KR100445728B1 - Photosensitive Oligomer having Phenoxy Group and Production Method of the Same - Google Patents

Abstract

The present invention relates to a urethane acrylate oligomer and a method for producing the same, and an object thereof is to provide a urethane acrylate oligomer having improved adhesion and solvent resistance and a method for producing the same.

A polyol (A) having at least one hydroxyl group, a polyisocyanate (B) having at least two isocyanate groups, and an acrylate or methacrylate (C) having at least one phenoxy group and at least one hydroxy group The urethane acrylate oligomer of the following [Formula 1] which has a phenoxy group in the molecule | numerator obtained by making it react.

[Formula 1]

In formula, R <_1> is a main chain of a polyol, R <_2> is a main chain of a polyisocyanate, and A (MA) is an acrylate or methacrylate which hydroxy group was missing, and has a structure of following [Formula 2].

[Formula 2]

Wherein R ₃ is H or CH ₃ , and R ₄ is [CH ₂ CH ₂ O] x, [CH ₂ CH ₂ CH ₂ O] x, or [CO (CH ₂ ) ₅ O] x. However, it is an integer of x = 1-50.

Description

Photosensitive Oligomer Having Phenoxy Group and Production Method of the Same}

The present invention relates to a photosensitive oligomer and a method for producing the same, and more particularly, to a photosensitive urethane acrylate oligomer having at least one phenoxy group and a urethane group in a molecule, and having improved adhesion and solvent resistance.

The photosensitive oligomers cured by ultraviolet rays include epoxy (meth) acrylate oligomers, urethane (meth) acrylate oligomers, polyester (meth) acrylate oligomers, silicone (meth) acrylate oligomers, fluorine (meth) acrylate oligomers, and the like. Known.

Among them, urethane (meth) acrylate oligomers are widely used as various inks, coatings or adhesives in the form of curing by light due to high mechanical strength after curing, good chemical resistance, adhesion to various substrates, and processability. After reacting polyol and diisocyanate, (meth) acrylate is produced by addition reaction, but various attempts have been made such as introducing a functional group to obtain desired physical properties depending on the intended use.

For example, Korean Patent Laid-Open Publication No. 93-12889 discloses a urethane acrylate oligomer in which a polyalkylene glycol having a hydroxyl group at the end is added to give flexibility and antistatic ability, and Korean Patent Laid-Open Publication No. 93-12889 No. discloses a photosensitive urethane acrylate oligomer incorporating halogen to impart flame retardancy.

U. S. Patent No. 4,153, 778 discloses a photosensitive urethane acrylate oligomer in which carboxylic acid is reacted with acrylate to a reactant of polyol and diisocyanate to obtain a fast curing rate and low viscosity fiber coating. No. discloses a water-insoluble photosensitive urethane acrylate oligomer incorporating active hydrogen, and US Pat. No. 5,578,693 discloses a photosensitive urethane acrylate oligomer in which an alkoxy polyhydric alcohol is bound to a reactant of polyol and diisocyanate.

Japanese Patent Laid-Open Nos. Hei 6-27151 and Hei 6-166737 disclose a photosensitive urethane acrylate oligomer having an organooxycarbonylimide group bonded to a terminal having improved tensile strength and elongation. 35657 and Japanese Patent Laid-Open Nos. 11-349660 disclose photosensitive urethane acrylate oligomers having unsaturated groups having improved tensile strength and elongation.

However, the photosensitive urethane acrylate oligomers have a disadvantage in that the adhesion to the material and the solvent resistance thereof are not sufficiently good yet, so that they can be easily removed by the solvent or coated on the film.

It is an object of the present invention to provide a photosensitive urethane acrylate oligomer having improved adhesion and solvent resistance and a method for producing the same.

The photosensitive urethane acrylate oligomer of the present invention for achieving the above object is a polyol (A) having at least one hydroxyl group, a polyisocyanate (B) having at least two isocyanate groups, at least one phenoxy group and one A urethane acrylate oligomer having a phenoxy group represented by the following [Formula 1] obtained by reacting an acrylate or methacrylate (C) having the above hydroxyl group is characterized by having a phenoxy group in a molecule.

In formula, R <_1> is a main chain of a polyol, R <_2> is a main chain of a polyisocyanate, and A (MA) is an acrylate or methacrylate which hydroxy group was missing, and has a structure of following [Formula 2].

Wherein R ₃ is H or CH ₃ , and R ₄ is [CH ₂ CH ₂ O] x, [CH ₂ CH ₂ CH ₂ O] x, or [CO (CH ₂ ) ₅ O] x. However, it is an integer of x = 1-50.

Urethane acrylate oligomer of the present invention is characterized by having a phenoxy group in the molecule, a photocurable material having a viscosity of 15,000 ~ 40,000cps at 60 ℃, excellent adhesion, solvent resistance, elasticity, photosensitive coating agent, adhesive, It is useful for the manufacture of photoresist and the like.

Hereinafter, the present invention will be described in more detail.

The compound of [Formula 1] of the present invention is a method of reacting a polyisocyanate (B) and (meth) acrylate (C) and then reacting the reaction product and polyol (A), and polyol (A) and ( It may also be prepared by a method of mixing the meta) acrylate (C) and then adding a polyisocyanate (B) to react, but the oligomer having an isocyanate group at both ends by reacting the polyol (A) and the polyisocyanate (B) It is preferable to prepare through the two-step reaction of the step of producing and the step of reacting the first-step product with the acrylate or methacrylate (C).

It is preferable to make reaction ratio of a polyol (A), a polyisocyanate (B), and an acrylate or methacrylate (C) into 1: 1.5-2.5: 0.5-1.5 by equivalent ratio.

The polyol (A) above is selected from polyethylene glycol, polypropylene glycol, polytetrahydrofuran polyol, polyester polyol, polycaprolactone polyol, polybutadiene polyol, polycarbonate polyol or mixtures thereof with a molecular weight of 200 to 5,000.

Polyethylene glycol, polypropylene glycol, polytetrahydrofuran polyol of the polyols are classified into so-called polyether polyols such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, 2-methyl-tetrahydrofuran, 3-methylhydro It can obtain by ring-opening-polymerizing furan or oxetane.

Polyester polyols include ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,6-hexane diol, neopentyl glycol, 3-methyl-1,5-pentanediol, 1, It can be obtained by reaction of a polyhydric alcohol selected from 9-nonanediol or 2-methyl-1,8-octanediol with a polybasic acid selected from maleic acid, fumaric acid, adipic acid, sebacic acid or succinic acid.

Polycaprolactone polyols are ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,2-polybutylene glycol, 1,6-hexanediol, neopentyl glycol or 1,4 It can be obtained by reaction of dihydric alcohol selected from butanediol with epsilon caprolactone.

The polycarbonate polyols are selected from 1,6-hexanedicarbonate, 1,9-nonanedipolycarbonate, 2-methyl-1,8-octanepolycarbonate or mixtures thereof.

When the polyol has a molecular weight of less than 200, it is easy to break or crack after curing, and when the polyol exceeds 5,000, curing by ultraviolet rays or electron beams is too slow.

Polyisocyanates (B) having two or more isocyanate groups include methylene-bis (4-cyclohexyl isocyanate), 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethylcyclohexane, 2, 2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, noborane diisocyanate, dimer acid diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, hydrogenated 2,4-toluene diisocyanate, hydrogenated 2,6-toluene diisocyanate, meta-phenylene diisocyanate, para-phenylene diisocyanate, 1,3-dimethylphenyl-2,4-diisocyanate, 1,3- Dimethylphenyl-4,6-diisocyanate, 1,4-dimethylphenyl-2,5-diisocyanate, 1-chlorophenyl-2,4-diisocyanate, 4,4-diphenyl diisocyanate, 3,3-dimethyl -4,4-diphenyldiisocyanate, 2,4-di Phenyl diisocyanate, 3,3-dimethoxy-4,4-diphenylmethane diisocyanate, 3,3-dimethyl-4,4-diphenylmethane diisocyanate, 4,4-diphenylmethane diisocyanate, 1,4 Naphthalene diisocyanate, 1,5-naphthalene diisocyanate, 2,6-naphthalene diisocyanate, 2,7-naphthalene diisocyanate, para-xylene diisocyanate, meta-xylene diisocyanate, 1,4-tetramethylene diisocyanate Isocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,7-heptamethylene diisocyanate, 1,8-octamethylene diisocyanate, 1,9-nonamethylene diisocyanate, 1,10 -Decamethylene diisocyanate, 2,2,4-trimethyl-1,5-pentamethylene diisocyanate, 2,2-dimethyl-1,5-pentamethylene diisocyanate, 3-methoxy-1,6-hexamethylene di Isocyanate, 3-butoxy-1,6-hexamethylene Diisocyanate, 1,4-cyclo hexyl diisocyanate, 1,3-cyclo hexyl diisocyanate, or mixtures thereof.

The oligomer of the present invention is prepared through, for example, the following process.

The polyol (A) and the polyisocyanate (B) together with the polymerization inhibitor are added to the reactor at an equivalence ratio of 1: 1.5 to 2.5, and the temperature is raised to 45 ± 5 ° C. while stirring. . When NCO% of the reactants reaches the theoretical value, acrylate or methacrylate (C) having at least one phenoxy group and at least one hydroxy group is added in an equivalence ratio of 1: 0.5 to 1.5 with respect to the polyol (A), and 70 ±. The reaction is carried out at 5 ° C. for about 20 hours. Termination of the reaction confirms the complete disappearance of the -NCO peak at 2250-2270 cm ^-1 by FT-IR.

In the reaction, the polymerization inhibitor is hydroquinone, hydroquinone monomethyl ether, tertiary butyl catechol, para-benzoquinone, hydroquinone, phenoxyazine, butylated hydroxytoluene, pyrogallol, monotertiary-butyl Hydroquinone and differential butylhydroquinone are used, and 0.1 to 1% by weight based on the total weight of the reactants.

The catalyst in the reaction is triethylamine, triethylenediamine, dibutyltindilaurate, stannous chloride, tetra-N-butyltin, tri-N-butyltinacetate, N-butyltin trichloride, trimethyltin hydroxide , Dimethyltin dichloride, etc. are used, and 0.1 to 1% by weight based on the total weight of the reactants.

The configuration and effects of the present invention will be apparent from the embodiments described below.

<Example 1>

Into a 1 L four-necked flask, 339.0 g of polypropylene glycol having a molecular weight of about 400, 284.7 g of 1,6-hexamethylene diisocyanate and 1.0 g of hydroquinone were added with a polymerization inhibitor, and the mixture was gradually heated to 45 ° C while stirring. Subsequently, 1.0 g of dibutyltin dilaurate was added as a catalyst, and the temperature was gradually raised to 70 ° C, followed by reaction. 376.3 g of 2-hydroxy-3-phenoxypropyl acrylate was added when the NCO% reached 11.4%. And reacted at 70 ° C. for 20 hours.

925 g of a polymerization product having a viscosity of 30,000 cps at 60 ° C. were obtained, and it was confirmed that the -NCO peak disappeared at 2250˜2270 cm ⁻¹ by FT-IR.

<Example 2>

233.1 g of polypropylene glycol having a molecular weight of about 400 as polyol (A), 305.4 g of methylene-bis (4-cyclohexyl isocyanate) as polyisocyanate (B), 2-hydroxy-3 as acrylate or methacrylate (C) The procedure was carried out in the same manner as in Example 1, except that 461.5 g of-(propoxylated 3-mol addition) phenoxy propylacrylate was used.

2-hydroxy-3- (propoxylated 3-molar addition) phenoxy propylacrylate was added when the NCO% of the reaction product of polypropylene glycol and methylene-bis (4-cyclohexyl isocyanate) reached 12.3% 910 g of a polymerization product having a viscosity of 35,000 cps at 60 ° C was obtained.

<Example 3>

361.6 g of polypropylene glycol having a molecular weight of about 700 with polyol (A), 173.5 g of 1,6-hexamethylene diisocyanate with polyisocyanate (B), 2-hydroxy-3- () with acrylate or methacrylate (C) It carried out by the same method as Example 1 except having used 464.9 g of epsilon caprolactone 2 molar addition type) phenoxy propyl acrylate.

2-hydroxy-3- (epsilon caprolactone 2-mole addition) phenoxy propyl acrylate was added when the NCO% of the reaction product of polypropylene glycol and 1,6-hexamethylene diisocyanate reached 8.1% and was 60 ° C. 935 g of a polymerization product having a viscosity of 28,000 cps was obtained.

<Example 4>

535.3 g of polyethylene glycol having a molecular weight of about 1,000 in polyol (A), 179.9 g of 1,6-hexamethylene diisocyanate in polyisocyanate (B), 2-hydroxy-3- (in acrylate or methacrylate (C) The same procedure as in Example 1 was carried out except that 284.8 g of oxylated 1 mol addition) phenoxy propyl acrylate was used.

2-hydroxy-3- (ethoxylated 1 mole addition) phenoxy propylacrylate was added when the NCO% of the reaction product of polyethylene glycol and 1,6-hexamethylene diisocyanate reached 6.3%. 940 g of a polymerization product having a viscosity of 28,500 cps at 占 폚 were obtained.

Example 5

519.7 g of polyethylene glycol having a molecular weight of 2,000 with polyol (A), 136.2 g of methylene-bis (4-cyclohexyl isocyanate) with polyisocyanate (B), 2-hydroxy-3- with acrylate or methacrylate (C) The same procedure as in Example 1 was carried out except that 344.1 g of (ethoxylated 10 mol addition) phenoxy propyl acrylate was used.

2-hydroxy-3- (ethoxylated 10 molar addition) phenoxy propylacrylate was added when the NCO% of the reaction product of polyethylene glycol and methylene-bis (4-cyclohexyl isocyanate) reached 3.3%. 910 g of a polymerization product having a viscosity of 37,000 cps at 60 ° C were obtained.

<Example 6>

261.0 g of polytetrahydrofuran polyol having a molecular weight of about 1,000 with polyol (A), 87.7 g of 1,6-hexamethylene diisocyanate with polyisocyanate (B), 2-hydroxy-3 with acrylate or methacrylate (C) The procedure was carried out in the same manner as in Example 1, except that 651.3 g of-(epsilon caprolactone 9 mol addition) phenoxy propylacrylate was used.

2-hydroxy-3- (epsilon caprolactone 9 molar addition) phenoxy propylacrylate was added when the NCO% of the reaction product of polytetrahydrofuran polyol and 1,6-hexamethylenediisocyanate reached 6.3%. 910 g of a polymerization product having a viscosity of 38,500 cps at 60 ° C were obtained.

<Example 7>

618.8 g of polytetrahydrofuran polyol having a molecular weight of 2,000 with polyol (A), 162.1 g of methylene-bis (4-cyclohexyl isocyanate) with polyisocyanate (B), 2-hydroxy with acrylate or methacrylate (C) The same procedure as in Example 1 was carried out except that 219.1 g of 3- (ethoxylated 3-mol addition) phenoxy propylacrylate was used.

2-hydroxy-3- (ethoxylated 3-molar addition) phenoxy propylacrylate may have reached a 4.5% NCO% of the reaction product of polytetrahydrofuran polyol and methylene-bis (4-cyclohexylisocyanate). 930 g of a polymerization product having a viscosity of 31,500 cps at 60 ° C was obtained.

<Example 8>

719.4 g of polycaprolactone polyol having a molecular weight of 2,000 with polyol (A), 120.9 g of 1,6-hexamethylene diisocyanate with polyisocyanate (B), 2-hydroxy-3- with acrylate or methacrylate (C) The same procedure as in Example 1 was conducted except that 159.7 g of phenoxy propyl acrylate was used. 2-Hydroxy-3-phenoxy propyl acrylate was prepared by polycaprolactone polyol and 1,6-hexamethylene diisocyanate. When the NCO% of the reaction product reached 3.6%, it was charged and 925 g of a polymerization product having a viscosity of 33,000 cps at 60 ° C was obtained.

Example 9

719.4 g of polyester polyols having a molecular weight of 2,000 in polyol (A), 120.9 g of 1,6-hexamethylene diisocyanate in polyisocyanate (B), 2-hydroxy-3-phenoxy as acrylate or methacrylate (C) The same procedure as in Example 1 was carried out except that 159.7 g of cipropyl acrylate was used.

2-hydroxy-3-phenoxy propyl acrylate was introduced when the NCO% of the reaction product of the polyester polyol and 1,6-hexamethylene diisocyanate reached 3.6% and a polymerization product having a viscosity of 34,000 cps at 60 ° C. 920 g was obtained.

<Example 10>

466.4 g of polyester polyol having a molecular weight of about 1,000 as polyol (A), 244.4 g of methylene-bis (4-cyclohexyl isocyanate) as polyisocyanate (B), 2-hydroxy-3 as acrylate or methacrylate (C) The procedure was carried out in the same manner as in Example 1, except that 289.2 g of (ethoxylated 2-mol addition) phenoxy propyl acrylate was used.

2-hydroxy-3- (ethoxylated 2-mole addition) phenoxy propylacrylate was added when the NCO% of the reaction product of polyester polyol and methylene-bis (4-cyclohexyl isocyanate) reached 7.4% 940 g of a polymerization product having a viscosity of 32,500 cps at 60 ° C was obtained.

Comparative Example 1

569.5 g of polyethylene glycol having a molecular weight of about 1,000 with polyol (A), 298.4 g of methylene-bis (4-cyclohexyl isocyanate) with polyisocyanate (B), 2-hydroxy without phenoxy group with acrylate or methacrylate (C) The procedure was the same as in Example 1 except that 132.1 g of hydroxy ethyl acrylate was used. 2-hydroxy ethyl acrylate was obtained by NCO% of the reaction product of polyethylene glycol and methylene-bis (4-cyclohexyl isocyanate). When it reached 7.4%, 950 g of a polymerization product having a viscosity of 16,000 cps at 60 ° C was obtained.

Comparative Example 2

569.5 g of polypropylene glycol having molecular weight of about 1,000 with polyol (A), 298.4 g of methylene-bis (4-cyclohexyl isocyanate) with polyisocyanate (B), 2- without phenoxy group with acrylate or methacrylate (C) The same procedure as in Example 1 was carried out except that 132.1 g of hydroxyethyl acrylate was used.

2-hydroxy ethyl acrylate was added when the NCO% of the reaction product of polyethylene glycol and methylene-bis (4-cyclohexyl isocyanate) reached 7.4% and 950 g of a polymerization product having a viscosity of 15,000 cps at 60 ° C. was obtained. .

<Example 11>

The viscosity of the oligomer obtained in Examples 1, 4, 5, 7, 9 and Comparative Examples 1 and 2 was measured, and 95 parts by weight of the oligomer and the photoinitiator 2-hydroxy-2-methyl-1-phenyl-propan-1-one After mixing 5 parts by weight and removing bubbles, the coating was coated with a thickness of 20 m to measure adhesion and solvent resistance. Each physical property was measured by the following method.

Viscosity was measured at 60 ° C. with Brookfield Rotational Viscosity Spindle No. 4 at 12 rpm (ASTM D1084) .Adhesiveness was applied to the coating surface by 1.5mm of line width and 11 lines of 11 lines to make 100 cells, then 3M. 600 cello tapes were attached and removed immediately to count the remaining cells in 100 cells (ASTM D3359), and the solvent resistance was counted by rubbing them with methyl ethyl ketone on a soft cloth until the coating surface was peeled off. (ASTM D1308).

The results are shown in the following [Table 1].

division Example Comparative example One 4 5 7 9 One 2 Viscosity (cps, 60 ℃) 30,000 28,500 37,000 31,500 34,000 16,000 15,000 Adhesion 1 (Note 1) (100/100) 100/100 100/100 100/100 100/100 100/100 30/100 20/100 Adhesion 2 (Note 2) (100/100) 100/100 100/100 100/100 100/100 100/100 15/100 8/100 Adhesion 3 (Note 3) (100/100) 100/100 100/100 100/100 100/100 100/100 35/100 29/100 Number of solvents (Note 4) 290 285 290 270 295 180 125

Note 1: Polycarbonate Plate

Note 2: Copper Plate

Note 3: polymethyl methacrylate plate

Note 4: methyl ethyl ketone

From the above [Table 1], the photosensitive urethane acrylate oligomer of the present invention in the adhesion test, all 100 scales until the end of the experiment (600 times) for all of the polycarbonate plate, copper plate and polymethyl methacrylate plate It can be seen that the adhesion is significantly improved, and the solvent resistance is also improved by about 2 times.

By using the photosensitive oligomer having the phenoxy group of the present invention, it is possible to prepare coatings, adhesives, printing inks and photoresists and the like with improved adhesion and solvent resistance.

Claims (8)

A polyol (A) having at least one hydroxyl group, a polyisocyanate (B) having at least two isocyanate groups, and an acrylate or methacrylate (C) having at least one phenoxy group and at least one hydroxy group The urethane acrylate oligomer which has a phenoxy group of the following [formula 1] obtained by making it react. [Formula 1] Wherein R ₁ is the main chain of the polyol, R ₂ is the main chain of the polyisocyanate, and A (MA) is an acrylate or methacrylate having no hydroxyl group, and has the structure of formula (2). [Formula 2] Wherein R ₃ is H or CH ₃ , and R ₄ is [CH ₂ CH ₂ O] x, [CH ₂ CH ₂ CH ₂ O] x, or [CO (CH ₂ ) ₅ O] x. However, it is an integer of x = 1-50. Reacting a polyol (A) having at least one hydroxyl group with a polyisocyanate (B) having at least two isocyanate groups, a reaction product of the polyol (A) with a polyisocyanate (B) and at least one phenoxy group; A method for producing a urethane acrylate oligomer having the phenoxy group according to claim 1, which comprises reacting an acrylate or methacrylate (C) having at least one hydroxyl group. The urethane acrylate according to claim 2, wherein the reaction ratio of polyol (A), polyisocyanate (B), and acrylate or methacrylate (C) is 1: 1.5 to 2.5: 0.5 to 1.5 in an equivalent ratio. Method for producing oligomers. The polyol (A) having at least one hydroxy group according to claim 1, wherein the polyol (A) having at least one hydroxy group is a polyethylene glycol, polypropylene glycol, polytetrahydrofuran polyol, polyester polyol, polycaprolactone polyol, polybutadiene polyol, poly Urethane acrylate oligomer, characterized in that selected from carbonate polyols or mixtures thereof. The method of claim 4 wherein the polyester polyol is ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,6-hexane diol, neopentyl glycol, 3-methyl-1,5 Obtained by the reaction of a polyhydric alcohol selected from pentanediol, 1,9-nonanediol or 2-methyl-1,8-octanediol with a polybasic acid selected from maleic acid, fumaric acid, adipic acid, sebacic acid or succinic acid Urethane acrylate oligomer characterized by the above-mentioned. The process of claim 4 wherein the polycaprolactone polyol is selected from the group consisting of ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,2-polybutylene glycol, 1,6-hexanediol, neo A urethane acrylate oligomer obtained by reaction of a dihydric alcohol selected from pentyl glycol or 1,4-butanediol with epsilon caprolactone. The urethane of claim 4, wherein the polycarbonate polyol is selected from 1,6-hexanedicarbonate, 1,9-nonanedipolycarbonate, 2-methyl-1,8-octanepolycarbonate, or mixtures thereof. Acrylate oligomers. The polyisocyanate (B) having two or more isocyanate groups, according to claim 1, which is methylene-bis (4-cyclohexylisocyanate), 1-isocyanato-3-isocyanatomethyl-3,5,5- Trimethylcyclohexane, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, noborane diisocyanate, dimer acid diisocyanate, 2,4-toluene diisocyanate, 2,6- Toluene diisocyanate, hydrogenated 2,4-toluene diisocyanate, hydrogenated 2,6-toluene diisocyanate, meta-phenylene diisocyanate, para-phenylene diisocyanate, 1,3-dimethylphenyl-2,4-di Isocyanate, 1,3-dimethylphenyl-4,6-diisocyanate, 1,4-dimethylphenyl-2,5-diisocyanate, 1-chlorophenyl-2,4-diisocyanate, 4,4-diphenyl diisocyanate , 3,3-dimethyl-4,4-diphenyldiiso Anate, 2,4-diphenyl diisocyanate, 3,3-dimethoxy-4,4-diphenylmethane diisocyanate, 3,3-dimethyl-4,4-diphenylmethane diisocyanate, 4,4-di Phenylmethane diisocyanate, 1,4-naphthalene diisocyanate, 1,5-naphthalene diisocyanate, 2,6-naphthalene diisocyanate, 2,7-naphthalene diisocyanate, para-xylene diisocyanate, meta-xylene diisocyanate , 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,7-heptamethylene diisocyanate, 1,8-octamethylene diisocyanate, 1,9- Nonamethylene diisocyanate, 1,10-decamethylene diisocyanate, 2,2,4-trimethyl-1,5-pentamethylene diisocyanate, 2,2-dimethyl-1,5-pentamethylene diisocyanate, 3-methoxy -1,6-hexamethylene diisocyanate, 3-butoxide 1,6-hexamethylene diisocyanate, 1,4-cyclohexylene sildi diisocyanate, 1,3-cyclohexyl diisocyanate, or a urethane acrylate oligomer, characterized in that is selected from a mixture thereof.