JPS58160313A - Photosetting resin - Google Patents

Abstract

PURPOSE:A photosetting resin good in storage stability and luster and useful as a binder for photosetting printing inks or photosetting paints, comprising a specified disproportionated rosin-modified urethanized unsaturated resin. CONSTITUTION:A photosetting resin comprising a disproportionated rosin-modified urethanized unsaturated resin containing 100pts.wt. disproportionated rosin having an abietic acid content of below 1%, 20-100pts.wt. polyisocyanate (e.g., tolylene diisocyanate) and 10-60pts.wt. polyfunctional alcohol (e.g., 2-hydroxyethyl (meth)acrylate) as binding components and having at least one polymerizable unsaturated group per molecule and a hydroxyl value of below 80. This resin is easily cured with light and can be used chiefly as a binder for photosetting printing inks as well as for photosetting paints.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a photocurable resin that is easily cured by light and is mainly used as a binder for photocurable printing inks, but can also be used as a binder for photocurable paints.

Conventional photocurable printing inks include epoxy acrylate resin, phletane acrylate resin, and polyester acrylate resin. In particular, epoxy acrylate resin contains reactive diluents, photosensitizers, and pigments as main components, and other additives as necessary. Compositions containing additives are generally known.

Compared to conventional solvent-based printing inks, this type of printing ink eliminates the problem of environmental pollution caused by volatilization of organic layer agents, does not dry out on the printing press, and improves productivity through high-speed printing. It has the following advantages.

However, on the other hand, it tends to polymerize and turn into a gel, resulting in poor storage stability, poor wettability with pigments, and poor gloss.
(Especially in the case of offset printing, the ink is highly hydrophilic and has poor emulsion resistance, resulting in poor gloss and sharpness. Also, it is difficult to clean the printing press rolls with aliphatic hydrocarbon solvents, etc.) Solvent pear mark 11 due to its drawbacks
It has not reached the point where it has replaced 1J ink.

JP-A No. 54-118499 discloses a photocurable resin obtained by reacting a rosin-modified unsaturated resin ester with a metal alkoxide, which overcomes the drawbacks of conventional photocurable resins. However, since this resin uses an epoxy resin for its resin skeleton, it has many hydroxyl groups that are highly water-soluble, and as a result has the disadvantage of poor solubility in aliphatic hydrocarbons.

In view of the above circumstances, it is an object of the present invention to provide a photocurable printing ink binder that has good storage stability, good gloss and clearness, and is easy to clean with aliphatic hydrocarbons. It is an object of the present invention to provide a photocurable resin that can also be used as a binder.

The optically modified resin of the present invention includes (l) asymmetric rosin 100 having an abietic acid content of 1% (wt%, same hereinafter) or less;
(2) 1-20 to 100 parts by weight of polyvalent incyane, (3) 10 to 60 parts by weight of polyfunctional alcohol as bonding components, and contains 1 atopically unsaturated group per molecule. It is made of an asymmetric rosin-modified urethanized unsaturated resin having a hydroxyl value of 80 or less, and optionally a reactive diluent, such as a (meth)acryloyl compound (representing a methacryloyl compound and/or an acryloyl compound). , hereinafter the same), a vinyl group-containing compound can be added.

In the present invention, the disproportionated rosin is, for example, rosin 2
It is a modified rosin product in which abietic acids are mainly subjected to a disproportionation reaction using catalysts such as yokudo, iraq, and selenium at temperatures of 0.00 °C or higher, and the stability is increased by reducing the number of conjugated double bonds. This is what I did. Therefore, the degree of disproportionation was indicated by the content of abietic acid because, during disproportionation, isomers with conjugated double bonds, such as 1-ballast phosphoric acid and neoabietic acid, change to abietic acid. It is from.

The reason why the photocurable resin of the present invention contains asymmetric rosin is that the presence of this rosin improves the storage stability of the photocurable resin and has a high affinity for pigments without impairing photocurability. This is because it exhibits excellent effects such as improved gloss due to its strong hydrophobicity, improved emulsion resistance due to its strong hydrophobicity, and improved roll cleanability due to its high solubility in aliphatic hydrocarbons.

The use of 20 to 100% by weight of slender polyvalent isocyanate results in the formation of phletane bonds, which increases flexibility by +3.
3) This is because there are effects such as improvement in emulsification resistance and solubility in aliphatic hydrocarbon solvents due to the reduction or disappearance of highly water-soluble hydroxyl groups.

Examples of the polyvalent incyanate used in the present invention include l-lylene diisocyanate, diphenylmethane diisocyanate, hexametin diisocyanate, isophorone diisocyanate, xylidene diisocyanate, naphthalene diisocyanate, polymers of various diisocyanates, and the above-mentioned polyvalent incyanates and active hydrogen compounds. di- or polyisocyanates such as adducts of When the amount of polyvalent incyanate is less than 2 or parts by weight, the curability and emulsification resistance are low due to the decrease in the phrethane component and the hydroxyl value is J11'1M, and when it is more than 100 parts by weight. is undesirable because it causes high viscosity and gelation.

Polyfunctional alcohols include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, allyl alcohol, ethylene glycol, propylene glycol, diethylene glycol, 1.3-7' tyrene glycol, 1 .6-
Hexanediol, neobentanediol, glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, dipentaerythritol, etc. contain one or more alcoholic hydroxyl groups in one molecule, and when there is one alcoholic hydroxyl group, triple bond, (meta)
It has a functional group such as an acryloyl group.

In the present invention, an epoxy group-containing compound having one or more hydroxyl groups and a glycidyl group in one molecule,
For example, glycidyl (meth)acrylate, bisphenol A diglycidyl ether, condensates thereof, alkylphenol diglycidyl ether, alkylene glycol diglycidyl ether, persatic acid glycidyl ester, gimaric acid glycidyl ester, epoxidized parts, epoxidized polybutadiene, etc. Since it has a hydroxyl group and a glycidyl group, it is included in the polyfunctional alcohols mentioned above.

The amount of the alcohol component used is 10 to 6 of the photocurable resin.
It is appropriate to set the amount to 0 parts by weight.

In addition to the disproportionated rosin, the photocurable resin of the present invention also contains non-resin carboxylic acids such as benzoic acid, T"l; acids, phthalic anhydride, isophthalic acid,
Contains monobasic or dibasic acids such as tetrahydrophthalic anhydride, trimellitic anhydride, various vegetable oil fatty acids, and their polymerized products such as dimer acid, maleic anhydride, hexamaric acid, itaconic acid, and (meth)acrylic acid. May be used as

All of these non-resin carboxylic acids can undergo an esterification reaction, and among these, dibasic acids have the effect of bonding with two hydroxyl groups and linking atomic groups through ester bonds.

The above-mentioned asymmetric rosin, non-resin carboxylic acid, isocyanate, and polyfunctional alcohol mutually undergo a chemical reaction and bond. At this time, the constituent carboxylic acid of the asymmetric rosin and the non-resin carboxylic acid or The constituent carboxylic acids of the disproportionated rosin react with hydroxyl groups to form Nisder bonds, and the incyanate groups of polyvalent isocyanates react with active hydrogen, mainly the active hydrogen of hydroxyl groups, to form phrethane bonds. (b) A predetermined amount of asymmetric rosin, a non-resin carboxylic acid, a polyfunctional alcohol, or a) asymmetric rosin and a polyfunctional alcohol are simultaneously evaporated and then esterified, and then subjected to a phretanization reaction with an isocyanate. It can be easily obtained by

Next, in order to cause curing by light, at least one polymerizable compound per molecule must be present. It is axiomatic that it must have the l group.

[The reason why the monohydroxyl value is set to 80 or less is because if it is 80 or more, the emulsification resistance is poor and the solubility in the aliphatic hydrochloric agent decreases.

The photocurable resin of the present invention has a working viscosity, curability, properties of a cured film, etc. of 11. ! It is desirable that the disproportionate rosin be symmetrically adjusted, and for that purpose, the disproportionated rosin #1
After carboxylic acid, polyvalent isocyanate, polyfunctional (7) You can change the type and mixing ratio of alcohol, but as mentioned above, Kibatsu L! Further adding a reactive diluent, for example, a compound containing a (meth)acryloyl group, a compound containing a vinyl group, etc., to the photocurable resin of J1, and a substance having monofunctional and vinylic polymerizable unsaturated groups. Among these, (meth)acryloyl compounds are particularly preferred.

An example of a (meth)acryloyl compound is methyl (
Meg)acrylate, ethyl(meth)acrylate, butyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, tetrahydrofurfuryl(meth)acrylate, butoxyethyl(meth)acrylate, glycidyl(meth)acrylate, 2-hydroxyethyl(meth)acrylate,
meth)acrylic notes, 2-hydroxypropyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, (meth)acrylamide, ethylene glycol di(meth)acrylate, neopencundiol (meth)acrylate, 1,6-hexane Shiorji (Meg)
Acrylate, diethylene (8) glycol di(meth)acrylate, hydroxypivalic acid neopentanediol di(,meth)acrylate,
Polyethylene glycol di(meth)acrylate, bisphenol di(oxyethyl) diether di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(,meg)acrylate, diventaerythritol 1,000, quip(meth)acrylate Examples include.

In addition, when using ultraviolet rays as actinic rays, photosensitivity [I
J, benzoin series, benzophenone series, azo series,
It goes without saying that it is advantageous to use known sensitizers such as peroxide sensitizers.

Example 1: Equipped with a thermometer, cooler, gas blowing pipe, and stirrer Contents 11
! Tolylene diisocyanate (TD:
[-80) 300 parts (heavy weight parts, the same hereinafter) and 0.5 parts of dibutyltin silacrate were charged, and heated under a nitrogen gas stream for 6 hours.
Heat to 0°C. Next, 1 part of hydroquinone was dissolved in 2
-Hydroxyethyl acrylate) was added dropwise over 3 hours and kept at the same temperature for 2 hours to obtain acrylated isocyanate (I) with an NCO group percentage of 13.8%.

Next, a thermometer, a gas blowing tube, a stirrer, a water separator, and a condenser were added to a 1 liter four-bottle flask, and a symmetrical rosin pan with an abietic acid content of 0% and a dehydroabietic acid content of 7. 263 parts of Dis G-100S (manufactured by Harima Kasei Kou Awa), 25 parts of succinic anhydride, and 68 parts of penquerythritol were heated at 270°C under a nitrogen gas stream.
After reacting for 8 hours to bring the acid value to 6, the mixture was cooled to 100°C, and 200 parts of butyl acetate was added to bring the temperature to 60″C.

To this, the above-mentioned acrylated incyane) u)
After adding 145 parts over 1 hour and holding at 60°C for 2 hours,
After raising the temperature and reacting for 4 hours under refluxing butyl acetate, it was confirmed that the Neo group peak at 2250 am had disappeared in the infrared spectrum, and then butyl acetate was distilled off under reduced pressure to give an acid value of 4, a hydroxyl value of 33, A photocurable resin (4) having a softening point of 75°C was obtained.

Example 2 The same treatment as in Example 1 was carried out except that 140 parts of dimer acid (Versagym 216, manufactured by Henguru Nikki) was used instead of 25 parts of succinic anhydride, and the acid value was 3, the hydroxyl value was 28, and the material was softened. A photocurable resin (B) having a temperature of 55°C was obtained.

Example 3 Into the same apparatus used to obtain acrylated isocyanate (1) in Example 1, 01 part of TD Any and 0.5 part of digtyltin silaclate were charged and heated to 60'C under a nitrogen stream. Next, 278 parts of benquerythritol triacrylate prepared by dissolving 1 part of hydroquinone was added dropwise over 3 hours.
The temperature was maintained at the same temperature for a period of time to obtain an acrylated isocyanate (2) having an IJCo group% of 8.8.

Next, among the raw materials used in Example 2, 145 m of acrylated isocyanate was added to the above acrylated isocyanate.
The same process was carried out except that 21,236 parts per day was used, and the acid value was 4.
, a photocurable resin with a hydroxyl value of 26 and a softening point of 62°C (+)
) 'Ft-obtained.

Example 4 In the same equipment (11) in which the photocurable +-m t@(A) was made in Example 1, the disproportionated rosin Pandys (w 100826
3, pentaerythritol 68s was charged and reacted at 270°C for 8 hours under a nitrogen gas stream to give an acid value of 7.
Cool to 100° C. and add 200 parts of butyl acetate to obtain composition (2).

In addition to this, TD Any 044 part and acrylic incyane)
A mixture with 145 parts of ul was added over 1 hour and heated to 60°C.
After holding the temperature for 2 hours, the temperature was raised and the reaction was carried out under butyl acetate reflux for 4 hours, and an NOO group peak (225
After confirming the disappearance of 0cIn-'), butyl acetate was distilled off under reduced pressure to obtain a photocurable resin φ) having an acid value of 5, a hydroxyl value of 33, and a softening point of 82°C.

Example 5 Inphorone dicyanate 333@ and 0.7 parts of dibutyl tin lactate were charged into the same equipment used to obtain acrylated incyanate UL in Example 1, and the mixture was heated under a nitrogen gas stream for 6 hours.
Heat to 0°C. Next, 1 part of hydroquinone was dissolved in 2
-Hydroxyethyl acrylate-) 174 fM-3
Neo group%1
Acrylated isocyanate (12) (3) of 2.2 was obtained.

Next, using the same equipment that made the photocurable resin in Example 1,
A product was treated in the same manner except that 169 parts of the above acrylated incyanate was used in place of 1145 parts of the acrylated isocyanate in Example 1, with an acid value of 5, a hydroxyl value of 33, and a softening point of 72.
℃ photocurable resin (obtained).

Example 6 In the same apparatus used to prepare the acrylated isocyanate in Example 1, 336 parts of hexamethylene diisocyanate and 0.8 parts of dibutyltin laphrate were charged and heated to 60°C under a nitrogen gas stream. Next, 232 parts of 2-hydroxyethyl acrylate in which 1 part of hydroquinone was dissolved was added dropwise over 3 hours, and the temperature was kept at the same temperature for 2 hours.
．． Acrylated cyanate (4) of No. 5 was obtained.

Next, using the same equipment used to obtain the photocurable resin (4) in Example 1, 145 parts of acrylated isocyanate (tl+) among the raw materials used in Example 1 was replaced with 41,142 parts of the above-mentioned acrylated incyane (tl+). A photocurable resin (F
) was obtained.

Example 7 280 parts of Pandis G-100s and epoxy equivalent of 19 were added to the same equipment in which the photocurable resin (1) was made in Example 1.
152 parts of epoxy resin Evototo YD-128 (trade name, manufactured by Tobu Kasei Co., Ltd.) and 0.3 parts of tetramethylammonicum chloride were reacted for 2 hours at 170°C under a nitrogen gas stream to give an acid value of 1.5. After that, cool it to 100℃,
Add 200 parts of butyl acetate and bring the temperature to 60°C. Next, 209 parts of the acrylated incyane) ul shown in Example 1 was added over 1 hour, held at 60°C for 2 hours, heated, and reacted for 6 hours under refluxing butyl acetate.
After confirming the disappearance of the o group peak (2250 am 2 ), butyl acetate was distilled off under plate pressure to obtain a photocurable resin (G) having an acid value of 1, a hydroxyl value of 9, and a softening point of 70°C.

Example 8 In the same apparatus as that used to make the photocurable resin (1) in Example 1, 35 minutes of disproportional rosin Nodandis fi-1008 was heated.
0 parts and 136 parts of pentaerythritol were charged and reacted at 270° C. for 5 hours under a nitrogen gas stream to give an acid value of 5. After cooling to 110° C., 250 parts of toluene was added to dilute. Next, 108 parts of acrylic acid, no-hydroquinone o, and 5 parts of atL'p-toluenesulfonic acid were added,
The mixture was reacted for 15 hours under toluene reflux while blowing air to give an acid value of 7, and then cooled to 60°C. moreover,
87 parts of TD Any 0, 0.
3s was added over 1 hour, the reaction was carried out at the same temperature for 4 hours, and Ne was determined by infrared absorption spectrum.

After confirming the disappearance of the group (2250 am-'), it was cooled, neutralized by adding 2 parts of potassium hydroxide, washed with water, and the volatile components were distilled off under plate pressure. Photocurable resin (obtained odor).

Example 9 Among the raw materials used in Example 1, abietic acid content 0 was added to the same equipment used to produce the photocurable resin +1) in Example 1.
．． Acid value 4. ＼Hydroxyl value 3 (softening point 73°)
A photocurable resin CI) of C was obtained.

Comparative Example Ratio 1 Among the raw materials used in Example 1, abietic acid content of 2.3% and dehydroabietin were added as the disproportionated rosin to the same equipment used to produce the photocurable resin (1) in Example 1. A photocurable resin (ratio A) having an acid value of 5 and a hydroxyl value of 3 (softening point of 74° C.) was obtained by processing in exactly the same manner as in Example 1, except that a resin having an acid content of 41% was used.

Comparative Example Ratio 2 Among the raw materials used in Example 1, Pandis G-100 was added to the same equipment used to make the photocurable resin +ll in Example 1.
The reaction was carried out in exactly the same manner as in Example 1, except that Ogam rosin (grade X from the People's Republic of China) was used, and the acid value was 4.5 and the hydroxyl value was 34. Photocurable 1 sealant with a softening point of 73°C (ratio B)
I got it.

Comparative Example Ratio 3 Into the same equipment used to make the photocurable lit fat TL in Example 1, asymmetric rosin bumps with an abietic acid content of 0, 100,849 parts of phosphoric anhydride, and 50 parts of phosphoric anhydride were added. , 134 parts of trimethylolpropane were charged and reacted at 250°C for 6 hours under a nitrogen gas stream to give an acid value of 2.
Cool to 0℃, add 200 yakubutyl, and cool to 60℃.
It was set as C. Next, 290 parts of the acrylated isocyanate (1) shown in Example 1 was added over 1 hour, held at 60°C for 2 hours, heated, and reacted for 4 hours under reflux of #acid butyl acid. Neo group (2250,,-'
) After confirming the disappearance of the peak, butyl acetate was distilled off under reduced pressure.
A photocurable resin (ratio C) having an acid value of 1.5 and a hydroxyl value of 9\softening point of 70°C was obtained.

Comparative Example Ratio 4 Of the raw materials used in Example (8), 2 TD Eny 0 was added to the same equipment used to make the photocurable resin ill in the Example process.
The reaction was the same except that the amount was reduced to 6 parts, and the acid value was 5 and the hydroxyl value was 1.
22, a photocurable resin (ratio D) having a softening point of 45°C was obtained.

The photocurable resins obtained in the above examples and comparative examples were kneaded with 3 nerol in the formulation shown in Table 1, and the tack was 12 to 14.
(Measured with Toyo Seiki Incometer B-45 model)
was obtained, and the performance test was performed as follows.

1 Curable Each test printing ink 0.200 was spread on art paper using a two-part roll of R-Etester (manufactured by Yo Seisakusho), and immediately after spreading, it was passed under a high-pressure mercury illusion of 80 W/cm on a variable speed conveyor. The curing time (seconds) is determined from the conveyor speed required for each spreadable ink film to harden to the touch.
I asked for

2 Gloss Regarding the solid printed matter completely cured in the above ultraviolet curing test, the gloss value was measured and judged using a gloss meter at a reflection angle of 60°. Evaluation method: Gloss value 60 or higher: ◎, 60-50
◯, 50 to 40 as Δ, and 40 or less as ×.

3 Emulsification Resistance A mixture of 70 parts of each test printing ink and 100 parts of dampening water was stirred at high speed, separated water was removed, and the amount of water converted into $L in the ink was determined.

4. Fluidity (Flow) Using a parallel plate viscometer, the radius (1a+) of the ink spread after 1 minute was measured in a constant temperature room at 25°C.

Table 1 Notes (a) Trimethylolpropane triacrylate was used.

(1)) Benzoin isopropyl ether was used.

(C) Using carmine 6B

Claims (1)

[Claims] Contains 100 parts by weight of a disproportionated rosin with an abietic acid content of 1% or less, 20 to 100 parts by weight of a polyvalent isocyanate, and 10 to 60 parts by weight of a polyfunctional alcohol as bonding components, and has 1 polymerizable unsaturated group. A photocurable resin comprising a symmetrical rosin-modified phrethanized unsaturated resin having one or more hydroxyl groups per molecule and a hydroxyl value of 80 or less.