JP3141437B2 - UV curable resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel and useful ultraviolet-curable resin composition. More specifically, the present invention comprises, as an essential component, a specific urethane acrylate, in particular, curability, abrasion resistance after resin curing,
The present invention relates to an ultraviolet-curable resin composition having excellent stain resistance, flexibility and weather resistance (light resistance).

[0002] The resin composition of the present invention can be used as a general paint or a surface treatment agent for paper, woodwork, plastic or metal, and other organic or inorganic materials.
It is extremely useful.

[0003]

2. Description of the Related Art In recent years, active energy ray-curable resins are:
In particular, UV-curable resins have been widely used, including surface treatment agents such as paints.

[0004] This is because, as compared with the conventional curing method, it has a remarkably fast curing property, is a non-heat-curing type, can be made solvent-free, and can save the space of the line. This is because it has many advantages such as good energy efficiency required for curing.

[0005] As such an active energy ray-curable resin, a resin system having an α, β-double bond (polymerizable unsaturated bond) is used. Specifically, polyester (meth) acrylate, Representative examples include unsaturated polyesters, polyether (meth) acrylates, polyurethane (meth) acrylates, and the like.

[0006] By the way, the active energy ray-curable resin system up to the present is suitable for the design of a hard cured film, and as a typical example, the surface hardness of a hard coat is very high, and abrasion resistance is very high. Those with excellent properties have been developed.

[0007] However, with respect to those having flexibility, it has been difficult to achieve a combination of curability, abrasion resistance, solvent resistance and stain resistance. In general, the curability, hardness, and flexibility of an active energy ray-curable resin are determined by the concentration of a crosslinking point at which a functional group that reacts directly or indirectly with the active energy ray is generated in the system, and the molecular skeleton structure. It has a significant effect.

[0008] From these viewpoints, it is possible to increase the number of functional groups that form cross-linking points in the molecule, to make the molecular structure hard, and to increase the curability and hardness.
As a result, both the solvent resistance and the stain resistance are improved.

[0009] However, by designing the properties of the coating film to be hard as described above, flexibility, flexibility, elongation, and the like are lost. Was unsuitable for use.

Further, if the crosslinking density is lowered or the molecular skeleton structure is made soft, flexibility, elongation, etc. can be obtained, but inevitably curability, solvent resistance, stain resistance, etc.
Actually, the wear resistance and the abrasion resistance are lost and the use is greatly restricted.

[0011]

However, in view of the above-mentioned problems in the prior art, the present inventors have found that they can be used for applications requiring flexibility, elongation, etc., and furthermore, they have curability, solvent resistance, and resistance to solvent. An object of the present invention is to provide a novel type of ultraviolet curable resin composition having properties such as stain resistance, abrasion resistance, abrasion resistance and weather resistance (light resistance). As a researcher, I did my best.

[0012]

Means for Solving the Problems Accordingly, the present inventors have:
As a result of intensive studies with an eye on the problems to be solved by the invention as described above, a compound having at least one (meth) acryloyl group and a hydroxyl group in one molecule, and a specific polycarbonate diol And a resin obtained by reacting with a polyisocyanate having an isocyanurate structure, comprising a specific urethane acrylate, in particular, curability, scratch resistance after resin curing, stain resistance, flexibility, light resistance, etc. The present invention has now been completed by finding an ultraviolet-curable resin composition excellent in the above.

That is, the present invention aims to provide a specific ultraviolet-curable urethane (meth) acrylate-based resin composition called a polycarbonate-modified polyurethane acrylate. A compound (a-1) having at least one (meth) acryloyl group and a hydroxyl group in one molecule, a polycarbonate diol (a-2) having a molecular weight of 300 to 3,000, and isocyanurate Polyisocyanate having a structure (a-
3), a resin obtained by reacting these essential constituents [hereinafter also referred to as resin (A). ) And a compound having both a (meth) acryloyl group and a group that generates a radical by light [hereinafter, also referred to as compound (B). It is an object of the present invention to provide a curable resin composition containing a so-called modified photoinitiator as an essential component and capable of being cross-linked and cured by the action of ultraviolet light.

Here, at least one molecule is used in one molecule used as an essential constituent of the urethane acrylate.
As the compound (a-1) having both (meth) acryloyl groups and hydroxyl groups, known compounds can be used,
Of those, only typical ones are exemplified, and 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2
-Hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, pentaerythritol tri (meth) acrylate or Glycidyl methacrylate
(Meth) acrylic acid adduct,

As described above, ring-opening products of various (meth) acrylate compounds having a hydroxyl group with ε-caprolactone are exemplified. In addition, if only typical examples of the above-mentioned polycarbonate diol (b-2) are exemplified, diphenyl carbonate, bischlorophenyl carbonate, dinaphthyl carbonate, phenyl-toluyl-carbonate, phenyl-chlorophenyl-carbonate or 2 -Tolyl-4-
A diaryl- or dialkyl carbonate, such as tolyl-carbonate or dimethyl carbonate or diethyl carbonate;

Ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol , 1,9-nonanediol, 1,10-decanediol, 2,2,4-trimethyl-1,3-pentanediol, 3-methyl-
1,5-pentanediol, dichloroneopentylglycol, dibromoneopentylglycol, neopentylglycol hydroxypivalate, cyclohexanedimethylol, 1,4-cyclohexanediol, trimethylolethane, trimethylolpropane,
Glycerin, 3-methylpentane-1,3,5-triol, pentaerythritol, spiro glycol, tricyclodecane dimethylol, hydrogenated bisphenol A,

Or "New Coal PM-870I"
L, BA-E4, BA-EP or BA-PG "(manufactured by Nippon Emulsifier Co., Ltd., ethylene oxide or propylene oxide adduct of bisphenol A), or various polyols as described above, and the following: And a class of carbonate derivatives obtained by a reaction with a polyol represented by a transesterification reaction with a polyester diol such as a reaction product with a polycarboxylic acid.

The above-mentioned polycarboxylic acid includes:
Of course, various known and commonly used carboxylic acids or their anhydrides can be used. Of those, maleic acid, fumaric acid, itaconic acid, citraconic acid, if only typical ones are exemplified. , Tetrahydrophthalic acid, hetonic acid, hymic acid, chlorendic acid, dimer acid, adipic acid, succinic acid, alkenylsuccinic acid, sebacic acid, azelaic acid, 2,2,4-trimethyladipate, 1,4-cyclohexane Dicarboxylic acid,
Terephthalic acid, 2-sodium sulfoterephthalic acid, 2
Di-lower alkyl esters of 5-sodium-sulfoisophthalic acid, such as potassium sulfoterephthalic acid, isophthalic acid, 5-sodium sulfoisophthalic acid, 5-potassium sulfoisophthalic acid, or dimethyl or diethyl ester, or orthophthalic acid Acid, 4
-Sulfophthalic acid, 1,10-decamethylenedicarboxylic acid, muconic acid, oxalic acid, malonic acid, glutanic acid, trimellitic acid, hexahydrophthalic acid, tetrabromophthalic acid, methylcyclohexentricarboxylic acid or pyromellitic acid, or these Acid anhydrides and the like.

The polycarbonate diol (a-2)
When incorporated as a main chain skeleton of urethane acrylate, those having a molecular weight of 300 or more and 3,000 or less from the viewpoint of application are preferable.

The urethane bond of the urethane (meth) acrylate has at least one (meth)
The compound (a-1) having an acryloyl group and a hydroxyl group is obtained by reacting a polycarbonate polyol, particularly a hydroxyl group component in the polycarbonate diol (a-2), with an isocyanate compound. Preferred are polyisocyanates in a modified form.

It is a matter of course that a polyisocyanate in an isocyanurated form may be used in combination with an isocyanate compound. If only typical isocyanate compounds are exemplified, dicyclohexylmethane may be used. Various alicyclic diisocyanate compounds such as diisocyanate or isophorone diisocyanate; or various aliphatic diisocyanate compounds such as hexamethylene diisocyanate or lysine diisocyanate; hydrogenated xylylene diisocyanate or hydrogenated diphenylmethane-4,4'-diisocyanate And various compounds.

Further, as a so-called modified photoinitiator, which is also referred to as a compound (B) having both the (meth) acryloyl group and a group capable of generating a radical by light,
Co-reactive photopolymerization initiators and the like described in JP-A-63-254105 can be used. Examples of commercially available photopolymerization initiators include "Darocur 2959" [Merck 4- (2- (Hydroxyethoxy) -phenyl-2
-(2-hydroxy) propyl ketone] is a typical example.

As the benzophenone derivative, one having a compound having a reactive group can be used.
Among them, particularly typical ones are exemplified by benzophenone tetracarboxylic acid, benzophenone tetracarboxylic dianhydride or benzophenone tetracarboxylic acid alkyl ester.

By introducing a (meth) acryloyl group into the modified photoinitiator compound (B), it is possible to further improve the curability and physical properties of the coating film.

A typical example thereof is a (meth) acrylate compound having a reactive functional group such as a carboxyl group, a hydroxyl group, an isocyanate group, or an epoxy group at the terminal.

Among them, (meth) acrylic acid is a typical carboxyl group-containing (meth) acrylate, and (meth) acrylic acid and ε-caprolactone ring-opened product, or hydroxyl group-containing (meth) acrylate Ring-opened products of (meth) acrylate with various acid anhydrides such as succinic anhydride, phthalic anhydride, trimellitic anhydride or pyromellitic anhydride can be mentioned.

Next, as the (meth) acrylate containing a hydroxyl group, the compounds listed above can be used. Examples of the (meth) acrylate containing an isocyanate group include "Karenz MOI" (2-methacryloyloxyethyl isocyanate manufactured by Showa Denko KK), and the reaction between the above-mentioned (meth) acrylate containing a hydroxyl group and a polyisocyanate compound. Examples include urethane (meth) acrylate containing an active isocyanate group.

Further, as the epoxy group-containing (meth) acrylate, glycidyl (meth) acrylates,
Or a compound obtained by reacting a carboxyl group-containing (meth) acrylate with a polyglycidyl compound.

In the modified photoinitiator (B),
By introducing a polysiloxane structure, the surface appearance and surface curability and frictional resistance can be further improved.
It can be good.

As a method for introducing such a siloxane structure, a polysiloxane whose terminal is modified with a reactive functional group such as hydroxyl group, amine, epoxy, alkoxysilane or thiol is reacted with the above-mentioned modified photoinitiator. Alternatively, the reaction may be carried out during the synthesis of the modified photoinitiator.

The reaction includes a reaction between a hydroxyl group and an isocyanate group, a reaction between a hydroxyl group and a carboxyl group, a reaction between an isocyanate group and an amino group, a reaction between an isocyanate group and a carboxyl group, a reaction between an epoxy group and an amine, A reaction between an epoxy group and a carboxyl group, a reaction between an epoxy group and a thiol group, or a reaction between a hydroxyl group and a silanol group can be used.

These various reactions may be carried out alone or in combination, and there is no restriction as long as the desired compound is obtained. Also, by the urethanization reaction,
It is possible to impart mechanical properties, particularly, toughness, etc. of the cured coating film.

The urethanization reaction referred to here refers to a polycondensation of a hydroxyl group and an isocyanate group, and includes a hydroxyl group-containing siloxane compound, a hydroxyl group-containing photopolymerization initiator compound or a hydroxyl group-containing (meth) acrylate compound, or an isocyanate group. By reacting the group-containing (meth) acrylate compound with a polyisocyanate compound or another hydroxyl group-containing compound (polyol), an intended urethane bond-containing compound can be obtained.

The polycarbonate-based urethane acrylate (A) and the modified photoinitiator (B) are 30 to 90 parts of the urethane acrylate (A) and 1 to 20 parts of the modified photoinitiator (B). It is particularly desirable that the ratio be composed of parts.

The UV-curable resin composition of the present invention may further contain other components, if necessary. These other components include solvents, reactive diluents, photo (polymerization) initiators, polymers, polymerization inhibitors, antioxidants,
Dispersants, surfactants, inorganic fillers, inorganic pigments, or organic pigments can be added.

As typical solvents, only typical ones are exemplified. Aromatic hydrocarbons such as toluene or xylene; ketones such as methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone; methyl acetate, ethyl acetate or butyl acetate Alcohols such as methanol, ethanol, propanol or butanol; aliphatic hydrocarbons such as hexane and heptane, as well as cellosolve acetate;
Examples include carbitol acetate, dimethylformamide or tetrahydrofuran.

As the reactive diluent (C), monofunctional ones to polyfunctional ones are widely used. Among them, only typical representative ones are exemplified. For example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate,
2-ethylhexyl (meth) acrylate, N-vinylpyrrolidone, 1-vinylimidazole, isobornyl (meth) acrylate, tetrahydrofurphyryl (meth) acrylate, carbitol (meth) acrylate, phenoxyethyl (meth) acrylate, dicyclopentadiene (Meth) acrylate, 1,3-butanedi (meth) acrylate, 1,6-hexanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, hydroxypivalic acid ester neopentyl glycol di (meth) acrylate, trimethylol Propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate or dipentaerythritol hexa (meth) Acrylate, and the like.

The polycarbonate-based urethane acrylate (A) and the reactive diluent (C) are 30 to 90 parts of the urethane acrylate (A) and 0 to 70 parts of the reactive diluent (C). Is particularly desirable.

Further, as the reactive diluent (C),
When the monofunctional (meth) acrylate having an aliphatic cyclic structure accounts for 20% or more of the total reactive diluent, the curability and the coating properties of the ultraviolet-curable resin composition of the present invention are obtained. It is particularly desirable because it has a great effect on aspects such as:

Further, as the monofunctional (meth) acrylate having an aliphatic cyclic structure, isobornyl (meth) acrylate is used in view of the viscosity of the composition of the present invention, various physical properties of a cured coating film, and skin irritation. , Which is extremely useful.

Then, the mixing ratio of the resin (A) and the compound (B), respectively, or the resin (A), the compound (B), and the reactive diluent (C ) Is 30 to 95 of the resin (A).
Suitably, there are from 1 to 20 parts of compound (B) and 0 to 70 parts of reactive diluent (C).

In the present invention, when the resin composition of the present invention is cured by using the above-mentioned ultraviolet ray as a so-called energy ray, the radical is dissociated by the ultraviolet ray having a wavelength of 1,000 to 8,000 angstroms. Such a photo (polymerization) initiator should be used. As such a photo (polymerization) initiator, in addition to the above-mentioned modified photoinitiator, any known and commonly used photoinitiator can be used in combination. Representative examples include acetophenones, benzophenone, Michler's ketone, benzene, benzoin benzoate, benzoin, benzoin methyl ethers, benzyl dimethyl ketal,
α-acyloxime esters, thioxanthones, anthraquinones and various derivatives thereof.

In addition, a known and commonly used photosensitizer can be used in combination with such a photo (polymerization) initiator. However, if only typical photosensitizers are exemplified, only typical photosensitizers are exemplified. Examples include amines, ureas, sulfur-containing compounds, phosphorus-containing compounds, chlorine-containing compounds, nitriles and other nitrogen-containing compounds.

The above-mentioned polymer may be any of a saturated or unsaturated polymer. The polymer can be added for the purpose of modifying the physical properties of a cured coating film or reducing the cost.

Examples thereof include acrylic resins, polyester resins, polyamide resins, epoxy resins, polyurethane resins, vinyl chloride-vinyl acetate copolymers, polyvinyl butyral resins, cellulose resins, and chlorinated polypropylene. I can do it.

Representative examples of the above-mentioned inorganic filler include barium sulfate, calcium carbonate, talc, mica,
Clay, barium carbonate, gypsum, alumina white, silica, calcium silicate, magnesium carbonate silica powder, colloidal silica, asbestos powder, extender pigments such as aluminum hydroxide, zinc stearate; chromium such as graphite, zinc chromate or molybdate orange Acid salts, ferrocyanides such as navy blue, metal oxides such as titanium oxide, zinc white, red iron oxide, chromium carbide green, metal sulfides such as cadmium yellow, cadmium red or mercury sulfide, selenide or lead sulfate. Sulphate, silicate like ultramarine, or carbonate,
Phosphate or aluminum powder, zinc powder, brass powder, magnesium powder, iron powder, metal powder such as copper powder or nickel powder, such as cobalt violet or manganese purple, and inorganic pigments such as carbon black; or
Azo pigments, phthalocyanine blue, phthalocyanine
Organic pigments such as copper phthalocyanine pigments such as green or quinacridone pigments.

The ultraviolet-curable resin composition of the present invention thus obtained may be usually cured as it is by irradiating it with ultraviolet rays as described above. The ultraviolet-curable resin composition of the present invention can be used for a paint, a surface modifier, or a printing ink, and is extremely practical.

[0048]

Next, the present invention will be described more specifically with reference examples, examples, comparative examples, and test results, but the present invention is not limited to only these examples.
In the following, all parts and percentages are by weight unless otherwise specified.

Reference Example 1 (Preparation Example of Polycarbonate-Modified Polyurethane Acrylate) In a flask equipped with a thermometer, a stirrer and a condenser, “Varnock DN-901” as hexamethylene diisocyanate in the form of isocyanurate was added.
S "(product of Dainippon Ink and Chemicals, Inc.) and 150 g of methyl ethyl ketone (MEK) were charged.
After evenly stirring, “Placcel CD220HL”
200 g of [Polycarbonate diol manufactured by Daicel Chemical Industries, Ltd.] was added, and a reaction was performed at 80 ° C. for 2 hours.

Next, 48 g of 2-hydroxyethyl acrylate was added, and the mixture was further reacted at the same temperature for 2 hours to obtain a desired polycarbonate-modified polyurethane acrylate. Hereinafter, this is abbreviated as resin (A-1).

REFERENCE EXAMPLE 2 (Same as above) A flask equipped with a thermometer, a stirrer and a condenser was charged with 54.7 g of "Varnock DN-901S", 16.8 g of hexamethylene diisocyanate and 150 g of methyl ethyl ketone, and stirred uniformly. Thereafter, 100 g of "Placcel CD210PL" (polycarbonate diol manufactured by Daicel Chemical Industries, Ltd.) was added, and the mixture was reacted at 80 ° C for 2 hours.

Next, 34.8 g of 2-hydroxyethyl acrylate was added, and the mixture was further reacted at the same temperature for 2 hours to obtain a desired polycarbonate-modified polyurethane acrylate. Hereinafter, this is referred to as resin (A-2).
Abbreviated.

Reference Example 3 (Same as above) A flask equipped with a thermometer, a stirrer, and a condenser was charged with 55.0 g of "Varnock DN-901S" and 150 g of methyl ethyl ketone, and stirred uniformly. 70 "(carbonate diol manufactured by Toa Gosei Chemical Industry Co., Ltd.) was added, and the reaction was carried out at 80 ° C for 2 hours.

Next, 134 g of "TONE M-100" (caprolactone-modified hydroxyethyl acrylate manufactured by Union Carbide) was added, and the mixture was further reacted at the same temperature for 2 hours to obtain the desired polycarbonate-modified polyurethane acrylate. I got Hereinafter, this is abbreviated as resin (A-3).

Reference Example 4 (Same as above) In a flask equipped with a thermometer, a stirrer and a condenser, 110 g of "Varnock DN-901S", 50 g of isobornyl acrylate, 50 g of carbitol acrylate and 3 g of hexamethylene diacrylate were added.
To a place where 0 g was charged and uniformly stirred, 70 g of "carbodiol C-700 was added, and the reaction was carried out at 80 ° C for 2 hours.

Next, 13 of "TONE M-100"
5 g was added, and the reaction was carried out at the same temperature for another 2 hours to obtain the desired polycarbonate-modified polyurethane acrylate. Hereinafter, this is abbreviated as (A-4).

Reference Example 5 (Preparation Example of Urethane Acrylate) In a flask equipped with a thermometer, a stirrer, and a condenser, 1 part of diphenylmethane diisocyanate (MDI) was added.
00g and 50g of MEK were charged, the temperature was raised to 60 ° C, and the uniformly stirred MDI was dissolved in “PEG 60”.
0 "[polyethylene glycol manufactured by NOF CORPORATION] was added, and the reaction was carried out at 80 ° C for 2 hours. Next, 25 g of 2-hydroxyethyl acrylate was added, and the mixture was further reacted at the same temperature for 2 hours to obtain a control compound (A′-1).

Reference Example 6 (Preparation Example of Modified Photoinitiator) 55 g of "Barnock DN-901S" was placed in a flask.
And 4- (2-hydroxyethoxy) phenyl-2-
45 g of a solution obtained by diluting (2-hydroxy) propyl ketone to 50% with methyl ethyl ketone and 13 g of 2-hydroxypropyl acrylate were charged and reacted at 80 ° C. for 4 hours with stirring. Thereafter, it was confirmed by infrared spectrum that the characteristic absorption of the isocyanate group had disappeared, and an acryloyl group-containing modified photoinitiator was obtained as the desired photopolymerization initiator.
Hereinafter, this is abbreviated as compound (B-1).

Reference Example 7 (same as above) 55 g of "Barnock DN-901S" was placed in a flask.
And a bis (2-hydroxylated group having a hydroxyl value of 112 mg-KOH / g
50 g of (hydroxyethoxypropyl) polydimethylsiloxane was charged and reacted at 80 ° C. for 4 hours with stirring, and then 4- (2-hydroxyethoxy) phenyl-2- (2-hydroxy) propyl ketone was added. Of a solution diluted to 50% with methyl ethyl ketone
g and 13 g of 2-hydroxypropyl acrylate were added, and the mixture was reacted at 80 ° C. for 4 hours with stirring.

Thereafter, it was confirmed by infrared spectrum that the characteristic absorption of the isocyanate group had disappeared, and a modified acryloyl group-containing photoinitiator was obtained as the intended photopolymerization initiator containing a siloxane bond.

Hereinafter, this is abbreviated as compound (B-2). Reference Example 8 (same as above) In a flask, 52.4 g of 4,4′-dicyclohexylmethane diisocyanate and a hydroxyl value of 50 mg-KO were added.
H / g of 2-dimethylolbutoxypropylmethylpolydimethylsiloxane (224 g) was charged and reacted with stirring at 80 ° C. for 4 hours.
50% of (2-hydroxyethoxy) phenyl-2- (2-hydroxy) propyl ketone with methyl ethyl ketone
45 g of the diluted solution and 30 g of pentaerythritol triacrylate are added, and while stirring, 80 g is added.
The reaction was carried out at 4 ° C. for 4 hours.

Thereafter, it was confirmed by infrared spectrum that the characteristic absorption of the isocyanate group had disappeared, and an intended acryloyl group-containing modified photoinitiator was obtained as the intended siloxane bond-containing photopolymerization initiator.

Hereinafter, this is abbreviated as compound (B-3). Reference Example 9 (same as above) In a flask, bis [3 having an epoxy value of 490 g / mol was added.
-(Oxiranylmethoxy) propyl] 98 g of polydimethylsiloxane and 15 g of acrylic acid were charged, and 1
The reaction was performed at 00 ° C. for 10 hours.

Next, 45 of isophorone diisocyanate
g was added and the reaction was carried out at 80 ° C. for 6 hours. Then, 4- (2-hydroxyethoxy) phenyl-2-
95 g of a solution obtained by diluting (2-hydroxy) propyl ketone to 50% with methyl ethyl ketone was added, and the mixture was reacted at 80 ° C. for 4 hours while stirring.

Thereafter, it was confirmed by infrared spectrum that the characteristic absorption of the isocyanate group had disappeared, and a modified acryloyl group-containing photoinitiator was obtained as the desired siloxane bond-containing photopolymerization initiator.

Hereinafter, this is abbreviated as compound (B-4). Examples 1 to 6 According to the following composition table, a target ultraviolet curable paint was produced.

[0067]

[Table 1]

[0068]

[Table 2]

Example 7 100 parts of the polycarbonate-modified polyurethane acrylate resin (A-4) was mixed with "Darocur ZL"
13331 "[4- (2-acryloyloxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, manufactured by Merck Ltd.] was added and mixed uniformly.

Comparative Example 1 Control urethane acrylate compound (A'-1)
Was added to 100 parts of benzyldimethyl ketal, and the mixture was homogeneously mixed.

Comparative Example 2 50 parts of trimethylolpropane triacrylate, 30 parts of carbitol acrylate, 20 parts of hexamethylene diacrylate, and 3 parts of benzyl dimethyl ketal were added and uniformly mixed.

Test Result Example 1 Each of the ultraviolet curable resin compositions obtained in each of the Examples and Comparative Examples was separately placed on a glass plate so as to have a dry film thickness of about 100 μm (μm). It was applied with a bar coater.

Next, for Examples 1 to 4 and Comparative Examples 1 and 2, predrying was carried out at 80 ° C. for 10 minutes, while for Examples 5 and 6, after application of the paint, With an 80W high-pressure mercury lamp,
Ultraviolet irradiation with an intensity of 0 microjoules / square centimeter was performed.

Thereafter, each coated plate thus obtained was subjected to odor immediately after irradiation with ultraviolet rays, and at the same time, a Taber abrasion test was performed 100 times with a load of 500 g using a wear wheel “CS-10F”. And the change in haze (ΔHAZE) were measured.

Further, the coating film itself was subjected to a 50% elongation test, and the appearance of the coating film was observed. Further, the cured coating film was subjected to a scratch test using “Osaka Diamond No. 1”. The results are summarized in Table 2.

Test Result Example 2 Each coating film cured in the same manner as in Reference Example 1 was
After performing a heat resistance test at 100 ° C. for 1,000 hours and simultaneously using a “light-fast superfade meter” at a film surface temperature of 83 ° C. for 1,000 hours (irradiation on a glass surface). A test for Taber abrasion after the durability test was performed to measure the change in haze. The results are summarized in Table 3.

[0077]

Table 2 Surface curability Odor ΔHAZE Elongation test Scratch test Example 11 None 2.8 ７００ 700 g 21 None 3.2 650 g 31 None 3.1 750 g 4-1 None 3.3 ６００ 600 g 5 1 None 3.0 ○ 600 g 61 None 2.8 ○ 650 g 71 1 None 3.6 ○ 600 g ────────────────────────── ──────── Comparative Example 1 5 Yes 15.8 ○ 10g 22 Yes 25.4 × 10g ■ ─────────────────────── ───────────

[0078]

[Table 4] Table 3 ΔHAZE elongation test Scratch test ■ ────────────────────────────────── Example 1 3.5 700 g 2 4.2 600 g 3 4.3 700 g 4 4.6 550 g 5 3.8 600 g 6 3.5 600 g 7 4.8 600 g ───────────────────────── Comparative Example 1 Measurement is impossible due to non-uniform film surface. 9 x 10g ■■ ──────────────────────────────────

[0079]

[Footnotes to Tables 2 and 3] Surface curability: 15 from high pressure mercury lamp of 80 w / cm
UV irradiation at a distance of 10 cm and a line speed of 10 m / min, indicating the number of passes that become tack-free. Odor: 15 from a high-pressure mercury lamp of 80 w / cm.
UV irradiation at a distance of 10 cm and a line speed of 10 m / min.
“Have”, “None” ΔHAZE: The change in haze before and after the Taber abrasion test is expressed as a percentage (%). (Visual judgment) is indicated by “O” or “X” ○: No distortion or breakage, and no defects in the coating film ×: Coating films such as distortion or breakage When defects are found Scratch test ……… Indicated by the allowable load of scratching with “Osaka Diamond No. 1” and the maximum load after 24 hours, such as when the coating film is scratched, torn or distorted.

[0080]

As is clear from the results shown in Tables 2 and 3, the ultraviolet-curable resin composition of the present invention is particularly suitable for curing, abrasion resistance, abrasion resistance and weather resistance (light resistance). It can be seen that the film gives an excellent coating film such as

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁷ Identification symbol FI C09D 175/16 C09D 175/16 (56) References JP-A-53-8697 (JP, A) JP-A-61-50939 (JP) JP-A-2-202507 (JP, A) JP-A-2-292307 (JP, A) JP-A-2-292315 (JP, A) JP-A-4-31422 (JP, A) 5-70534 (JP, A) JP-A-63-254105 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 290/00-290/14 C08F 299/00-299 / 08 C08F 2/00-2/60 C08G 18/00-18/87 C09D 1/00-201/10

Claims (11)

(57) [Claims] 1. A compound (a-1) having at least one (meth) acryloyl group and a hydroxyl group in one molecule.
And a resin (A) obtained by reacting a polycarbonate diol (a-2) having a molecular weight of 300 to 3,000 with a polyisocyanate (a-3) having an isocyanurate structure, and a (meth) acryloyl group And a compound (B) having a group capable of generating a radical by light as an essential component. 2. A compound (a-1) having at least one (meth) acryloyl group and a hydroxyl group in one molecule.
And a resin (A) obtained by reacting a polycarbonate diol (a-2) having a molecular weight of 300 to 3,000 with a polyisocyanate (a-3) having an isocyanurate structure, and a (meth) acryloyl group (B) having both a compound and a group that generates a radical by light
And a reactive diluent (C) as an essential component. 3. A compound having at least one (meth) acryloyl group and a hydroxyl group in one molecule as described above (a)
-1), 30 to 95 of a resin (A) obtained by reacting a polycarbonate diol (a-2) having a molecular weight of 300 to 3,000 with a polyisocyanate (a-3) having an isocyanurate structure. Parts, 1 to 20 parts of the compound (B) having both the (meth) acryloyl group and the group generating a radical by light, and 0 to 70 parts of the reactive diluent (C), as essential components. The UV-curable resin composition according to claim 1, wherein the resin composition comprises: 4. The resin (A) according to claim 1, wherein the polycarbonate diol (a-2) comprises a compound having an alicyclic structure. 3. The ultraviolet-curable resin composition according to item 1. 5. The resin (A) according to claim 1, wherein the polyisocyanate (a-3) having an isocyanurate structure is a compound derived from hexamethylene diisocyanate. The ultraviolet-curable resin composition according to any one of the above. 6. A compound (B) having both the (meth) acryloyl group and a group capable of generating a radical by light.
Is 4- (2-acryloyloxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone. The ultraviolet-curable resin composition according to claim 1, wherein 7. A compound (B) having both the (meth) acryloyl group and a group capable of generating a radical by light,
The ultraviolet-curable resin composition according to any one of claims 1 to 3, which is a compound derived from 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone. 8. A compound (B) having both the (meth) acryloyl group and a group capable of generating a radical by light as described above,
A compound having both a hydroxyl group and a (meth) acryloyl (oxy) group, the 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone,
The ultraviolet-curable resin composition according to any one of claims 1 to 3, which is obtained by reacting with a polyisocyanate. 9. A compound (B) having both the (meth) acryloyl group and a group capable of generating a radical by light as described above,
A compound having both a hydroxyl group and a (meth) acryloyl (oxy) group, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, a polyisocyanate, and a hydroxyalkyl-modified polysiloxane. Claim 1 which is obtained by a reaction.
3. The ultraviolet-curable resin composition according to any one of 3. 10. The reactive diluent (C) wherein monofunctional (meth) acrylate having an aliphatic cyclic structure accounts for at least 20% of the diluent (C). Item 4. The ultraviolet-curable resin composition according to item 2 or 3. 11. The reactive diluent (C) wherein the monofunctional (meth) acrylate having an aliphatic cyclic structure is, in particular, isobornyl (meth) acrylate. The ultraviolet-curable resin composition according to item 10.