JPS6115096B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is applicable to inks, paints, etc., containing a curable resin in which α,β-unsaturated carboxylic acid is esterified to a hydroxyl-excess alkyd resin produced using a resinous polyol, and a viscosity adjusting monomer. The present invention relates to a curable resin composition for coating. In the field of recent printing inks and paints, quick-drying,
There is also a noticeable trend towards solvent-free printing inks, which are curable with actinic rays such as ultraviolet rays and electron beams.
The use of paints, etc. is progressing. Conventionally, resins that can be cured by actinic rays (hereinafter referred to as curable resins) include epoxy acrylate, fatty acid-modified alkyd acrylate,
Acrylates made from fatty acid-modified alkyds in polyisocyanate media are known. However, these curable resins had the following drawbacks. Epoxy acrylate has excellent curability, but due to the hydroxyl groups present in the molecule, it has a high viscosity relative to its molecular weight and has poor workability during printing or painting. Further, the fluidity of the ink before curing, the transferability of the ink, etc. are highly dependent on temperature, and workability is poor in this respect as well. Furthermore, the cured film exhibits large distortions, resulting in poor adhesion to the substrate. Furthermore, the cured film is brittle and lacks workability. Fatty acid-modified alkylated acrylates have a softened cured film due to plasticization with resin acids, and therefore have poor solvent resistance. Acrylates prepared using polyisocyanate media of fatty acid-modified alkyds have high viscosity due to urethane bonds in the molecule and have poor workability. Further, when lowering the viscosity, the proportion of reactive diluent used increases, resulting in a disadvantage that curability deteriorates. In addition to the above-mentioned curable resins, acrylates of copolymers consisting of dicyclopentadiene and allyl alcohol have been reported in JP-A-49-124133. However, this curable resin had the disadvantage that it had a large temperature dependence due to its low molecular weight, and its curability was not sufficient, and furthermore, it did not have sufficient pigment dispersibility due to its low polarity curing. In order to improve these shortcomings, the present inventor has conducted intensive research and found that the molecular weight distribution is wide, solubility, curability,
We have now invented a curable resin composition for coating that can be used in inks, paints, etc., which contains a curable resin with excellent film processability and a viscosity-adjusting monomer. That is, the object of the present invention is (A) the following general formula (In the formula, R represents an organic residue having 1 to 3 carbon atoms, m and n are each an integer, and m+n=6
(B) a compound having a polymerizable double bond and a hydroxyl group in the same molecule; Resin with hydroxyl group obtained by
Alternatively, a resin () in which only the double bonds of the resin () are selectively hydrogenated or a mixture of the resin () and the resin () are used as part of the polyol component during the production of an alkyd resin. A curable resin (2) produced by producing an alkyd resin (2) with excess hydroxyl groups, and esterifying the alkyd resin (2) with an α,β-unsaturated carboxylic acid;
Viscosity adjusting monomer, sensitizer if necessary,
An object of the present invention is to provide a curable resin composition containing additives such as pigments. The curable resin composition of the present invention does not deteriorate its solubility by increasing its molecular weight like conventional curable resins, or deteriorate its curability by increasing the proportion of plastic substances. There is no such thing as doing that. That is, the curable resin composition of the present invention uses a resinous polyol with high molecular weight and good solubility as a part of the polyol component when producing the alkyd resin. It becomes a molecular weight alkylated acrylate. As a result, when producing a curable resin composition for coating printing ink, paint, etc. using the curable resin composition of the present invention, it has excellent curability, pigment dispersibility, processability, and adhesion, and also has excellent temperature The dependence is small and workability can be improved. Further details of the present invention are described below.Resin ()
As component (A), cyclopentadiene, dicyclopentadiene, tricyclopentadiene, tetracyclopentadiene, etc. and substituted products thereof, preferably lower alkyl substituted products having 1 to 3 carbon atoms (for example, methyldicyclopentadiene), etc. One or more of these are used. In addition, as component (B), (meth)allyl alcohol, 2-hydroxyethyl (meth)acrylate
One or more of esters, 1,4-butene diol, 1,3-butene diol, 2-hydroxypropyl (meth)acrylate, etc. are used. In the present invention, when reacting component (A) and component (B), the molar ratio of component (A)/component (B) is 30/70 to 95/5, preferably 40/60 to 80/20. Between 150℃ and 350℃
°C in the presence of a radical catalyst or without a catalyst,
under pressure, if desired in the presence of a solvent, from 3 to
Let the polymerization reaction take place for 10 hours. After the polymerization reaction is completed, low molecular weight substances and unreacted substances are removed under reduced pressure at 180 to 230°C to obtain resin (), which has the following structure () with a melting point of 60 to 150°C. a), (b), (c)
and (d), of which:
The compound having the structure (c) accounts for 80% by weight or more. Therefore, in the present invention, the mixture is referred to as a resinous polyol. Above (A),
(B) In the reaction of both components, cyclopentadiene or dicyclopentadiene is often used as the A component, and allyl alcohol is often used as the B component. (In the formula, n represents a positive integer from 1 to 3), (In the formula, n is 1 to 3, n' is 1 to 3, n'' is 1 to
(3, m represents a positive integer from 1 to 5, respectively) Resin () is obtained by selectively hydrogenating only the double bonds of the resin (), and the resin () is mixed with platinum, palladium, etc. In the presence of a hydrogenation catalyst such as a noble metal, nickel, copper-chromium, etc., and if desired in the presence of a solvent, hydrogenation is carried out at room temperature to 250°C and under pressure of normal pressure to 100 kg/cm ² to form hydroxyl groups. Hydrogenated without reducing the amount. 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 bonds of the resin (). The resin (2) hydrogenated in this way has less yellow coloring and has a lower odor than the resin (2). (Hereinafter, resin () and/or resin () will be collectively referred to as DCPD polyol.) In the present invention, the above-mentioned DCPD polyol is used as a polyol when producing the hydroxyl-excessive alkyd resin () described below. -Used as part of the oil component. Polyol components other than DCPD polyol in the hydroxyl-excessive alkyd resin include glycerin, trimethylolpropane, pentaerythritol,
Aliphatic polyols such as dipentaerythritol and tripentaerythritol, ethylene glycol
diethylene glycol, propylene glycol
glycol, dipropylene glycol, tripropylene glycol, neopentyl glycol, etc.
One or more of cyclic polyols such as polyol, trimethylol isocyanurate, trimethylolmelamine, and hexamethylolmelamine are used. In addition, the polybasic acid components of the hydroxyl-excessive alkyd resin include adipic acid, succinic acid, fumaric acid,
One or more of maleic acid, maleic anhydride, isophthalic acid, phthalic anhydride, terephthalic acid, trimellitic acid, trimectic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and the like are used. In addition, in order to produce the hydroxyl-excessive alkyd resin (), linseed oil, rice bran oil, castor oil, dehydrated castor oil, coconut oil, tung oil, or these fatty acids, caproic acid, caprylic acid, capric acid, Saturated fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, arachic acid,
One or more of unsaturated fatty acids such as oleic acid, linoleic acid, linolenic acid, eleostearic acid, ricinolenic acid, rosin, hydrated rosin, disproportionated rosin, polymerized rosin, etc. are used as polyols and polybasic acids.
It can be used in combination with an upper limit of 50 parts by weight. If it exceeds 50 parts by weight, the molecular weight of the hydroxyl-excessive alkyd resin decreases, and furthermore, the cured film becomes plasticized and the solvent resistance deteriorates. Furthermore, if necessary, methanol, ethanol, propanol, butanol, hexanol, etc.
It is also possible to use monohydric alcohols such as alcohol, octanol, benzyl alcohol, cyclohexanol, ethylene glycol monoalkyl ether, and oxo alcohol. In the present invention, hydroxyl-excessive alkyd resin ()
The synthesis method includes 20 to 80 parts by weight of DCPD polyol, 5 to 50 parts by weight of polyol other than DCPD polyol, 10 to 50 parts by weight of polybasic acid, and if necessary, the above-mentioned fatty oils and fatty acids. , rosin, monohydric alcohol, etc. for a total of 100 parts by weight of polyol and polybasic acid.
Add up to 50 parts by weight, charge these into a four-necked flask with a stirrer and condenser, and add 150 parts by weight.
C. to 280.degree. C. while removing water produced during condensation, the acid value is set to 20 or less, preferably 10 or less, to obtain a hydroxyl-excessive alkyd resin (2). During the above synthesis, the amount of DCPD polyol was 20 to 80
If it is less than 20 parts by weight, the polyester part due to the reaction of polyols other than DCPD polyol and polybasic acid will increase, resulting in an increase in the melting point and a lower resistance to mineral oil. Solubility deteriorates. When printing ink, paint, etc. are made using the finally obtained curable resin, fluidity, gloss, etc. of printed matter deteriorate. Furthermore, when the amount of DCPD polyol exceeds 80 parts by weight, the crosslinkable portion decreases and the molecular weight of the hydroxyl-excessive alkyd resin () decreases, resulting in poor printability, setting properties, and drying properties when producing printing inks, etc. to degrade. In addition, during the above synthesis, polybasic acid and DCPD were partially used.
If you want to avoid polyester by-formation due to the reaction of polyols other than polyols, use DCPD polyol.
It is preferable to carry out an esterification reaction with polybasic acid, fatty oil, fatty acid, rosin, and monohydric alcohol if necessary, and then add polyols other than DCPD polyol. In the present invention, the hydroxyl-excessive alkyd resin () is produced as described above, and the excess amount of hydroxyl groups in the hydroxyl-excessive alkyd resin () is OH
The equivalent weight is 120 to 1260, preferably 150 to 300. In the present invention, the hydroxyl-excessive alkyd resin (2) obtained as described above is esterified with an α,β-unsaturated carboxylic acid to obtain a product curable resin (2). As this α,β-unsaturated carboxylic acid, one or more of acrylic acid, methacrylic acid, crotonic acid, sorbic acid, etc. are used, but the solubility of the curable resin from which acrylic acid or methacrylic acid is obtained and more preferable in terms of curability. In addition, when α,β-unsaturated carboxylic acid is used in an amount of 5 to 50 parts by weight, preferably 10 to 35 parts by weight, based on 95 to 50 parts by weight of the hydroxyl-excessive alkyd resin (), the resulting curable resin () hardenability,
Molecular weight distribution, solubility, etc. can be improved. In addition, hydroxyl group-excessive alkyd resin () and α,
For the reaction with β-unsaturated carboxylic acid, add 95 to 50 parts by weight of the hydroxyl-excessive alkyd resin (), 10 parts by weight of a refluxing solvent such as cyclohexane, and 0.1 part by weight of a thermal polymerization inhibitor such as hydroquinone using a stirrer and a condenser directly connected to a separating tube. α, β at about 80℃ in a four-necked flask with
- Add 5 to 50 parts by weight of an unsaturated carboxylic acid, and react at 100 to 120°C while blowing air while removing water produced during condensation to obtain an acid value of 30 or less, preferably
When the temperature becomes 20 or less, the refluxing solvent such as cyclohexane is removed and the curable resin according to the present invention is pumped out. The curable resin () according to the present invention solves various conventional drawbacks and is suitable as a constituent resin of a curable resin composition for coating printing inks, paints, etc. When applied to an ultraviolet curable printing ink using the curable resin composition of the present invention, the composition includes 15 to 65 parts by weight of the curable resin () according to the present invention,
1 to 25 parts by weight of a sensitizer, 5 to 50 parts by weight of a pigment, 5 to 50 parts by weight of a viscosity adjusting monomer, and other additives may be added as necessary. The composition of the ultraviolet curable paint includes 5 to 20 parts by weight of the curable resin () according to the present invention, 1 to 25 parts by weight of sensitizer, 0 to 60 parts by weight of pigment, and 15 to 60 parts by weight of viscosity adjusting monomer. Other additives can be added as necessary. Sensitizers used in the production of UV-curable coating compositions include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin butyl ether, benzophenone, benzyl, xanthone, Thiozanthone, methylbenzoylbenzoic acid, ethylbenzoylbenzoic acid, acetophenone, 4-dimethylaminoacetophenone, P-dimethylaminobenzaldehyde, methyl P-dimethylaminobenzoate,
Ethyl m-dimethylaminobenzoate, amyl P-dimethylaminobenzoate, m-dimethylaminobenzoic acid, amyl O-dimethylaminobenzoate,
One or more types of 4,4'-bisdiethylaminobenzophenone and the like are used. In addition, as viscosity adjusting monomers, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol polyacrylate, dipentaerythritol polymethacrylate, triallyl isocyanurate, triallyl citrate, polyethylene glycol diacrylate, ethylene glycol dimethacrylate, polypropylene glycol diacrylate
one or two of phenyl glycidyl acrylate, phenyl diglycol diacrylate, etc.
More than one species is used. In addition, in the present invention, azo pigments (Hanzai Yellow, Benzidine Yellow, Lake Red C,
Carmine 6B, Permanent Red 2B, etc.) various organic pigments such as phthalocyanine pigments (phthalocyanine blue, phthalocyanine green, etc.), quinacridone pigments, isoindolinone series, quinophthalone series, and titanium white, Inorganic pigments such as carbon black, red iron oxide, zinc white, and calcium carbonate can be used. Further, when the curable resin composition according to the present invention is cured by heating, an organic peroxide can be used alone or in combination with cobalt naphthenate, manganese naphthenate, or the like. Next, the present invention will be described in more detail with reference to Examples and Comparative Examples. In the examples, parts indicate parts by weight. Example 1 660 g of dicyclopentadiene with a purity of 96%, 300 g of allyl alcohol, and 500 g of commercially available mixed xylene were charged into an autoclave equipped with a stirrer, and reacted at a temperature of 260 DEG C. for 5 hours. After the reaction was completed, the autoclave was cooled and the contents were distilled to remove unreacted monomers, low polymers and xylene, yielding 750 g of Resin (2)-1. 100g of this resin ()-1
was dissolved in 75 g of commercially available mixed xylene, 1 g of palladium carbon with a palladium concentration of 5% (5% Pd-C standard product manufactured by Engelhard Japan) was added, and the mixture was heated at 150°C under a hydrogen pressure of 30 Kg/cm ² for about 1 hour. A hydrogenation reaction was carried out and the solvent was distilled off to obtain hydrogenated resin (2)-1. The properties of Resin ()-1 and Resin ()-1 are as follows.

[Table] Next, add 45 parts of resin ()-1 and 29 parts of phthalic anhydride.
and 26 parts of trimethylolpropane were charged into a four-necked flask equipped with a stirrer and a condenser directly connected to the separating tube.
Reacted at 240℃ for 7.5 hours under _N2 gas flow, acid value 7.8
A hydroxyl-excessive alkyd resin ()-1 was obtained.
This hydroxyl-excessive alkyd resin ()-1 80
parts, 20 parts of acrylic acid, 1 part of para-toluenesulfonic acid
1 part and 0.1 part of hydroquinone were charged into a four-necked flask equipped with a stirrer and a condenser directly connected to a separating tube, and reacted at 80 to 120°C for 15 hours under reflux of cyclohexane/methyl isobutyl ketone (2:1) to give an acid value of 20.5. The refluxing solvent (cyclohexane/methyl isobutyl ketone (MIBK)) was distilled off at 115° C. to obtain a curable resin ()-1 with an acid value of 18.3. Example 2 45 parts of the resin (2) obtained in Example 1 and 29 parts of Rikasid TH (tetrahydrophthalic anhydride manufactured by Shin Nippon Chemical Co., Ltd.) were mixed in a stirrer and a condenser directly connected to a separation tube.
Commercially available mixed xylene was prepared in a 4-necked flask and reacted for 1.5 hours at 150°C while blowing _N2 gas under reflux. 26 parts of trimethylolpropane was added, and 200 parts of trimethylolpropane was added.
The reaction was carried out at .degree. C. for 5 hours to obtain hydroxyl-excessive alkyd resin (2) having an acid value of 8.7. 80 parts of this alkyd resin ()-2, 1 part of para-toluenesulfonic acid, 0.1 part of hydroquinone,
Cyclohexane/MIBK (2:1) mixed solvent 15
20 parts of acrylic acid was added to the temperature at 80°C, and while blowing air, the reaction was carried out at 100°C for 16 hours to give an acid value of 18.3. The solvent was distilled off at 115°C for 3 hours to obtain a curable resin. ()-2 acid value of 16.4 was obtained. The infrared absorption spectrum of this curable resin ()-2 is as shown in Figure 1, with peaks based on the ester groups of the resin at 1730 cm ^-1 and 1190 cm ^-1 .
I was able to recognize that. In addition, the resin ()-
The molecular weight distribution of Example 2 is shown in Figure 2, and the molecular weight (Mw) of this resin is 3765, the number average molecular weight Mn is 638, and Mw/Mn = 5.9. Resin ()-2 82 parts, para-toluenesulfonic acid 1 part,
Hydroquinone 0.1 part, cyclohexane/MIBK
(2:1) Prepare 15 parts of mixed solvent, add 18 parts of methacrylic acid at 80℃, and while blowing air.
React at 100℃ for 14 hours to obtain an acid value of 19.7.
The solvent was distilled off at 115°C over 3 hours to obtain curable resin ()-3 with an acid value of 17.8. Example 4 43 parts of resin ()-1 obtained in Example 1, rosin
10 parts, adipic acid 23.5 parts, pentaerythritol
24 parts were reacted in the same manner as in Example 1 to obtain hydroxyl-excessive alkyd resin ()-4 with an acid value of 10.6 and an acid value of 16.9. This hydroxyl group-excessive alkyd resin ()-4 75
and 25 parts of acrylic acid were reacted in the same manner as in Example 1 to obtain curable resin (2)-4. Example 5 27 parts of the resin ()-1 obtained in Example 1, 11.2 parts of 2-ethylbutanol, 32.5 parts of Rikaside HH (hexahydrophthalic anhydride manufactured by Shin Nippon Chemical Co., Ltd.), and 29.2 parts of trimethylolpropane were mixed with Example 2. React in the same manner, and hydroxyl-excessive alkyd resin ()-
Got 5. This hydroxyl-excessive alkyd resin ()-5 78
22 parts of acrylic acid were reacted in the same manner as in Examples 1 and 2 to obtain curable resin ()-5 with an acid value of 16.3. Example 6 Printing ink was produced using the curable resins obtained in Examples 1 to 5. 65 parts of each curable resin and phenylene diglyco
An ink vehicle was made with 35 parts of Ludia acrylate. 43 parts of each ink vehicle, 40 parts of CR80 (Titanium White manufactured by Ishihara Sangyo), 10 parts of benzyl, 0.2 parts of 4-dimethylaminoacetophenone, and 7 parts of phenylene diglycol diacrylate were mixed into inks using a three-roll mill. Inks 1 to 5 corresponding to each of the curable resins ()-1 to ()-5 were obtained. Comparative Example 1 78 parts of resin ()-1 obtained in Example 1, 1.0 part of p-toluenesulfonic acid, 0.1 part of hydroquinone,
15 parts of a cyclohexane/MIBK (2:1) mixed solvent was charged into a four-necked flask equipped with a stirrer and a condenser directly connected to a separation tube, and 22 parts of acrylic acid was added at 80°C. The titer was adjusted to 18.0, and then cyclohexane/
The MIBK (2:1) mixed solvent was distilled off to obtain a curable resin ()-6 with an acid value of 15.4. Comparative Example 2 75 parts of Epicoat 828 (epoxy resin manufactured by Shell Petrochemicals), 0.1 part of hydroquinone, and 0.2 parts of ethylenediamine were placed in a four-necked flask with a stirrer and condenser, and 25 parts of acrylic acid was added at 80°C.
Curable resin with acid value 3 that reacts at 100℃ for 18 hours ()-
I got a 7. Using curable resins ()-6 and ()-7, inks 6 and 7 corresponding to resins ()-6 and ()-7, respectively, were obtained in the same manner as in Example 6. Properties and evaluations of the curable resins and inks obtained in Examples and Comparative Examples are shown in Tables 1 and 2, respectively.

【table】

[Table] From the results in Table 1, it can be seen that the curable resin composition of the present invention has good compatibility with alkylbenzene and phenylene diglycol. From the results shown in FIG. 3, it can be seen that the solubility range is wide and the dispersibility is good, indicating that the solubility is close to that of rosin-modified phenolic resin. Further, from the graph shown in FIG. 2, it can be seen that the curable resin composition of the present invention has a considerably wide molecular weight distribution. Furthermore, when the composition of the present invention is applied to ink, as can be seen from Table 2, gloss, drying properties,
It can be seen that this ink is extremely superior in terms of adhesion, processability, printability, etc., compared to inks made from conventionally known resins.

[Brief explanation of the drawing]

Figure 1 shows the infrared rays of curable resin (2).
FIG. 2 is a graph showing the molecular weight distribution of curable resin (2), and FIG. 3 is a graph showing the tolerance range of 90% or more for curable resin (2). The explanation of the numbers in FIG. 3 is as follows. 1... Osol-H, 2... cyclohexane, 3... carbon tetrachloride, 4... xylene, 5... benzene, 6... trichloroethylene, 7... dichlorobenzene , 9
...Nitrobenzene, 10...Propylene glycol, 11...Ethyl acetate, 12...
Cellosolve acetate, 131-chlorobutane, 14...DMF, 15...Ethanolamine, 16...Diethylene glyco-
17...Water, 18...Ethylene glycol
19... n-butanol, 20... iso-octyl alcohol, 21... ethyl cellosolve, 22... ethyl alcohol, 23... tetrahydrofuran, 24... morpholine, 25...
Pyridine, 26...Methyl carbitol, 27
... n-butyl acetate, 28 ... cyclohexanol, 29 ... DP, 30
...DMP, 31...DOP, 32...Tributyl monoacetyl
Cytrate, 33...DBM, 3
4...DA, 35...2-ethyl butanol, 36...dipropylene glyco-
37...Butyronitrile, 38...Cyclohexyl chloride, 39...Diacetone alcohol.

Claims (1)

[Claims] 1 (A) The following general formula [Formula] (wherein, R represents an organic residue having 1 to 3 carbon atoms, m and n are each an integer, and m+n=6
5-membered ring compounds having an unsaturated conjugated double bond represented by
compound, (B) a compound having a polymerizable double bond and a hydroxyl group in the same molecule, and/or a resin () having a hydroxyl group obtained by reacting with the compound, and/or selectively removing only the double bonds of the resin (). A hydrogenated resin () is used as a part of the polyol component in producing an alkyd resin to produce a hydroxyl-excessive alkyd resin (), and the hydroxyl-excessive alkyd resin () is added with α,
A curable resin composition containing a curable resin obtained by esterifying a β-unsaturated carboxylic acid, a viscosity adjusting monomer, and optionally additives such as a sensitizer and a pigment. 2. The curable resin composition according to claim 1, wherein the resin () and/or the resin () are used in an amount of 20 to 80% by weight as a polyol component in producing the alkyd resin. 3. The above claims, wherein component (A) of the resin () is at least one of cyclopentadiene, dicyclopentadiene, tricyclopentadiene, tetracyclopentadiene, and lower alkyl substituted products having 1 to 3 carbon atoms thereof. first or second
The curable resin composition described in . 4 Component (B) of the resin () is (meth)allyl alcohol, 2-hydroxyethyl (meth)acrylate, 1,4-butenediol, 1,3-butenediol, 2-hydroxypropyl ( The curable resin composition according to claim 1, which is at least one meth)acrylate. 5 The resin () has the following structural formula [formula] [formula] (wherein n represents a positive integer from 1 to 3) or (In the formula, n is 1 to 3, n' is 1 to 3, n'' is 1 to
3, and m represents a positive integer of 1 to 5). 6. Claims 1 to 6, wherein the α,β-unsaturated carboxylic acid is at least one of acrylic acid, methacrylic acid, crotonic acid, and sorbic acid.
The curable resin composition according to any one of Item 5. 7 Claims 1 to 6 used for coating
The curable resin composition according to any one of Items. 8 Consists of 15 to 65 parts by weight of the curable resin (), 1 to 25 parts by weight of the sensitizer, 5 to 50 parts by weight of the pigment, 5 to 50 parts by weight of the viscosity adjusting monomer, etc.
The curable resin composition according to claim 7, which can be used as an ultraviolet curable printing ink. 9 Comprising 5 to 20 parts by weight of the curable resin (), 1 to 25 parts by weight of the sensitizer, 0 to 60 parts by weight of the pigment, 15 to 60 parts by weight of the viscosity adjusting monomer, etc., for ultraviolet curable paints. The curable resin composition according to claim 7, which can be used as a curable resin composition.