment was carried out except for the above to obtain a photocurable IfI fat (6) with a softening point of 74°C.

Example 5 300 parts of TDI-80 and 1 part of dibutyltin laphrate were charged into the same apparatus as used for obtaining acrylated isocyanate (I) in Example 1, and heated to 60°C. Next is Hydroquinone 11! 514 parts of St-esterified pentaerythritol triacrylate were added over 3 hours and kept at the same temperature for 2 hours to form an acrylated incyanate ΦE'xtG with 8.7% of NCO groups.

Of the raw materials used in Example 1, 86 parts of the above acrylated incyanate was used in place of 106 parts of acrylated incyanate (CI), and substantially the same treatment was carried out except for the following, to obtain a material with a softening point of 75°C. Example 6 Add 300 parts of inphoron diisocyanate and 1 part of dibutyltin laflate to the same equipment used in Example 1 to prepare the acrylated isocyanate (I). 157 parts of hydroxyethyl acrylate dissolved in 1 part of hydroquinone was added dropwise over a total of 3 hours while heating to 0°C, and left at the same temperature for 5 hours to obtain acrylated incyanate (V) with 12.2% of NCO groups. .

Next, of the fC raw material used in Example 1, 124 parts of the above acrylated isocyanate (I) was used instead of 106 parts of acrylated isocyanate (I), but substantially the same treatment was used, and the softening point was 75℃ photocured resin stool) was obtained.

Example 7 Silkworms The same treatment as in Example 4 was carried out except that 50 parts of pentaerythritol was used in place of 110 parts of AE-300 in Example 4, and a photocurable resin (with a softening point of 75°C) was treated with j4.
Ta.

Example 8 Thermometer, gas blowing pipe, stirrer, cooling pipe included, l>'c
A 4-day flask with an internal volume of 11 was charged with 248 volumes of polymerized rosin and heated to 200° C. under a nitrogen stream. Next, epoxy resin (Tobu Kashu Co., Ltd., 70-manufactured "Usui Meiko Bototo YD-128")
, 122 parts of epoxy (190), 0.2 parts of tetramethylammonicum taroride, and 4 parts at 220°C.
After a period of reaction to give an acid value of 1, the mixture was cooled to 150'C, and 200 g of butyl was added thereto to bring the temperature to 60°C.

This material was treated with 130 parts of the acrylated incyanate obtained in Example 4, just as in Example 1, to obtain a photocurable resin having a softening point of 70°C. 1 Photocurable fffr resin in Example 1? In the same equipment used in Example 1, 65 parts of p-tart-butylbenzoic acid and 30 parts of isophthalic acid were used in place of 284 parts of polymerized rosin. Example 90 A photocurable resin (ratio A) with a softening point of 65° C. was obtained by the same treatment. Among the raw materials used in production, acrylic isocyanate (
I) Instead of 106%, acrylated incyanate (22 parts D) was used, except that the rotation and substantial VCl51
A photocurable resin (ratio B) with a softening point of 72° C. was obtained through all the treatments.

Implementation-j Ratio 3 1 In a 4-day flask with a ξl internal volume of 1J, equipped with a meter, a stirrer, and a condenser, add Epotot YD-128380m, 83% of isophthalic acid, 72% of acrylic acid, and 0.5% of hydroquinone. 1 part, 1 part of tetramethylammonicum chloride, reacted at 110'C for 8 hours to give an acid value of 1, and a photocurable resin having a softening point of 60°C (ratio C).

Test eyelids: Using the photocurable resin obtained in the above Examples and Comparative Examples, a face was prepared with the formulation shown in Table 1, and a performance test was conducted as follows.1. 1. Ink adjustment rosin modified phenolic resin (Yokoma Kasei Kogyo Product name: Harifeno/L/P-170% softening point 163°C) Kneaded with gold powder, sprinkled with Daiichi Mugi, and kneaded with Miki rolls. I made sure to adjust the red ink.

2. Apply hardening OP varnish gold to the tin plate using a 3-bar coater. ! Cloth, 80W/σ convex pressure water lamp (manufactured by Iwasaki Electric ■) ZKW
Place 10 levers under the l lamp on a variable speed conveyor and pass through, and the dryness disappears at 9 to the touch, and at the conveyor speed 2
Display.

'fJ1 Table 3, adjust the adhesion l, t oil-based red ink 0, 15ml RI
It was separated onto coated cardboard using a tester 2-split roll, and then coated with 0.15 m of OP varnish in the same way, and then immediately dried with an ultraviolet ring until dry to the touch. For this river stone tableware, Nichiban Cello Tape was used. , a tape peeling test was carried out, and the adhesion with oil-based ink was completely evaluated. .

4. For a printed matter with a gloss level of 1, use a gloss meter (GN-3D manufactured by Murakami Color Co., Ltd.) to measure the gloss jet at a reflection angle of 60°. Table 2 (Note) (a) Phenoxyethyl acrylate-H-Using ratio (b) Bisphenol AK ethylene oxide 4 mol adduct (trade name A-BPE-4, manufactured by Nakamura Chemical Co., Ltd.) Usage ratio.

Claims (1)

[Claims] 1 100 parts by weight of polymerized rosin and 5 parts by weight of polyvalent isocyanate
-70 parts by weight and 20 to 120 parts by weight of a polyfunctional alcohol and/or epoxy compound as bonding components, a modified polymerized rosin having one or more photopolymerizable unsaturated groups per molecule A photocurable resin made of urethanized unsaturated resin.