JPH03292373A - Resin composition curable with actinic radiation - Google Patents

Abstract

PURPOSE:To reduce the viscosity without impairing the curability, etc., by incorporating a tetra(meth)acrylate of a specific alcohol and a urethane (meth) acrylate having urethane linkages and (meth)acryloyl groups. CONSTITUTION:Pentaerythritol (i) is subjected to addition reaction with ethylene oxide in an amount of 4-10mol, an average, per mole of the component (i) at 160-180 deg.C in the presence of an alkali catalyst, thereby producing an alcohol (a). The component (a) is esterified with (meth)acrylic acid (b) by dehydrating in the presence of a strong acid by azeotropic distillation, thereby producing a tetra(meth)acrylate (A) of an alcohol obtained by the addition of the components (i) and (ii). 5-95wt.% component (A) is mixed with 95-5wt.% urethane (meth)acrylate having 2 or more urethane linkages and 2 or more (meth)acryloyl groups, and if desired, an organic solvent, a photopolymerization initiator, a photosensitizer, a photopromoter, an additive, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to an active energy ray-curable resin composition that has excellent radical polymerizability, low viscosity, and a cured film that has excellent flexibility.

[Prior art and problems to be solved by the invention] Until now, active energy ray-curable resin compositions have been made using urethane (meth), which has excellent curability and excellent abrasion resistance and flexibility of the cured film. Acrylate is known,
The problem is that the viscosity is high, and in order to dilute it to a viscosity that can be applied as a coating resin composition, a large amount of solvent and diluent monomer must be used. Considering the amount of energy required for drying and recovering the solvent, it is preferable to dilute it with a monomer. However, monomers with excellent dilutability generally sacrifice curability.

On the other hand, pentaerythritol tri(meth)acrylate, tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate are known as polyfunctional monomers with excellent curability. but,
Although these have excellent polymerizability, they have a high viscosity as a diluent monomer, so their dilution performance is poor, and the film obtained by polymerization is too hard and has poor flexibility. Even if mixed with urethane (meth), if the viscosity is adjusted to the appropriate level as a paint,
The acrylate content decreases, resulting in loss of wear resistance and flexibility.

The present inventors have found that as a means to solve these problems, by using a specific polyfunctional (meth)acrylate monomer as a diluent, the urethane (meth)acrylate can be cured without impairing its curability, flexibility, etc. The inventors have discovered that the viscosity can be effectively reduced, leading to the present invention.

[Means to solve the problem]

The gist of the present invention is as follows (A) and (B)
An active energy ray-curable resin composition characterized by containing Iff1 min.

(A) Add 1 ethylene oxide to pentaerythritol
5 to 95% by weight of alcohol tetra(meth)acrylate obtained by adding an average of 4 to 10 moles per molecule (B) Contains two or more urethane bonds and two or more (meth)acryloyl groups in one molecule Urethane (meth)acrylate in an amount of 95 to 5% by weight In the present invention, alcohol tetra(meth)acrylate obtained by adding an average of 4 to 10 moles of ethylene oxide per molecule to pentaerythritol is used as component (A). When the number of moles of ethylene oxide added is less than 4 on average, a film with excellent flexibility cannot be obtained, and when it exceeds 10, curability tends to decrease, both of which are not preferred.

Addition of ethylene oxide to pentaerythritol can be performed by a known method.

For example, pentaerythritol 1
If 5 moles of ethylene oxide are added to each mole and reacted for a sufficient period of time, the average number of moles added per molecule will be 5.
You can get alcohol.

Furthermore, alcohol tetra(meth)acrylate obtained by adding ethylene oxide to pentaerythritol can also be produced by a known method. For example, in the presence of a strong acid such as sulfuric acid or para-toluenesulfonic acid, the alcohol and (meth)acrylic acid are dehydrated and esterified by an azeotropic method;
It can be produced by a method such as transesterification with an acrylic acid ester.

As component (B), urethane (meth)acrylate having two or more urethane bonds and two or more (meth)acryloyl groups in one molecule is used. Examples include those to which a meth)acrylate monomer is added.

Various known polyisocyanate compounds can be used, and specific examples include tolylene diisocyanate, ethylene diisocyanate, 1,2-diisocyanatopropane, 1,3-diisocyanatopropane, bis(4 -isocyanatophenyl) °methane, xylylene diisonanate, tetramethylxylylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, bis(4-isocyanatocyclohexyl)methane, methylcyclohexane 2,4-diisocyanate, 1,3-his Polyisocyanate monomers such as (isocyanatoethyl)cyclohexane, isophorone diisonanate, trimethylhexamethylene diisocyanate, tetramethylene neusonanate, dimer acid diisonoanate, 2-isocyanatoethyl 2,6-diitunanatohexanoate, etc. , burettes and trimers thereof, and adducts of these with various polyol compounds.

Specific examples of polyol compounds used in the adduct include:
Examples include, but are not limited to, ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, trimethylolpropane, pentaerythritol,
These include alkyl polyols such as sorbitol, mannitol, and glycerin, polyether polyols of these alkyl polyols, polyester polyols synthesized from the above-mentioned alkyl polyols and polybasic acids, and polyester polyols such as polycaprolactone polyols.

Specific examples of hydroxyl group-containing (meth)acrylate monomers include 2-hydroxyethyl (meth)acrylate, 2
-Hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, 3-bromo-2-hydroxypropyl (meth)acrylate Acrylate, 2-chloro-
Examples include 1-(hydroxymethyl)ethyl (meth)acrylate and 2-bromo-1-(hydroxymethyl)ethyl (meth)acrylate.

In the present invention, urethane (meth)acrylate can be obtained by simultaneously mixing and reacting a polyisocyanate compound, a polyol compound, and a hydroxyl group-containing (meth)acrylate monomer. Another method is to react a polyol compound and a polyisocyanate compound to form a urethane isocyanate intermediate containing one or more isocyanate groups per molecule, and then combine this intermediate with a hydroxyl group-containing (meth)acrylate monomer. A method of reacting a polyisocyanate compound with a hydroxyl group-containing (meth)acrylate monomer to form a urethane (meth)acrylate intermediate containing one or more isocyanate groups per molecule; Examples include a method of reacting with a polyol compound.

The composition of the present invention contains pentaerythritol as component (A) with an average of 4 to 10 ethylene oxide per molecule.
Alcohol tetra(meth)acrylate obtained by molar addition is used in an amount of 5 to 95% by weight, but if it is less than 5% by weight, the viscosity of the composition cannot be sufficiently lowered;
Exceeding this percentage by weight tends to form a film that is too soft and has low strength, which is both undesirable.

The composition of the present invention may contain various reactive oligomer monomers as necessary within a range that does not impair the characteristics of the present invention.

Reactive oligomers are not particularly limited, but examples include polybasic acids such as phthalic acid, adipic acid, and trimellitic acid; polyhydric alcohols such as ethylene glycol, butanediol, trimethylolpropane, and pentaerythritol; Polyester poly (meth)acrylate obtained by reaction with meth)acrylic acid, epoxy poly(meth)acrylate obtained by reaction of epoxy resin with (meth)acrylic acid, etc., and polysiloxane and (meth)acrylic acid compound Examples include polysiloxane poly(meth)acrylate obtained by reacting with polyamide and polyamide poly(meth)acrylate obtained by reacting polyamide with a (meth)acrylic acid compound.

In addition, the monomer is not particularly limited, but for example, (meth)
Methyl acrylate, ethyl (meth)acrylate, (
Propyl meth)acrylate, n-(meth)acrylate
Butyl, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-(meth)acrylate
-nonyl, cyclohexyl (meth)acrylate, (
Benzyl meth)acrylate, Dicyclopentenyl (meth)acrylate, 2-synchropentenoquinethyl (meth)acrylate, Methoxyethyl (meth)acrylate, Ethoxyethyl (meth)acrylate, Butoxy (meth)acrylate Ethyl, methoxyethoxyethyl (meth)acrylate, ethquinethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 2-hydroquinethyl (meth)acrylate,
(Meth)acrylic acid monomers such as 2-hydroxypropyl (meth)acrylate, 4-hydroquinbutyl (meth)acrylate, (meth)acrylic acid, (meth)acryloylmorpholine, N-vinyl-2-pyrrolidone, N
-vinylimidazole, N-vinylcaprolactam, styrene, α-methylstyrene, vinyltoluene, allyl acetate, vinyl acetate, vinyl propionate, vinyl benzoate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, Triallyl cyanurate, triallylysonanurate, triallyl formal 1.3.5-triacryloylhexahydro-S triazine, bisphenol A-
Examples include diglinonol ether di(meth)acrylate, polypropylene glycol di(meth)acrylate, and polyethylene glycol di(meth)acrylate.

The resin composition of the present invention may contain an organic solvent in order to adjust the viscosity to a desired value. Examples of organic solvents include ketone compounds such as acetone, methyl ethyl ketone, and cyclohexanone; ester compounds such as methyl acetate, ethyl acetate, butyl acetate, ethyl lactate, and methoxyethyl acetate; and ether compounds such as diethyl ether, ethylene glycol dimethyl ether, and dioxane. ; Aromatic compounds such as toluene and xylene; Aliphatic compounds such as pentane and hexane; and halogenated hydrocarbons such as methylene chloride, chlorobenzene and chloroform.

Additionally, additives such as lubricants, abrasives, rust preventives, and antistatic agents may be added to the resin composition of the present invention.

Examples of active energy rays used for curing the resin composition of the present invention include ultraviolet rays, electron beams, gamma rays, and the like.

When ultraviolet rays are used as active energy rays, it is usually preferable to include a photocatalytic compound consisting of one or more of a photopolymerization initiator, a photosensitizer, a photoaccelerator, etc. in the composition.

As the photocatalytic compound, any known compound can be used.

Specific examples of the photopolymerization initiator include benzoin monomethyl ether, benzoin isopropyl ether, benzophenone, benzyl dimethyl ketal, 2,2-jethoxyacetophenone, l-hydroxychlorohexyl phenyl ketone, and the like.

Specific examples of the photosensitizer include 2-chlorothioxanthone, 24-diethylthioxanthone, 2°4-diisopropylthioxanthone, and the like.

Specific examples of photoaccelerators include ethyl p-methylaminobenzoate, isoamyl p-dimethylaminobenzoate, and p-dimethylaminobenzoate.
2-n-butquinethyl-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, and the like can be mentioned.

Hereinafter, it will be explained in detail using examples. In addition, in the examples, parts indicate parts by weight.

Production Example 1 In a flask equipped with a stirrer, a condenser, a thermometer, and a dropping funnel, the amounts of polyisocyanate compound shown in Table 1, a diluting monomer, and butyltin in an amount of 0°02% based on the total amount were added. Dilaurate was charged, and while keeping the temperature at 40°C, a mixture of a polyol compound and a hydroxyl group-containing (meth)acrylate was added dropwise in the amount shown in Table 1, and then the temperature was raised to 70°C.
The urethane acrylate (
Bl) was obtained.

Production Example 2 In a flask equipped with a stirrer, a condenser, a thermometer, and a dropping funnel, the amounts of polyisocyanate compounds shown in Table 1, the diluent monomer, and butyltin in an amount of 0°02% based on the total amount were added. While preparing nolaurate and keeping it at 40°C,
The amount of polyol compound shown in Table 1 was added dropwise, the temperature was raised to 50°C, and after 2 hours, a mixture of hydroxyl group-containing (meth)acrylates was added dropwise, the temperature was further raised to 70°C, and the reaction was carried out for a sufficient period of time to form a urethane acrylate. (B-2) was obtained.

Production Example 3 Into a flask equipped with a stirrer, a condenser, a thermometer, and a dropping funnel, the amounts of the polyisocyanate compound shown in Table 1, the diluting monomer, and the amount of dibutyltinnolaurate that is 0.02% based on the total amount were added. After the hydroxyl group-containing (meth)acrylate was added dropwise in the amount shown in Table 1 while keeping the temperature at 40°C, the temperature was raised to 70°C and the reaction was carried out for a sufficient time to obtain urethane acrylate (B-3). .

Examples 1-3. Comparative Examples 1 to 6 Components (A) and (B) and a polymerization initiator in amounts shown in Table 2 were weighed and mixed uniformly to obtain a resin composition for evaluation.

The dilutability of component (A) was evaluated by measuring the viscosity of these compositions at 25°C using a B-type viscometer. To evaluate the curability, these compositions were coated with a bar coater #60 on a tin plate degreased with toluene, and passed through a 20 cm distance under an 80 W/am high-pressure mercury lamp at a speed of 20 m/min. This was done by checking the number of passes until it ran out. The flexibility and strength of the cured film were determined by applying these compositions to a tin plate degreased with toluene using a bar coater #60, and applying the composition under a high pressure mercury lamp of 80 W/am for 2 hours.
The coating was peeled off from an object that had passed through a distance of 0 cm five times at a speed of 10 m/min, a tensile test was conducted on the coating alone, and the elongation at break and maximum strength were evaluated.

The results are shown in Table 2.

(Table 1) TIJXOI ; Tetramethylxylylene diisocyanate PG Hε^ EMA HP^ 2-EH^ NPGO^ : Neobentyl glycol = 2-hydroxyethyl acrylate; 2-hydroxyethyl acrylate: 2-hydroxyethyl acrylate: 2-ethyl Hexyl acrylate, neobentyl glycol diacrylate [Effects of the invention] As explained above, the active energy ray-curable resin composition of the present invention has excellent radical polymerizability, low viscosity,
Moreover, it has the effect that the cured film has excellent flexibility.

Claims (1)

[Scope of Claims] An active energy ray-curable resin composition characterized by containing the following components (A) and (B). (A) Add 1 ethylene oxide to pentaerythritol
5 to 95% by weight of alcohol tetra(meth)acrylate obtained by adding an average of 4 to 10 moles per molecule (B) Contains two or more urethane bonds and two or more (meth)acryloyl groups in one molecule 95-5% by weight of urethane (meth)acrylate