JPH0570535A - Ultraviolet-curable resin composition - Google Patents

Abstract

PURPOSE:To provide a resin composition which is excellent especially in curability and can give a film excellent in scuffing and light resistances. CONSTITUTION:The title composition comprises a specified polycarbonate urethane acrylate obtained by reacting a vinyl monomer containing a (meth)acryloyl group and a hydroxyl group (e.g. 2-hydroxyethyl (meth)acrylate) with a polycarbonate diol (e.g. a reaction product of a diaryl carbonate or a dialkyl carbonate with a polyol) and a polyisocyanate having an isocyanurate structure and a compound containing a (meth)acryloyl group and a group which forms a free radical when irradiated with light (modified photoinitiator).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION 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, among others, curability, scratch resistance after resin curing,
The present invention relates to an ultraviolet curable resin composition having excellent stain resistance, flexibility and weather resistance (light resistance).

The resin composition of the present invention is used as a general coating material or a surface treatment agent for paper, woodworking, 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, it has come to be widely used as an ultraviolet curable resin, including surface treatment agents such as paints.

This is because it has much faster curability than conventional curing methods, is a non-heat curing type, can be solvent-free, and can save space in the line. This is because they have many advantages such as high energy efficiency required for curing.

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

By the way, the active energy ray-curable resin system up to now is suitable for designing a hard cured film, and as a typical example, a surface hardness such as a hard coat is very high and scratch resistance. Those with excellent properties have been developed.

[0007] However, as for flexible materials, it has been difficult to provide curability, abrasion resistance, solvent resistance and stain resistance together. Generally, the curability, hardness and flexibility of an active energy ray-curable resin are determined by the concentration of the cross-linking point at which functional groups that react directly or indirectly by the active energy ray are generated in the system and the molecular skeleton structure. It has a great influence.

From this point of view, it is necessary to increase the number of functional groups forming cross-linking points in the molecule, to make the molecular structure hard, and to increase the curability and hardness.
As a result, both solvent resistance and stain resistance are good.

However, by designing the properties of the coating film to be hard in this way, flexibility, flexibility, and elongation are lost, and especially, post-processing is required or a flexible base material. Was not suitable for use.

Further, if the crosslink density is lowered or the molecular skeleton structure is made soft, flexibility and elongation can be obtained, but inevitably curability, solvent resistance, stain resistance, and
The fact is that wear resistance and scratch resistance have been lost, and there are great restrictions on use.

[0011]

However, in view of the above-mentioned problems in the prior art, the inventors of the present invention can be used for necessary applications such as flexibility and elongation, and further, curability, solvent resistance, resistance to resistance, etc. The object of the present invention is to provide a novel UV curable resin composition having properties such as stain resistance, abrasion resistance, scratch resistance and weather resistance (light resistance). As a result, I eagerly studied.

[0012]

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

That is, the present invention is to provide a specific ultraviolet-curable urethane (meth) acrylate resin composition called polycarbonate-modified polyurethane acrylate, wherein the essential constituent substance of the urethane (meth) acrylate is A compound (a-1) each 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 structure (a-
Resin obtained by reacting these essential constituents with 3) [hereinafter also referred to as resin (A)]. ) And 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 crosslinked and cured by the action of ultraviolet rays.

Here, at least 1 is contained in one molecule used as an essential constituent of the urethane acrylate.
As the compound (a-1) having both (meth) acryloyl group and hydroxyl group, known and commonly used compounds can be used.
Among them, only typical ones are exemplified by 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 addition product,

As described above, there are ring-opening reaction products of (meth) acrylate compounds having various hydroxyl groups with ε-caprolactone. Further, only the 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 triaryl-carbonate, or a diaryl- or dialkyl carbonate such as 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, dichloroneopentyl glycol, dibromoneopentyl glycol, hydroxypivalic acid neopentyl glycol ester, cyclohexanedimethylol, 1,4-cyclohexanediol, trimethylolethane, trimethylolpropane,
Glycerin, 3-methylpentane-1,3,5-triol, pentaerythritol, spiroglycol, tricyclodecane dimethylol, hydrogenated bisphenol A,

Or "Newcol PM-870I
L, BA-E4, BA-EP or BA-PG "[ethylene oxide or propylene oxide adduct of bisphenol A manufactured by Nippon Emulsifier Co., Ltd.], or various polyols as listed above and the following: Such a kind of carbonate derivative obtained by the reaction with a polyol represented by a transesterification reaction with a polyester diol or the like such as a reaction product with a polycarboxylic acid.

The polycarboxylic acid referred to here is
Of course, various known and commonly used carboxylic acids or their acid anhydrides can be used, but among them, only typical ones are exemplified by maleic acid, fumaric acid, itaconic acid and citraconic acid. , Tetrahydrophthalic acid, het acid, hymic acid, chlorendic acid, dimer acid, adipic acid, succinic acid, alkenyl succinic acid, sebacic acid, azelaic acid, 2,2,4-trimethyladipic acid, 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, glutanoic acid, trimellitic acid, hexahydrophthalic acid, tetrabromophthalic acid, methylcyclohexenetricarboxylic acid or pyromellitic acid, or these Acid anhydrides and the like.

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

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

It is needless to say that an isocyanurate-form polyisocyanate and an isocyanate compound may be used in combination. If only representative isocyanate compounds are exemplified, dicyclohexylmethane is 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 , Various compounds and the like.

Further, as a so-called modified photoinitiator, which should be called a compound (B) having both the above-mentioned (meth) acryloyl group and a group which generates a radical by light,
The co-reactive photopolymerization initiators described in JP-A-63-254105 can be used, but as industrially available ones, "Darocur 2959" [4- (2- Hydroxyethoxy) -phenyl-2
-(2-hydroxy) propyl ketone] and the like are typical examples.

As the benzophenone derivative, a compound having a compound having a reactive group can be used.
Among them, benzophenone tetracarboxylic acid, benzophenone tetracarboxylic acid dianhydride, benzophenone tetracarboxylic acid alkyl ester, and the like can be given to exemplify only typical ones.

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

A typical example of such a compound 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, as a carboxyl group-containing (meth) acrylate, (meth) acrylic acid is a typical one, and (meth) acrylic acid and ε-caprolactone ring-opened products and hydroxyl group-containing ( Examples thereof include ring-opened products of various acid anhydrides such as meth) acrylate and succinic anhydride, phthalic anhydride, trimellitic anhydride or pyromellitic anhydride.

Then, as the (meth) acrylate having a hydroxyl group, the compounds as listed above can be used. Further, as the isocyanate group-containing (meth) acrylate, "Karenzu MOI" [2-methacryloyloxyethyl isocyanate manufactured by Showa Denko KK], a reaction of the above-mentioned hydroxyl group-containing (meth) acrylate with a polyisocyanate compound Examples of the product include urethane (meth) acrylate containing an active isocyanate group.

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

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

As a method of introducing such a siloxane structure, a polysiloxane modified at the terminal with a reactive functional group such as a hydroxyl group, an amine, an epoxy, an alkoxysilane or a thiol is reacted with the above modified photoinitiator. Alternatively, it may be reacted during the synthesis of the modified photoinitiator.

This 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, due to the urethanization reaction,
It is possible to impart mechanical properties, especially toughness, to the cured coating film.

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

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

If necessary, other components can be added to the ultraviolet-curable resin composition of the present invention. As these other components, a solvent, a reactive diluent, a photo (polymerization) initiator, a polymer, a polymerization inhibitor, an antioxidant,
A dispersant, a surfactant, an inorganic filler, an inorganic pigment, or an organic pigment can be added.

Specific examples of the solvent include only 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. Such as esters; alcohols such as methanol, ethanol, propanol or butanol; aliphatic hydrocarbons such as hexane and heptane, cellosolve acetate,
Examples thereof include carbitol acetate, dimethylformamide, tetrahydrofuran and the like.

As the above-mentioned reactive diluent (C), monofunctional ones to polyfunctional ones are widely used. Among them, only typical ones are exemplified. For example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate,
2-ethylhexyl (meth) acrylate, N-vinylpyrrolidone, 1-vinylimidazole, isobornyl (meth) acrylate, tetrahydrofurfurylyl (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, hydroxypivalate 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 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 occupies 20% or more of all the reactive diluents, the curability and coating film physical properties of the ultraviolet curable resin composition of the present invention It is particularly desirable because it has excellent effects in terms of the above.

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

Then, the compounding ratios of the resin (A) and the compound (B) listed above, or the resin (A), the compound (B) and the reactive diluent (C), respectively. ) Is 30 to 95 of the resin (A).
Suitably, 1 part to 20 parts of the compound (B) and 0 to 70 parts of the reactive diluent (C).

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

Further, a known and commonly used photosensitizer may be used in combination with such a photo (polymerization) initiator. However, only representative examples of such photosensitizers will be exemplified. Examples thereof include amines, ureas, sulfur-containing compounds, phosphorus-containing compounds, chlorine-containing compounds, nitriles and other nitrogen-containing compounds.

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

Examples thereof include acrylic resin, polyester resin, polyamide resin, epoxy resin, polyurethane resin, vinyl chloride-vinyl acetate copolymer resin, polyvinyl butyral resin, fibrin resin or chlorinated polypropylene. I can.

Typical examples of the above-mentioned inorganic fillers include barium sulfate, calcium carbonate, talc, mica,
Extension pigments such as clay, barium carbonate, gypsum, alumina white, silica, calcium silicate, magnesium carbonate silica powder, colloidal silica, asbestos powder, aluminum hydroxide, zinc stearate; chromium such as yellow lead, zinc chromate or molybdate orange. Acid salts, ferrocyanides such as dark blue, metal oxides such as titanium oxide, zinc white, red iron oxide, iron oxide, chromium carbide green, metal sulfides such as cadmium yellow, cadmium red or mercury sulfide, selenides or lead sulfates. Such as sulfate, silicate such as ultramarine, or carbonate,
Phosphate or aluminum powder such as cobalt violet or manganese purple, zinc powder, brass powder, magnesium powder, metal powder such as iron powder, copper powder or nickel powder, and inorganic pigment such as carbon black; or
Azo pigment, phthalocyanine blue, phthalocyanine
There are organic pigments such as copper phthalocyanine pigments such as green or quinacridone pigments.

The thus-obtained UV-curable resin composition of the present invention may be usually cured by directly irradiating it with the UV rays as described above. The ultraviolet-curable resin composition of the present invention can be used for paints, surface modifiers or printing inks, and is extremely highly practical.

[0048]

Next, the present invention will be described more specifically with reference to Reference Examples, Examples, Comparative Examples and Test Result Examples, but the present invention is not limited to these Examples.
In the following, all parts and% are based on 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, "Bernock DN-901" in the form of hexamethylene diisocyanate in an isocyanurate form was used.
S ”[Dainippon Ink and Chemicals, Inc. product] 110 g and methyl ethyl ketone (MEK) 150 g were charged,
After uniformly stirring, "Plaxel CD220HL"
200 g of [polycarbonate diol manufactured by Daicel Chemical Industries, Ltd.] was added, and the reaction was carried out at 80 ° C. for 2 hours.

Next, 48 g of 2-hydroxyethyl acrylate was added and the reaction was carried out at the same temperature for 2 hours to obtain the 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 "Bernock DN-901S", 16.8 g of hexamethylene diisocyanate and 150 g of methyl ethyl ketone and stirred uniformly. After that, 100 g of "Plaxel CD210PL" [polycarbonate diol manufactured by Daicel Chemical Industries, Ltd.] was added, and the reaction was carried out at 80 ° C for 2 hours.

Then, 34.8 g of 2-hydroxyethyl acrylate was added, and the reaction was continued for another 2 hours at the same temperature to obtain the desired polycarbonate-modified polyurethane acrylate. Hereinafter, this is a resin (A-2)
Is abbreviated.

Reference Example 3 (same as above) 55.0 g of "Bernock DN-901S" and 150 g of methyl ethyl ketone were charged into a flask equipped with a thermometer, a stirrer and a condenser, and the mixture was stirred uniformly and then "carbodiol C- 70 g of "700" (carbonate diol manufactured by Toagosei Kagaku Kogyo 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 Co.) was added, and the reaction was continued at the same temperature for 2 hours to obtain the desired polycarbonate modified polyurethane acrylate. 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 "Bernock DN-901S", 50 g of isobornyl acrylate, 50 g of carbitol acrylate and 3 of hexamethylene diacrylate were added.
To the 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 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) 1 flask of diphenylmethane diisocyanate (MDI) was placed in a flask equipped with a thermometer, a stirrer and a condenser.
Charge 00 g and 50 g of MEK, raise the temperature to 60 ° C., and stir evenly.
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 reaction was performed 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 "Bernock 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 the reaction was carried out at 80 ° C. for 4 hours while stirring. After that, it was confirmed by infrared spectrum that characteristic absorption of the isocyanate group had disappeared, and a modified photoinitiator containing an acryloyl group as a target photopolymerization initiator was obtained.
Hereinafter, this is abbreviated as compound (B-1).

Reference Example 7 (Same as above) 55 g of "Bernock DN-901S" was placed in a flask.
And bis (2- with a hydroxyl value of 112 mg-KOH / g
Hydroxyethoxypropyl) polydimethylsiloxane (50 g) was added, the reaction was carried out at 80 ° C. for 4 hours while stirring, and then 4- (2-hydroxyethoxy) phenyl-2- (2-hydroxy) propyl ketone. Of a solution of 50% diluted with methyl ethyl ketone
g and 13 g of 2-hydroxypropyl acrylate were added and reacted at 80 ° C. for 4 hours while stirring.

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

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 used.
H / g of 2-dimethylolbutoxypropylmethylpolydimethylsiloxane (224 g) was charged and reacted with stirring at 80 ° C. for 4 hours, then 4-
50% of (2-hydroxyethoxy) phenyl-2- (2-hydroxy) propylketone with methylethylketone
45 g of the diluted solution and 30 g of pentaerythritol triacrylate were added, and the mixture was stirred at 80
The reaction was carried out at 4 ° C for 4 hours.

Then, it was confirmed by infrared spectrum that characteristic absorption of the isocyanate group was lost, and a modified photoinitiator containing an acryloyl group was obtained as a desired 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 used.
Charge 98 g of-(oxiranylmethoxy) propyl] polydimethylsiloxane and 15 g of acrylic acid, and
The reaction was carried out at 00 ° C for 10 hours.

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

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

Hereinafter, this is abbreviated as compound (B-4). Examples 1 to 6 A desired ultraviolet curable coating material was prepared according to the following formulation table.

[0067]

[Table 1]

[0068]

[Table 2]

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

Comparative Example 1 A urethane acrylate compound (A'-1) as a control
3 parts of benzyl dimethyl ketal were added to 100 parts of the above and mixed uniformly.

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 mixed uniformly.

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 that the dry film thickness was about 100 microns (μm). It was applied with a bar coater.

Then, in Examples 1 to 4 and Comparative Examples 1 and 2, predrying was carried out at 80 ° C. for 10 minutes, while in Examples 5 and 6, after the coating was applied, respectively. 80W high pressure mercury lamp
Ultraviolet irradiation with an intensity of 0 microjoule / square centimeter was performed.

Thereafter, each coated plate thus obtained was subjected to a odor immediately after irradiation with ultraviolet rays and, at the same time, a Taber abrasion test was conducted 100 times under a load of 500 g using an abrasion wheel "CS-10F". , Change in haze (ΔHaze) was measured.

Further, the appearance of the coating film was observed by conducting a 50% elongation test on the coating film itself. Further, the cured coating film was subjected to a scratch test with "Osaka Diamond No. 1". The results are collectively shown in Table 2.

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

[0077]

[Table 3] Table 2 Surface Curability Odor ΔHAZE Stretching Test Scratch Test Example 1 1 None 2.8 ○ 700g 2 1 None 3.2 ○ 650g 3 1 None 3.1 ○ 750g 4 1 None 3.3 ○ 600g 5 1 None 3.0 ○ 600g 6 1 None 2.8 ○ 650g 7 1 None 3.6 ○ 600g ──────────────────────────── ──────── Comparative Example 1 5 Yes 15.8 ○ 10g 2 2 Yes 25.4 × 10g ■ ──────────────────────── ───────────

[0078]

[Table 4] Table 3 ΔHAZE extension test Scratch test ■ ────────────────────────────────── Example 1 3.5 ○ 700g 2 4.2 ○ 600g 3 4.3 ○ 700g 4 4.6 ○ 550g 5 3.8 ○ 600g 6 3.5 ○ 600g 7 4.8 ○ 600g ────────── ───────────────────────── COMPARATIVE EXAMPLE 1 ………………. 9 × 10g ■■ ───────────────────────────────────

[0079]

[Footnotes in Tables 2 and 3] Surface hardenability: 15 from a high pressure mercury lamp of 80 w / cm
Ultraviolet rays are radiated at a distance of 10 cm, and the line speed of 10 m / min is displayed to indicate the number of passes that are tack-free. Odor:… from a high pressure mercury lamp of 80 w / cm 15
Irradiate UV rays with a distance of cm, and at a line speed of 10 m / min, the odor of the coating film after one pass,
Displayed as “Yes” or “None” ΔHASE ………… Displays the change in haze before and after the Taber abrasion test as a percentage (%) Extension test ………… 50% extension test coating appearance ( (Visual judgment) is indicated by "○" and "×" ○: No distortion or breakage is observed, and no defects are observed in the coating film. When defects are found Scratch test: Displayed using the allowable load for scratching with "Osaka Diamond No. 1" and the maximum load until scratches, tears, and distortions of the coating film after 24 hours

[0080]

As is clear from the results shown in Tables 2 and 3, the ultraviolet-curable resin composition of the present invention has, inter alia, curability, abrasion resistance, scratch resistance and weather resistance (light resistance). It is known that it gives a coating film excellent in

Claims (11)

[Claims] 1. A compound (a-1) having at least one (meth) acryloyl group and a hydroxyl group in one molecule.
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. An ultraviolet-curable resin composition comprising, as an essential component, a compound (B) having both a group capable of generating a radical by light and a group (B). 2. A compound (a-1) having at least one (meth) acryloyl group and a hydroxyl group in one molecule.
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 that generates a radical by light
And a reactive diluent (C) as essential components, an ultraviolet-curable resin composition. 3. A compound (a) having at least one (meth) acryloyl group and a hydroxyl group in one molecule.
-1), a polycarbonate diol (a-2) having a molecular weight of 300 to 3,000, and a polyisocyanate (a-3) having an isocyanurate structure, 30 to 95 of a resin (A) obtained. Parts, 1 to 20 parts of the compound (B) having both the (meth) acryloyl group and a group that generates a radical by light, and 0 to 70 parts of the reactive diluent (C) are essential components. The ultraviolet curable resin composition according to claim 1, which is contained as. 4. The resin (A) according to claim 1, wherein a compound having an alicyclic ring structure is used as the polycarbonate diol (a-2). The ultraviolet-curable resin composition according to item 1. 5. The resin (A), wherein a compound derived from hexamethylene diisocyanate is used as the polyisocyanate (a-3) having the isocyanurate structure. 7. The ultraviolet curable resin composition according to any one of 1. 6. A compound (B) having both the above-mentioned (meth) acryloyl group and a group which generates a radical by light.
Is 4- (2-acryloyloxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, The ultraviolet curable resin composition according to any one of claims 1 to 3. 7. A compound (B) having the above-mentioned (meth) acryloyl group and a group capable of generating a radical by light,
The ultraviolet curable resin composition according to claim 1, which is a compound derived from 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone. 8. A compound (B) having the above-mentioned (meth) acryloyl group and a group capable of generating a radical by light,
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 above-mentioned (meth) acryloyl group and a group which generates a radical by light,
Of a compound having both a hydroxyl group and a (meth) acryloyl (oxy) group, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, polyisocyanate, and hydroxyalkyl-modified polysiloxane It is obtained by the reaction,
3. The ultraviolet curable resin composition according to any one of 3 above. 10. The above-mentioned reactive diluent (C) is such that 20% or more of the diluent (C) is occupied by a monofunctional (meth) acrylate having an alicyclic structure. Item 2. The ultraviolet curable resin composition according to Item 2 or 3. 11. The reactive diluent (C), wherein as the monofunctional (meth) acrylate having an alicyclic structure, isobornyl (meth) acrylate is particularly used. 11. The ultraviolet curable resin composition according to 10.