JPH04110303A - Active energy ray-curable resin composition - Google Patents

Abstract

PURPOSE:To significantly improve the surface curability, resistance to surface scratch, odor, surface slipperiness, and chemical resistance of an active energy ray-cured film by compounding a compd. having specific structural units in the molecule as an essential film-forming component into the title compsn. CONSTITUTION:The title compsn. contains, as an essential component, a compd. having a siloxane backbone of formula 1 (wherein R and R' may be the same or different and are each a monovalent org. group; and l is an integer of 1-300) and a group generating a free radical when exposed to light. A compd. having the siloxane backbone, the free radical-generating group, and an alpha,beta-- ethylenically unsatd. double bond or a compd. having the siloxane backbone, the free radical-generating group, the alpha,beta-ethylenically unsatd. double bond, and a urethane bond may be used as the essential component. Pref. the free radical-generating group has a structure of formula II.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a new and useful active energy ray-curable resin composition, which has properties such as surface curability, surface scratch resistance, odor, surface smoothness, and chemical resistance. The object of the present invention is to provide an extremely useful active energy ray-curable resin that has significantly improved properties.

More specifically, the present invention relates to a novel active energy ray-curable resin composition comprising a compound having a specific structural unit in the molecule as an essential film-forming component.

[Conventional technology]

In recent years, this type of active energy ray-curable resin has been used as a variety of surface treatment agents, especially for paints.
It has become widely used.

This is a much faster curing process compared to conventional curing methods.
This is because it has many advantages, such as non-thermal curing and solvent-free curing, saving space on the line, and being energy efficient for curing.

These active energy ray-curable resins include α,
A resin system containing β-ethylenically unsaturated double bonds is used, and polyester (meth)acrylate,
Typical examples include unsaturated polyester, polyether (meth)acrylate, and polyurethane (meth)acrylate.Furthermore, these resin systems can be blended with photoinitiators, photosensitizers, etc. It can also be cured by irradiating it with light such as.

However, conventional active energy ray-curable resins have had the disadvantage of poor surface curability, particularly due to inhibition of polymerization by oxygen in the air.

In other words, the actual situation is that the surface of the cured resin is not easily scratched or leaves a tacky feeling on the surface, which causes problems during use.

For this reason, methods such as adding a large amount of photoinitiator or curing in an atmosphere of an inert gas such as nitrogen have been adopted.

However, if a large amount of photoinitiator is added, there will inevitably be a large amount of unreacted photoinitiator, and molecular growth in the photoradical reaction will not occur as much, resulting in poor solvent resistance and mechanical properties of the cured coating film. This results in adverse effects such as deterioration of performance.

Curing under an atmosphere of an inert gas such as nitrogen or the like requires special equipment, and such a method cannot be said to be a general-purpose method.

Furthermore, adding a photoinitiator or a photosensitizer to the resin has the disadvantage that it generates an odor after curing.

[Problem to be solved by the invention]

In this way, as long as the conventional techniques are followed, no product has been found that has no odor, has excellent hardening properties, has improved surface scratch resistance, and also has excellent solvent resistance. The reality is that it is not.

Therefore, in view of the problems in the prior art described above, the present inventors have particularly focused on surface hardening, surface scratching, odor,
In order to find an extremely useful active energy ray-curable resin that can significantly improve all properties such as surface lubricity and chemical resistance, we have undertaken extensive research.

Therefore, the problem to be solved by the present invention lies in - being able to significantly improve properties such as surface hardening, surface scratch resistance, odor, surface smoothness, and chemical resistance;
An object of the present invention is to provide an extremely useful active energy ray-curable resin.

[Means to solve the problem]

Therefore, the inventors of the present invention set their sights on the above-mentioned invention and the problems to be solved, and as a result of intensive studies, they discovered an active energy ray-curable resin composition that exhibits many of the excellent features described above. By discovering this, we have completed the present invention.

In other words, the present invention comprises, as essential components, a compound having both a siloxane skeleton and a group that generates radicals when exposed to light, or a siloxane skeleton and a group that generates radicals when exposed to light, and an αβ-ethylenic compound. A compound containing an unsaturated double bond, or a siloxane skeleton and a group that generates radicals when exposed to light, α,
If an active energy ray-curable resin composite containing a compound having both a β-ethylenically unsaturated double bond and a urethane bond is used, in other words, to summarize further,
If an active energy ray-curable resin adhesive containing a compound having both a siloxane skeleton and a group that generates radicals when exposed to light as an essential film-forming component is used, the active energy rays will cure the surface, resulting in surface hardening and surface hardening. The present invention was completed by discovering that properties such as scratch resistance, odor, surface smoothness, and chemical resistance can be significantly improved.

Here, the above-mentioned siloxane skeleton has, for example, a repeating unit represented by the general formula %. Therefore, in order to introduce such a siloxane skeleton into a molecule, it is necessary to Some silicon atoms (
A compound having a reactive functional group that directly bonds to Si) is used.

Particularly desirable as R and R' in the above-mentioned formula CI' are monovalent organic groups such as alkyl or allyl groups, with methyl, ethyl or phenyl groups usually being suitable. be.

In addition, the reactive functional groups mentioned here include, for example, the general formula % -NH2, -←CH7te1O-CH2-CH-CH2,
\1 1←CH→2 (a) COC=CH2, -H or -OR
These reactive functional groups are bonded in a pendant manner at terminal sites in the siloxane skeleton or as side chains. (Hereinafter, these are also referred to as siloxanes containing reactive functional groups.) Furthermore, in order to introduce into the molecule the group that generates radicals when exposed to light, the method described in JP-A No. 61-254105 can be used. Co-reactive photopolymerization initiators can be used, but among these compounds having groups that generate radicals when exposed to light, industrially available compounds include Darocure 2959j manufactured by Merck & Co., West Germany. Like, 4-(
A typical example is 2-hydroxyethoxy)-phenyl-2-(2-hydroxy)propyl ketone.

Furthermore, benzophenone derivatives having a reactive group can also be used to introduce a group that generates radicals when exposed to light. Particularly representative are acid, benzophenonetetracarboxylic dianhydride, benzophenonetetracarboxylic acid alkyl ester, and the like.

In addition, by introducing into the resin (A) a functional group having the above-mentioned α,β-ethylenically unsaturated double bond, it is possible to further modify the layer, curability, and physical properties of the coating film. It is possible.

Typical examples of compounds with such functional groups are α
, β-ethylenically unsaturated compounds, and the like.

Among them, (meth)acrylic acid is the best example of α, β-ethylenically unsaturated compounds containing carboxyl groups, but cyclic compounds between (meth)acrylic acid and ε-caprolactone and hydroxyl group-containing (meth) Mention may also be made of acrylates and acid anhydrides, such as ring-opened products such as succinic anhydride, phthalic anhydride, trimellitic anhydride or pyromellitic anhydride.

α, β-ethylenically unsaturated compounds containing hydroxyl groups [hereinafter referred to as
Also called hydroxyl group-containing (meth)acrylate. ], known and commonly used ones can be used; typical examples include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 3-hydroxy Butyl (meth)acrylate, 4-hydroxybutyl (meth)
Examples include acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, pentaerythritol tri(meth)acrylate, or glycidyl methacrylate-(meth)acrylic acid adduct.

Isocyanate group-containing α,β-ethylenically unsaturated compound [hereinafter also referred to as isocyanate group-containing (meth)acrylate. ], to exemplify only the most representative ones, "Calendar MOIJ (2-methacryloyloxyethyl isocyanate manufactured by Showa Denko K.K.)",
Alternatively, the active isocyanate group-containing urethane (meth)acrylate, which is a reaction product of the above-mentioned hydroxyl group-containing (meth)acrylate and a polyisocyanate compound, may be used.

Typical examples of epoxy group-containing α,β-ethylenically unsaturated compounds include glycidyl (meth)acrylate, or carboxyl group-containing (meth)acrylate] and polyglycidyl compounds. Examples include compounds obtained by reaction with.

A compound having both a siloxane skeleton and a radical-generating group can be obtained by directly or indirectly reacting a siloxane containing a reactive functional group and a reactive photoinitiator such as those listed in ``2''. Obtainable.

In this reaction, 1.
Reaction between hydroxyl group and carboxyl group, reaction between incyanate group and amine group, reaction between incyanate group and carboxyl group, reaction between epoxy group and amine, reaction between epoxy group and carboxyl group, reaction between epoxy group and thiol group, etc. There are various types of reactions, such as reactions between hydroxyl groups and silanol groups.

Similarly, meth)acrylate compounds having reactive functional groups can be treated with resins (
A) It can also be introduced inside.

These various types of reactions may, of course, be carried out singly or in combination, and are not subject to any limitations as long as the desired compound can be obtained.

Furthermore, it is possible to impart mechanical properties, particularly toughness, to the cured coating film through the urethanization reaction.

The urethanization reaction referred to here refers to a polycondensation reaction between a hydroxyl group and an isocyanate group, and includes a hydroxyl group-containing siloxane compound, a hydroxyl group-containing photoinitiator compound, and/or a hydroxyl group-containing (meth)acrylate compound or an isocyanate group. Containing (meth)acrylate compounds, etc.
By reacting with a polyisocyanate compound or another hydroxyl group-containing compound (polyol), the desired urethane bond-containing compound can be obtained.

As the polyisocyanate compound used in the present invention, known and commonly used ones can be used, but typical examples include 24-
Tolylene diisocyanate, 2-]5-]6 rotolylene diisocyanate, 13-chiral 1/2-diisocyanate-1-114-xylylene diisocyanate h
, diphenylmethane-44'-diisocyanate, 3
- Diisocyanate compounds with an aromatic ring such as methyl-diphenylmethane diisocyanate-1 or 15-naphthalene diisocyanate; cycloaliphatic diisocyanate compounds such as dicyclohexylmethane diisocyanate or isophorone diisocyanate; or hexamethylene diisocyanate or lysine diisocyanate. Aliphatic diisocyanate compounds such as; or isocyanate compounds obtained by hydrogenating diisocyanate compounds having a dug aromatic ring; for example, hydrogenated xylylene diisocyanate-1- or hydrogenated diphenylmethane-44'-diisocyanate; Biulet-type polyisocyanate compound 2-isocyanatoethyl- obtained by reacting each diisocyanate compound with water
Examples include trifunctional incyanate compounds such as 26-dicyanate hexanoate; and multimers obtained by converting Dobori's diisocyanate compounds into incyanurates.

In addition, as other hydroxyl group-containing compounds (polyols) for earth digging, known and commonly used compounds can be used, but only the most representative ones can be mentioned: ethylene glycol, 13-propylene glycol. , 1,2-propylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol,] .

]10-Decanediol2. 2. 4-1-limethyl=1,3-bentanediol, 3-methyl-1°5-bentanediol, dichloroneopentyl glycol, dibromoneopentyl glycol, hydroxypivalic acid neopentyl glycol ester, cyclohexane dimethylol, 1.4- Cyclohexanediol, trimethylolethane, trimethylolpropane, glycerin,
3-methylpentan-1,3,5-to')ol, pentaerythritol, spiroglycol, trisiflothicane dimethylol or hydrogenated bisphenol A1 or "Nukol PM-8701L, BA-E 4, B
A-EP or BA-PGj [ethylene oxide or propylene oxide adduct to bisphenol manufactured by Nippon Nyukazai ■] or "carbodiol"
[Carbonate diol manufactured by Toagosei Kagaku Kogyo Co., Ltd.], etc.

Further, there are polyester polyols obtained by esterification reactions of these various polyols with various known and commonly used carboxylic acids or their acid anhydrides as listed below.

Particularly representative of such carboxylic acids or their anhydrides are maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, het's acid,
Himic acid, Chlorendic acid, Timer acid, Adipic acid, Succinic acid, Alkenylsuccinic acid, Sepatic acid,
Azelaic acid, 2, 2. 4-trimethyladipic acid, terephthalic acid, 2-sodium sulfoterephthalic acid,
2-Potassium sulfoterephthalic acid, isophthalic acid, 5-sodium sulfoisophthalic acid, 5-potassium sulfoisophthalic acid, di-lower alkyl 5-sodium-sulfoisophthalate (such as -dimethyl or -diethyl), orthophthalic acid, 4 -sulfophthalic acid, 1.10
-Decamethylene dicarboxylic acid, Mucon L-L oxalic acid,
Examples include malonic acid, gluconic acid, trimellitic acid, hexahydrophthalic acid, tetrabromophthalic acid, methylcyclohexenetricarboxylic acid or pyromellitic acid, or acid anhydrides thereof.

In the present invention, there is no restriction at all that other components may be added for the purpose of modifying the layer, workability, storage stability, appearance of the cured product, and various physical properties.

Other components in these forms include reactive diluents, reactive oligomer and polymer solvents, photoinitiators, polymers, polymerization inhibitors, antioxidants, dispersants, surfactants,
Inorganic fillers, inorganic pigments, or organic pigments, etc. can be added.

The above-mentioned reactive diluents, reactive oligomers, and polymers are widely used, ranging from monofunctional to polyfunctional ones, but only the most representative ones will be exemplified. For example, 2-hydroxyethyl (meth)acrylate, 2hydroxypropyl (meth)acrylate, 2ethylhexyl (meth)acrylate, N-
Vinylpyrrolidone, 1-vinylimidazole, isobornyl (meth)acrylate, tetrahydrofurphyryl (meth)acrylate, carpitol (meth)acrylate, phenoxyethyl (meth)acrylate, dicyclopentadiene (meth)acrylate, 1,3-butanedi (meth)acrylate, 1,6-hexanethiol di(meth)acrylate, polyethylene glycol di(meth)acrylate, hydroxypivalic acid ester neopentyl glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate pentaerythritol tri( meth)acrylate, pentaerythritol tetra(meth)acrylate or dipentaerythritol hexa(meth)acrylate, as well as urethane(meth)acrylate, epoxy(meth)acrylate, polyester(meth)acrylate, polyether(meth)acrylate, etc. Acrylates can be used without restrictions such as molecular weight or number of (meth)acrylate functional groups.

In addition, to exemplify only typical solvents, 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, propatool or butanol; aliphatic hydrocarbons such as hexane or heptane, as well as cellosolve acetate, carpitol acetate, dimethylformamide, or tetrahydrofuran.

Furthermore, when curing organic materials using ultraviolet rays as active energy rays, a photo(polymerization) initiator may be used in combination within a range that does not improve unpleasant odors, which is one of the objectives of the present invention. good.

As such a luminous polymerization initiator, any known and commonly used initiator can be used, but some of the most representative ones include acetin, phenones, benzophenone, Michler's ketone, benzyl, benzoin, etc.
These include benzoate, benzoin, benzoin methyl ethers, hensyl dimethyl ketal, α-aziroxime ester, thioxanthone, anthraquinone, and various derivatives thereof.

Furthermore, known and commonly used photo-sensitizers can be used in combination; typical examples of such photo-sensitizers include amines, ureas, sulfur-containing compounds, phosphorus-containing compounds,
Examples include chlorine-containing compounds, nitrogen compounds, and other nitrogen-containing compounds.

In addition, saturated or unsaturated polymers can be used, and among them, particularly representative ones include acrylic resin, polyester resin 1, polyamide resin, epoxy resin, polyurethane resin, and vinyl chloride-vinyl acetate resin. Examples include copolymer resin, polyvinyl butyral resin, cellulose resin 1, and chlorinated polypropylene.

Typical inorganic fillers include barium sulfate, calcium carbonate, talc, mitsuno, barium clay carbonate, gypsum, alumina white, silica, calcium silicate, magnesium carbonate, silica paratercolloidal silica, asbestos powder, aluminum hydroxide, Extender pigments such as zinc stearate; chromates such as yellow, zinc chromate or molybdate orange, ferrocyanides such as deep blue, titanium oxide, zinc white, red iron oxide, iron oxide,
metal oxides such as chromium carbide green, metal sulfides such as cadmium yellow, cadmium red or mercury sulfide, or sulfates such as selenide or lead sulfate;
Silicates such as ultramarine, or carbonates, phosphates such as cobalt violet or manganese violet; or metal powders such as aluminum powder, zinc powder, brass powder, magnesium powder, iron powder, copper powder or nickel powder; Ka=
23- Inorganic pigments such as bomb black; or organic pigments such as ab pigments, copper phthalocyanine pigments such as phthalocyanine blue, phthalocyanine green, or quinacridone pigments.

The energy rays referred to in the present invention include electron beams, alpha rays, and beta rays.
It is a general term for ionizing radiation and light such as rays, gamma rays, X-rays, neutron beams, and ultraviolet rays.

In the present invention, when curing the resin composition using ultraviolet rays as energy rays, the wavelength is 1000 to 80.
00 Onges) - Low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, gallium lamps, metal halide lamps, carbon arc lamps, sunlight, etc., are used to generate ultraviolet rays in air or nitrogen.
All you have to do is irradiate it.

The energetic ray-curable resin phase composition of the present invention thus obtained can be used, for example, as a binder component for paints, adhesives, printing inks, magnetic recording media, etc. .

〔Example〕

Next, the present invention will be explained by reference examples, examples, and comparative examples.
Although the layers will be specifically explained, the present invention is not limited to these examples.

In the following, all parts and percentages are based on weight unless otherwise specified.

Reference Example 1 In a flask, 55 g of Parnock DN-901, SJ [manufactured by Dainippon Ink and Chemicals Co., Ltd., hexamethylene 1/1-converted hexamethylene] and a hydroxyl value of 1.12 KOHmg/g were added. 50 g of bis(2-hydroxyethoxypropyl)point methylsiloxane was reacted with stirring at 8°C for 4 hours, and then 4-di-2hydroxyethoxy)phenyl-2-(
Add 90 g of a 50% methyl ethyl (2-hydroxy)propyl ketone solution and, with stirring, bring the mixture to 8°0
The reaction was carried out for 4 hours at C.

After that, by infrared spectrum analysis (IR analysis),
After confirming that the characteristic absorption of the isocyanate group disappeared, the desired compound (1) containing a siloxane skeleton and a group that generates radicals when exposed to light was obtained.

Reference example 2 In a flask, put 55g of Burnock DN-901SJ.
and 5 of bis(2-hydroxyethoxypropyl)polydimethylsiloxane with a hydroxyl value of 112 KOHmg/g.
0 g was reacted at 80°C for 4 hours with stirring, and then 45 g of a 50% solution of 4-(2-hydroxyethoxy)phenyl-2-(2-hydroxy)propyl ketone in methyl ethyl ketone and 2 - 13 g of hydroxypropyl acrylate and, with stirring, 8
The reaction was carried out at 0°C for 4 hours.

After that, it was confirmed by IR analysis that the characteristic absorption of the isocyanate group had disappeared, and the target compound (2) containing a siloxane skeleton, a group that generates radicals when exposed to light, and an acryloyl group was obtained. Ta.

Reference Example 3 In a flask, 52.4 g of 4.4'-dicyclohexylmethane diisocyanate and a hydroxyl value of 5oKohm
g/g of 2-dimethylolbutoxyfuroylmethylpolydimethylsiloxane with stirring,
The reaction was carried out at 800C for 4 hours, and then 45 g of a 50% solution of 4-(2-hydroxyethoxy)phenyl-2-(2-hydroxy)propyl ketone in methyl ethyl ketone and 30 g of pentaerythritol triacrylate were added and stirred. The reaction was carried out at 80°C for 4 hours.

After that, it was confirmed by IR analysis that the characteristic absorption of the incyanate group had disappeared, and the target compound (3) containing a siloxane skeleton, a group that generates radicals when exposed to light, and an acryloyl group was obtained. Obtained.

Reference Example 4 A flask was charged with 98 g of bis[3-(oxiranylmethoxy)propyl]polydimethylsiloxane containing 49 t) g/mol of epoxy it and 15 g of acrylic acid, and reacted at 100'C for 10 hours. I did it.

Next, 45 g of inphorone diisocyanate was added, and the reaction was carried out at 80'C for 6 hours.

Thereafter, 95 g of a 50% solution of 4-(2-hydroxyethoxy)phenyl-2-(2-hydroxy)furobyl ketone in methyl ethyl ketone was added, and while stirring,
The reaction was carried out at 80°C for 4 hours.

After that, it was confirmed by IR analysis that the characteristic absorption of the isocyanate group had disappeared, and the target compound (4) containing a siloxane skeleton, 1, a group capable of deriving radicals by light, and an acryloyl group was obtained. I got it.

Reference Example 5 In a flask, 98 g of bis[3-(oxiranylmethoxy)furobylcopolydimethylsiloxane with an epoxy equivalent of 490 g/mol and 4(2-hydroxycarbonylmethoxy)phenyl 2-hydroxy-2-propyl ketone were placed in a flask. 47.6g of siloxane and reacted at 100°C for 10 hours. After confirming that the acid value was 0.5KOHmg/g or less, the target siloxane skeleton and radicals were generated by light. Compound (5) containing the group
I got it.

Reference Example 6 (Preparation example of urethane acrylate) In a flask, 100 g of polycaprolactone polyol with a hydroxyl value of 168 KOHmg/g, which is a ring-opening polymer of trimethylolpropane and epsiloncafrolactone, synthesized by a conventional method, and , and 67 g of inphorone diisocyanate were reacted with stirring at 80° C. for 4 hours, then 35 g of hydroxyethyl acrylate was added and reacted with stirring at 80° C. for 4 hours.

Thereafter, it was confirmed by IR analysis that the characteristic absorption of incyanate groups disappeared, and the desired urethane acrylate compound (1) was obtained.

Example 1 50 parts of compound (1) obtained in Reference Example 1 and Reference Example 6
The mixture was mixed with 50 parts of the compound (1) obtained in step 1, and applied onto a glass plate to a thickness of about 1100 d using an applicator.

Next, this was dried for 15 minutes in a dryer at 100°C.

After that, after the coated material had reached room temperature, it was irradiated with an 80W high-pressure mercury lamp, 000 m, 1/
Curing was carried out by irradiating ultraviolet rays so that the thickness was cm2.

Regarding this cured product, odor, coefficient of dynamic friction, scratch test with a diamond needle, and ml solvent property were measured. The results are summarized in Table 1.

Example 2 50 parts of compound (1) obtained in Reference Example 2 and Reference Example 6
The mixture was mixed with 50 parts of compound (1) obtained as above and applied to a glass plate to a thickness of about 100 μm using an applicator.

Next, 1. Drying was carried out in an OO'C dryer for 15 minutes.

However, after the coated material had reached room temperature, it was cured by irradiating it with ultraviolet rays using an 80 W high-pressure mercury lamp at an irradiation dose of 10,100 O/cm2.

Regarding this cured product, odor, coefficient of dynamic friction, scratch test with a diamond needle, and solvent resistance were measured. The results are summarized in Table 1.

Example 3 50 parts of compound (3) obtained in Reference Example 3 and Reference Example 6
The mixture was mixed with 50 parts of the compound (1) obtained in step 1 and applied to a glass plate to a thickness of about 100 μm using an applicator. This was then placed in a dryer at 1
Drying was performed for 5 minutes.

Then, after the coated material had reached room temperature, it was irradiated with an 80 W high-pressure mercury lamp at an irradiation amount of 1000 mj/cm2.
It was cured by irradiating it with ultraviolet rays so that it would become.

Regarding this cured product, odor, coefficient of dynamic friction, scratch test with a diamond needle, and solvent resistance were measured. The results are summarized in Table 1.

Example 4 50 parts of compound (4) obtained in Reference Example 4 and Reference Example 6
50 parts of the compound (1) obtained above were mixed and applied onto a glass plate to a thickness of about 100 μm using an applicator. This was then placed in a dryer at 100°C]5
Drying was performed for minutes.

After that, 1. After the coated material has reached room temperature, use an 80W high-pressure mercury lamp to irradiate it with a dose of 1,000 shoj/cm.
Curing was carried out by irradiating ultraviolet rays so that the temperature was 2.

Regarding this cured product, odor, coefficient of dynamic friction, scratch test with a diamond needle, and solvent resistance were measured. The results are summarized in Table 1.

Example 5 50 parts of compound (5) obtained in Reference Example 5 and Reference Example 6
The mixture was coated with 50 parts of the compound (2) obtained by using an applicator to a thickness of about 100 μm on a glass plate. This was then dried for 5 minutes in a dryer at 100°C.

Thereafter, after the coated material had reached room temperature, it was cured by irradiating ultraviolet rays with an 8 DEG W high-pressure mercury lamp at an irradiation dose of 1000 m, 1/cm2.

The cured product was measured for odor, coefficient of dynamic friction, scratch test with a diamond needle, and solvent resistance.

The results are shown in Table 1.

Comparative Example 1 100 parts of the compound (1) obtained in Reference Example 6 and 3 parts of benzyl dimethyl ketal were mixed and applied onto a glass plate to a thickness of about J○0 μm using an applicator. did. Next, this was dried for 15 minutes in a dryer at 100°C.

Thereafter, after the coated material had reached room temperature, it was cured by irradiating ultraviolet rays with an 80 W high-pressure mercury lamp at an irradiation dose of 10,100 O/cm2.

Regarding this cured product, odor, coefficient of dynamic friction, scratch test with a diamond needle, and solvent resistance were measured. The results are summarized in Table 1.

The outline of the evaluation method for each cured product obtained in each Example and Comparative Example is shown below.

Solvent resistance... Methyl ethyl ketone 5 on the sample surface
One drop of ~20 μm was applied, and after leaving it for 1 hour with a watch over it to prevent evaporation, the surface was wiped and the appearance was visually judged.

Odor: The sample after curing was smelled and determined based on the presence or absence of odor.

Odor dynamic friction coefficient: Osaka Diamond No. 1, load 10g, 100mm
Measurements were made using a diamond needle under the conditions of /sec.

Scratch test: Osaka Dia No. 1, load 20g, 100mm
A scratch test with a diamond needle was conducted under the following conditions: /sec.

Judgment was made based on the presence or absence of scratches after scratching.

〔Effect of the invention〕

As described above, the active energy ray-curable resin composition of the present invention has no odor, and has excellent surface curability, surface scratch resistance, surface smoothness, and chemical resistance. , all of which have been improved.

Agent: Patent Attorney Katsutoshi Takahashi

Claims (1)

[Claims] 1. General formula ▲ Numerical formula, chemical formula, table, etc. ▼... [I] However, R and R' in the formula may be the same or different, respectively. , represents a monovalent organic group, and l is an integer from 1 to 300. An active energy ray-curable resin composition comprising, as an essential component, a compound having both a siloxane skeleton represented by the formula and a group that generates radicals when exposed to light. 2. General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼... [I] However, R and R' in the formula each represent a monovalent organic group, which may be the same or different. It is also assumed that l is an integer from 1 to 300. An active energy ray characterized by containing, as an essential component, a compound having a siloxane skeleton represented by the above, a group that generates radicals when exposed to light, and an α,β-ethylenically unsaturated double bond. Curable resin composition. 3. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ...[I] However, R and R' in the formula each represent a monovalent organic group, which may be the same or different. and l is an integer from 1 to 300. A compound having a siloxane skeleton represented by the above, a group that generates radicals when exposed to light, an α,β-ethylenically unsaturated double bond, and a urethane bond as an essential component,
An active energy ray-curable resin composition comprising: 4. The group according to claim 1, 2 or 3, wherein the group that generates radicals when exposed to light has a structure represented by the formula ▲ Numerical formula, chemical formula, table, etc. ▼...[II] Active energy ray curable resin composition.