JP6876253B2 - Active energy ray-curable resin composition - Google Patents

Description

The present invention relates to an active energy ray-curable resin composition capable of forming a cured film having excellent transparency, surface hardness, and impact resistance by irradiation with an active energy ray such as an electron beam or ultraviolet rays.

Currently, various plastics are used in various fields such as the automobile industry, the home appliance industry, and the electronic / electrical industry because of their advantages such as light weight and low cost in addition to their transparency and workability. In particular, recently, from the viewpoint of light weight and thinness and improvement of safety, plastic substrates have begun to be used as substrates for display devices. A polyethylene terephthalate sheet in which a polymethylmethacrylate or polycarbonate substrate is used for the cover window and a transparent electrode such as ITO is formed on the touch panel is widely used.

Such a plastic substrate is required to have mechanical properties such as surface hardness and impact resistance as well as transparency. In particular, since a plastic material has a drawback that the surface is easily scratched, it is generally made to increase the surface hardness and improve the scratch resistance.

For example, as an active energy ray-curable resin composition having a high surface hardness and improved scratch resistance, Patent Document 1 describes a compound having a (meth) acryloyl group and a hydroxyl group in the molecule, such as pentaerythritol triacrylate. And, an active energy ray-curable resin composition containing a urethane (meth) acrylate reacted with 1,4-cyclohexyldiisocyanate has been proposed.

Further, Patent Document 2 describes urethane (meth) acrylate having one hydroxyl group and two or more (meth) acryloyl groups in one molecule such as pentaerythritol triacrylate and polyisocyanate such as norbornandiisocyanate. An active energy ray-curable resin composition containing a meta) acrylate has been proposed.

Further, Patent Document 3 describes urethane (a urethane obtained by reacting a polyfunctional (meth) acrylate having at least three (meth) acryloyl groups and a hydroxyl group in a molecule such as pentaerythritol triacrylate with a polyisocyanate such as isophorone diisocyanate. A radiation curable composition containing a meta) acrylate has been proposed.

Further, Patent Document 4 proposes an ultraviolet curable acrylate resin composition containing a hexafunctional or higher functional urethane acrylate oligomer and a polyoxyalkylene di (meth) acrylate in a specific ratio.

Japanese Unexamined Patent Publication No. 2002-338628 Japanese Unexamined Patent Publication No. 2006-328364 Japanese Unexamined Patent Publication No. 2009-196375 Japanese Unexamined Patent Publication No. 2016-45349

However, all of the compositions containing urethane (meth) acrylates described in Patent Documents 1 to 3 have a drawback that the crosslink density is improved, the surface hardness is increased, but the composition becomes brittle and the impact resistance is inferior. It was. Further, the resin composition described in Patent Document 4 can obtain a cured product having surface hardness and scratch resistance, but the impact resistance of the cured product made into a thin film is not sufficient.

An object of the present invention is to provide an active energy ray-curable resin composition capable of producing a cured product having various physical characteristics required for a substrate for a display device, specifically, a cured product having excellent transparency, surface hardness, and impact resistance. It is to be.

The present invention contains the following component (A) and component (B), and the mass ratio ((A) / (B)) of the mass of the component (A) to the mass of the component (B) is 1/99 to The present invention relates to an active energy ray-curable resin composition, which is characterized by being 30/70.
Ingredient (A):
Urethane, which is a reaction product of an alkyloxylane derivative (a1) represented by the following formula (1) and satisfying the relationship of the following formula (2) and an isocyanate (a2) containing two or more isocyanate groups in the molecule. Compound

Z- [O- (AO) _n- H] _x ... (1)

(In equation (1),
Z indicates a residue having 1 to 6 carbon atoms and 2 or 3 hydroxyl groups excluding all hydroxyl groups.
x is 2 or 3
AO represents an oxyalkylene group having 3 carbon atoms.
n represents a number of 25 or more and 120 or less. )

_{0.35 ≦ M L / M H ≦} 0.75 ··· (2)

(On a chromatogram in which the length of the perpendicular line from the maximum point K to the baseline B, which maximizes the refractive index intensity on the chromatogram obtained by gel permeation chromatography measurement, is L, and the refractive index intensity is L / 2. Of the two points, the one with the earlier dissolution time is designated as the point O, the one with the slower dissolution time is designated as the point Q, and the intersection of the straight line G connecting the points O and the point Q and the perpendicular line drawn from the maximum point K to the baseline is defined as the intersection. when is P, a distance between the point O and the intersection P and M _H, the distance between the point Q and the point of intersection P and M _L.)

Ingredient (B):
Urethane (meth) acrylate compound having 6 or more and 9 or less ethylenically unsaturated groups

According to the active energy ray-curable resin composition of the present invention, it is possible to provide a cured product having excellent transparency, surface hardness and impact resistance.

A model chromatograph chromatographic diagram for explaining the M _H and M _L.

(Ingredient (A))
The component (A) includes an alkyloxylane derivative (a1) represented by the following formula (1) and satisfying the relationship of the following formula (2), and an isocyanate (a2) containing two or more isocyanate groups in the molecule. It is a urethane compound which is a reaction product of.

Z- [O- (AO) _n- H] _x ... (1)

In the formula (1), Z represents a residue having 1 to 6 carbon atoms and 2 or 3 hydroxyl groups excluding all hydroxyl groups, and x is 2 or 3 . Yes, AO is an oxyalkylene group having 3 carbon atoms. n is the average number of moles of oxyalkylene group AO added, which is 25 or more and 120 or less .

In formula (1), Z is a residue having 1 to 6 carbon atoms and having 2 or 3 hydroxyl groups minus all hydroxyl groups, and x is the number of hydroxyl groups of the Z compound, which is 2 or. It is 3. Examples of the compound having 2 or 3 hydroxyl groups include ethylene glycol, propylene glycol and hexylene glycol when x = 2, glycerin and trimethylolpropane when x = 3. Further, a mixture thereof may be used as the compound having 1 to 6 hydroxyl groups. Most preferably x = 2.

AO is an oxyalkylene group having 3 carbon atoms. Further, n represents the average number of moles of oxyalkylene groups added. Since the improvement of workability is insufficient as n becomes smaller, n is 25 or more, more preferably 40 or more. Further, as n increases, the viscosity increases and handling becomes difficult, so n is 120 or less.

The alkylaxylane derivative (a1) of the present invention is defined by a chromatogram obtained using a differential refractometer in gel permeation chromatography (GPC). This chromatogram is a graph showing the relationship between the refractive index intensity and the elution time. In the alkyloxylan derivative of the present invention, the chromatogram is asymmetrical and satisfies the relationship of the formula (2). The _{closer the ML} / _MH is to 1, the more symmetrical the shape of the chromatogram is.

_{0.35 ≦ M L / M H ≦} 0.75 ··· (2)

Further, in the gel permeation chromatography of the alkyloxylane derivative (a1) shown in the present invention, when there are a plurality of maximum points of the refractive index intensity of the chromatogram, the point having the highest refractive index intensity among them is referred to as the maximum point K. To do. Further, when there are a plurality of maximum points having the same refractive index intensity, the one with the slower elution time is designated as the maximum point K of the refractive index intensity. At this time, peaks caused by the developing solvent used for gel permeation chromatography and pseudo peaks caused by baseline fluctuations caused by the columns and devices used are excluded.

M L _/ M _H is calculated from the chromatogram are as follows.
(1) A perpendicular line is drawn from the maximum point K of the refractive index intensity on the chromatogram to the baseline B, and the length of the perpendicular line is L.
(2) Of the two points on the chromatogram having a refractive index intensity of L / 2, the one with the earlier elution time is designated as point O, and the one with the slower dissolution time is designated as point Q.
(3) Let P be the intersection of the straight line G connecting the points O and Q and the perpendicular line drawn from the maximum point K of the refractive index intensity to the baseline B.
(4) point O and the intersection point P distance _{M H} of the distance of an intersection P and the point Q and _{M L.}

Alkyloxirane derivative represented by the present invention (a1) are those satisfying _{0.35 ≦ M L / M H ≦} 0.75. When M L _/ M _H is greater than 0.75, the molecular weight distribution approaches symmetrically, the effect of the impact resistance is lowered. _Therefore, although the 0.75 or less M L / _{M H,} and more preferably set to 0.62 or less.

Further, when M L _/ M _H is less than 0.35, deviation of the high molecular weight side is increased in the molecular weight distribution, the viscosity becomes high, the handling becomes difficult. _Therefore, although the a _M L / M _H 0.35 or more, and more preferably set to 0.36 or more.

In the present invention, _{gel permeation chromatography (GPC) for determining ML} and _MH is a system dedicated to SHODEX GPC101, a differential refractometer SHODEX RI-71S, a guard column SHODEX KF-GS, and a column SHODEX. Three KF804Ls were continuously attached, tetrahydrofuran was flowed as a developing solvent at a flow rate of 1 ml / min at a column temperature of 40 ° C., and 0.1 ml of a tetrahydrofuran solution of 0.1 parts by mass of the obtained reaction product was injected, and BROWIN GPC calculation was performed. The program is used to obtain chromatograms represented by refractometer intensity and elution time.

When producing the alkyloxylane derivative (a1) shown in the present invention, a propylene oxide having 3 carbon atoms is preferably ring-opened and added in the presence of a composite metal cyanide catalyst (hereinafter abbreviated as DMC catalyst). Let me. In the reaction vessel, a raw material alcohol having at least one hydroxyl group in the molecule and a DMC catalyst are added, and propylene oxide is continuously or intermittently added under stirring in an inert gas atmosphere for addition polymerization. Polyoxypropylene may be added under pressure or may be added under atmospheric pressure.

At this time, the average supply rate of propylene oxide is not limited, but it is desirable to change it depending on the amount of propylene oxide charged. Specifically, the speed between supplying 5 to 20 parts by mass of _{the total supply of propylene oxide is V 1} , and the speed between supplying 20 to 50 parts by mass of the total supply of propylene oxide is V ₂ , propylene. When the speed between supplying 50 to 100 parts by mass of the total amount of oxide supplied is V ₃ , V ₁ / V ₂ = 1.1 to 2.0, V ₂ / V ₃ = 1.1 to 1. It is preferable to control the average supply rate of propylene oxide so as to be 5. The reaction temperature is preferably 50 to 150 ° C, more preferably 70 to 110 ° C. If the reaction temperature is higher than 150 ° C, the catalyst may be deactivated, and if the reaction temperature is lower than 50 ° C, the reaction rate is slow and the productivity is poor.

When producing the alkyloxylane derivative (a1) shown in the present invention, as a raw material alcohol, a compound (Z (OH )) in which Z has 1 to 6 carbon atoms and the number of hydroxyl groups x is 2 or 3 in the formula (1). ) X) or those compounds to which propylene oxide is added can be used. Examples of the raw material alcohol include polyoxypropylene glycol and polyoxypropylene glyceryl ether.

The amount of water contained in the raw material alcohol and propylene oxide is not particularly limited, but the amount of water contained in the raw material alcohol is 0.5 parts by mass or less, and the amount of water contained in propylene oxide is 0.1 part by mass. It is desirable that it is as follows.

The amount of the DMC catalyst used is not particularly limited, but is preferably 0.0001 to 0.1 parts by mass, more preferably 0.001 to 0.05 parts by mass with respect to the alkyloxylane derivative to be produced. The DMC catalyst may be introduced into the reaction system all at once at the beginning, or may be introduced in a sequential manner. After completion of the reaction, the composite metal complex catalyst is removed. The catalyst can be removed by a known method such as filtration, centrifugation, or treatment with a synthetic adsorbent.

A known DMC catalyst can be used as the DMC catalyst used in producing the alkyloxylane derivative (a1) shown in the present invention, and can be represented by, for example, the formula (3).

Ma [M'x (CN) y] b (H ₂ O) c ・ (R) ・ ・ ・ (3)

In formula (3), M and M'are metals, R is an organic ligand, a, b, x and y are positive integers that vary depending on the valence and coordination number of the metal, and c and d are metals. It is a positive integer that changes depending on the coordination number of. Examples of the metal M include Zn (II), Fe (II), Fe (III), Co (II), Ni (II), Al (III), Sr (II), Mn (II), Cr (III), Examples thereof include Cu (II), Sn (II), Pb (II), Mo (IV), Mo (VI), W (IV), W (VI), and Zn (II) is preferably used.

Examples of the metal M'are Fe (II), Fe (III), Co (II), Co (III), Cr (II), Cr (III), Mn (II), Mn (III), Ni (II). , V (IV), V (V) and the like, and among them, Fe (II), Fe (III), Co (II) and Co (III) are preferably used.

As the organic ligand, alcohol, ether, ketone, ester and the like can be used, and alcohol is more preferable. Preferred organic ligands are water-soluble, and specific examples thereof include tert-butyl alcohol, n-butyl alcohol, iso-butyl alcohol, N, N-dimethylacetamide, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and the like. .. Particularly preferably, it is Zn ₃ [Co (CN) ₆ ] ₂ coordinated with tert-butyl alcohol.

The isocyanate (a2) of the present invention is an isocyanate containing at least two or more isocyanate groups in the molecule. Specific examples of the bifunctional isocyanate include aliphatic and alicyclic diisocyanates such as trimethylene diisocyanate, hexamethylene diisocyanate, 1,4-cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, and norbornan diisocyanate, and 1,4-tolylene diisocyanate. , 2,4-Toluene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,5-naphthalenediisocyanate, 4,4'-diphenylmethane diisocyanate and other aromatic diisocyanates.

Specific examples of the trifunctional isocyanate include 1,4-tolylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, and isophorone. Isocyanurate-modified isocyanurate by polycondensing diisocyanate such as diisocyanate and norbornan diisocyanate, adduct-modified diisocyanate, and biuret modified with diisocyanate and trivalent alcohol such as glycerin and trimethylolpropane. The body is mentioned.

Specific examples of the polyfunctional isocyanate containing four or more isocyanate groups include an isocyanate compound obtained by reacting the diisocyanate with a polyol or a polyamine.

The component (A) of the present invention is obtained by a urethanization reaction between an alkyloxylane derivative (a1) and an aliphatic, alicyclic or aromatic isocyanate (a2) containing two or more isocyanate groups in the molecule. It is a urethane compound.

In the urethanization reaction, the ratio of the component (a1) to the component (a2) is such that the isocyanate group in the polyisocyanate (a2) is usually 0.2 to 2 equivalents with respect to 1 equivalent of the hydroxyl group in the component (a1). 0.3 to 1.0 equivalent is preferable, and 0.4 to 0.9 equivalent is more preferable. The reaction temperature is usually 20 to 150 ° C., preferably 30 to 100 ° C., more preferably 40 to 80 ° C. The end point of the reaction ^{can be confirmed by the disappearance of the infrared absorption spectrum of 2270 cm -1} indicating the isocyanate group and the determination of the isocyanate group content by the method described in JIS K 7301.

Further, in the urethanization reaction, a catalyst can be used for the purpose of accelerating the reaction rate. Specific examples of the urethanization catalyst include tin compounds such as dibutyltin dilaurate and dioctyltin dilaurate, and zirconium compounds such as zirconium acetylacetonate and zirconium dibutoxybis (ethylacetacetate). These catalysts can also be used in the urethanization reaction of the present invention.

(Component (B))
The active energy ray-curable resin composition shown in the present invention contains the component (B) as an active ingredient. The component (B) used in the present invention may be a urethane (meth) acrylate having 6 or more and 9 or less ethylenically unsaturated groups.

Urethane (meth) acrylates having 6 or more and 9 or less ethylenically unsaturated groups usually contain polyisocyanate and hydroxyl group-containing (meth) acrylates having 6 or more and 9 or less ethylenically unsaturated groups. , And if necessary, a polyol compound may be reacted.
Examples of the polyisocyanate include aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, modified diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, phenylenedi isocyanate, and naphthalene diisocyanate, pentamethylene diisocyanate, and the like. Hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, lysine triisocyanate and other aliphatic polyisocyanates, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, 1,3-bis (isocyanate methyl) ) An alicyclic polyisocyanate such as cyclohexane, a trimeric compound or a multimer compound of these polyisocyanates, an allophanate type polyisocyanate, a bullet type polyisocyanate, an aqueous dispersion type polyisocyanate and the like can be mentioned.

As the hydroxyl group-containing (meth) acrylate, a hydroxyl group-containing (meth) acrylate containing one hydroxyl group and one or more (meth) acryloyl groups in the molecule is used. For example, hydroxyalkyls such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 6-hydroxyhexyl (meth) acrylate. (Meta) acrylate, 2-hydroxyethylacryloyl phosphate, 2- (meth) acryloyloxyethyl-2-hydroxypropylphthalate, caprolactone-modified 2-hydroxyethyl (meth) acrylate, dipropylene glycol (meth) acrylate, fatty acid-modified- Contains one ethylenically unsaturated group such as glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate. A hydroxyl group-containing (meth) acrylate-based compound; a hydroxyl group-containing (meth) acrylate-based compound containing two ethylenically unsaturated groups such as glycerindi (meth) acrylate and 2-hydroxy-3-acryloyl-oxypropyl methacrylate; penta Erislitol tri (meth) acrylate, caprolactone-modified pentaerythritol tri (meth) acrylate, ethylene oxide-modified pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, caprolactone-modified dipentaerythritol penta (meth) acrylate, ethylene oxide Examples thereof include hydroxyl group-containing (meth) acrylate-based compounds containing three or more ethylenically unsaturated groups such as modified dipentaerythritol penta (meth) acrylate.

Examples of the polyol compound include aliphatic polyols, alicyclic polyols, polyether-based polyols, polyester-based polyols, polycarbonate-based polyols, polyolefin-based polyols, polybutadiene-based polyols, (meth) acrylic-based polyols, and polysiloxane-based polyols. Can be mentioned.

The urethane (meth) acrylate having two or more ethylenically unsaturated groups of the component (B) can be produced by reacting each of the above components by a known reaction means.

Usually, the above-mentioned polyisocyanate, hydroxyl group-containing (meth) acrylate, and polyol compound used as needed can be charged into a reactor collectively or separately and urethanized by a known reaction means to produce a polyol compound. When used, a method of reacting a reaction product obtained by reacting a polyol compound with a polyisocyanate compound in advance with a hydroxyl group-containing (meth) acrylate is a method of producing the urethanization reaction with stability and by-products. It is useful in terms of reducing the amount of

In the above urethanization reaction, a urethane (meth) acrylate having two or more ethylenically unsaturated groups is terminated by terminating the reaction when the residual isocyanate group content of the reaction system becomes 0.5% by weight or less. Is obtained.

Further, in the urethanization reaction, it is preferable to use a catalyst for the purpose of accelerating the reaction, and examples of such a catalyst include dibutyltin dilaurate, dibutyltin diacetate, trimethyltin hydroxide, tetra-n-butyltin, and the like. Organic metal compounds such as bismuth acetonate zinc, zirconium tris (acetyl acetonate) ethyl acetoacetate, zirconite tetraacetyl acetonate, tin octate, zinc hexanoate, zinc octate, zinc stearate, zirconium 2-ethylhexanoate , Metal salts such as cobalt naphthenate, bismuth chloride, bismuth chloride, potassium acetate, triethylamine, triethylenediamine, benzyldiethylamine, 1,4-diazabicyclo [2,2,2] octane, 1,8-diazabicyclo [ 5,4,0] Amin-based catalysts such as undecene, N, N, N', N'-tetramethyl-1,3-butanediamine, N-methylmorpholin, N-ethylmorpholin, bismuth nitrate, bismuth bromide, In addition to bismuth iodide, bismuth sulfide, etc., organic bismuth compounds such as dibutyl bismuth dilaurate and dioctyl bismuth dilaurate, 2-ethylhexanoic acid bismuth salt, naphthenic acid bismuth salt, isodecanic acid bismuth salt, neodecanoic acid bismuth salt, bismuth laurylate, etc. Organic acid bismuth salts such as salt, maleic acid bismuth salt, stearate bismuth salt, oleic acid bismuth salt, linoleic acid bismuth salt, bismuth acetate bismuth salt, bismuth bismuth neodecanoate, disalicylic acid bismuth salt, dicalcified bismuth salt, etc. Bismuth-based catalysts and the like are mentioned, and among them, dibutyltin dilaurate and 1,8-diazabicyclo [5,4,0] undecene are preferable. These can be used alone or in combination of two or more.

In the urethanization reaction, an organic solvent having no functional group that reacts with an isocyanate group, for example, esters such as ethyl acetate and butyl acetate, ketones such as methyl ethyl ketone and methyl isobutyl ketone, and aromatics such as toluene and xylene. Organic solvents such as the same can be used.

The reaction temperature is usually 30 to 90 ° C., preferably 40 to 80 ° C., and the reaction time is usually 2 to 10 hours, preferably 3 to 8 hours.
Two or more types of urethane (meth) acrylates having two or more ethylenically unsaturated groups of the component (B) may be mixed and used.

(Composition ratio)
In the resin composition of the present invention, the mass ratio of the mass of the component (A) to the mass of the component (B) is (A) / (B) = 1/99 to 30/70, preferably 2/98 to 20/70. 80, more preferably 5/99 to 12/88. If the ratio (A) / (B) of the component (A) to the mass of the component (B) is less than 1/99, the impact resistance is lowered. On the other hand, even if the content mass ratio of (A) / (B) exceeds 30/70, there is no further positive effect on the impact resistance effect.

<Photopolymerization initiator>
A photopolymerization initiator may be added to the curable resin composition of the present invention. Examples of the photopolymerization initiator include benzoin or benzoin alkyl ether such as benzoin and benzoin methyl ether; aromatic ketones such as benzophenone and benzoyl benzoic acid; benzyl ketal such as benzyl dimethyl ketal and benzyl diethyl ketal; 1-hydroxycyclohexyl. Acetphenones such as phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propane-1-one; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) Examples thereof include acylphosphine oxides such as phenylphosphine oxides.

<Other ingredients>
Further, in the curable resin composition of the present invention, as optional components, a (meth) acrylic polymer, a surface conditioner, a leveling agent, a filler, a pigment, a silane coupling agent, an antistatic agent, an antifoaming agent, and an antistatic agent are used. A stain, an antioxidant, an ultraviolet absorber, a light stabilizer, a photopolymerization initiator, an organic solvent and the like can be blended.

As a method for curing the curable resin composition of the present invention, a light beam selected from a group of active energy rays such as infrared rays, visible rays, ultraviolet rays, X-rays, γ-rays and electron beams can be selected. As the method of irradiating the active energy rays, a usual method of curing the curable resin composition can be used. When ultraviolet rays are used as the active energy ray irradiation device, electrodeless lamps such as H-valves manufactured by Fusion UV Systems Co., Ltd., low-pressure mercury lamps, high-pressure mercury lamps, and ultra-high-pressure mercury lamps that have a spectral distribution in the wavelength range of 200 to 450 nm. , Xenon lamps, gallium lamps, metal halide lamps and the like. The dose of the active energy rays are usually 10~3,000mJ / cm ² as the accumulated light quantity is preferably ^{50~2,000mJ / cm 2, 100~1,000mJ / cm} 2 is more preferable. The atmosphere at the time of irradiation may be in air, or may be cured in an inert gas such as nitrogen or argon.

(Reference synthesis example: Synthesis of complex metal cyanide complex catalyst)
In an aqueous solution of 2.0ml containing zinc chloride 2.1 g, an aqueous solution of potassium hexacyanocobaltate _K 3 Co _{(CN) 6} and comprises 0.84 g 15 ml, was added dropwise with stirring over 15 minutes at 40 ° C.. After completion of the dropping, 16 ml of water and 16 g of tert-butyl alcohol were added, the temperature was raised to 70 ° C., and the mixture was stirred for 1 hour. After cooling to room temperature, a filtration operation was performed to obtain a solid. To this solid, 14 ml of water and 8.0 g of tert-butyl alcohol were added, and the mixture was stirred for 30 minutes and then filtered to obtain a solid. Further again, 18.6 g of tert-butyl alcohol and 1.2 g of methanol were added to this solid, and the mixture was stirred for 30 minutes and then filtered. The obtained solid was dried at 40 ° C. under reduced pressure for 3 hours to obtain a composite metal. 0.7 g of cyanide complex catalyst was obtained.

(Synthesis Examples 1 and 2: Synthesis of alkyloxylane derivatives (a1-1) and (a1-2))
Molecular weight obtained by reacting propylene oxide with propylene glycol in a stainless steel 5L pressure resistant reactor equipped with a thermometer, pressure gauge, safety valve, nitrogen gas blowing pipe, stirrer, vacuum exhaust pipe, cooling coil, and steam jacket. 200 g of 700 polyoxypropylene glycol and 0.1 g of the composite metal cyanide complex catalyst of the reference synthesis example were charged. After nitrogen substitution, the temperature was raised to 110 ° C., and 145 g of propylene oxide was charged from a nitrogen gas blowing tube under the condition of 0.3 MPa or less over 3 hours. At this time, the changes over time in the pressure and temperature in the reaction vessel were measured.

After 3 hours, the pressure in the reaction vessel decreased sharply. Then, while keeping the inside of the reaction vessel at 110 ° C., propylene oxide was gradually added from the nitrogen gas blowing tube under the condition of 0.6 MPa or less, and 1,230 g of propylene oxide was continuously pressurized and added under stirring. did. At this time, the time until 130 g of propylene oxide was added was 10 minutes, the time until 540 g was added was 55 minutes, and the time until 1230 g was added was 60 minutes.

After completion of the addition, the reaction was carried out at 110 ° C. for 1 hour, then 550 g was withdrawn from the reaction vessel, and while blowing nitrogen gas, the pressure was reduced at 75 to 85 ° C. and 6.7 to 13.3 kPa for 1 hour, and then filtration was performed. A compound (a1-1) represented by the formula (1) was obtained.

Further, the temperature of the residue in the reaction vessel was raised to 110 ° C., and 870 g of propylene oxide was added from a nitrogen gas blowing tube under the condition of 0.6 MPa or less over 80 minutes while keeping the inside of the reaction vessel at 110 ° C. After reacting at 110 ° C. for 1 hour, while blowing nitrogen gas, the compound (a1) represented by the formula (1) was subjected to decompression treatment at 75 to 85 ° C. for 1 hour at 6.7 to 13.3 kPa and then filtered. -2) was obtained.

The obtained reaction product was measured by gel permeation chromatography.
(Measurement of gel permeation chromatography)
For gel permeation chromatography, a system dedicated to SHODEX GPC101, a differential refractometer SHODEX RI-71S, a guard column SHODEX KF-GS, and three HOLDEX KF804L columns were continuously mounted, and the column temperature was 40 ° C. Tetrahydrofuran was flowed at a flow rate of 1 ml / min, 0.1 ml of a 0.1 mass% tetrahydrofuran solution of the obtained reaction product was injected, and a chromatogram represented by a refractive refractometer intensity and an elution time using a BROWIN GPC calculation program. Got _{When ML} / _MH was calculated from this chromatogram, (a1-1) was 0.65 and (a1-2) was 0.60.

(Comparative Synthesis Example 1: Synthesis of Alkyloxylan Derivative (a'1-1))
A stainless steel 5 liter (internal volume 4,890 ml) pressure resistant reactor equipped with a thermometer, pressure gauge, safety valve, nitrogen gas blow pipe, stirrer, vacuum exhaust pipe, cooling coil, and steam jacket, with 84 g of propylene glycol and water. 10.8 g of potassium oxide was charged. React 2588 g of propylene oxide at 100 ° C. to remove residual propylene oxide under reduced pressure at 0 ° C. for 30 minutes, transfer the reaction to a 5 L eggplant flask, quickly neutralize with 1N hydrochloric acid, and under a nitrogen gas atmosphere. After dehydration, filtration was performed to obtain compound (a'1-1).

The obtained reaction product (a'1-1) was measured by gel permeation chromatography. As a result, M
_L / _MH was 1.25.

(Synthesis Example 3: Synthesis of Urethane Compound (A-1))
A flask equipped with a stirrer, a gas introduction pipe, a cooling pipe and a thermometer was charged with 326 g of (a1-1) and 0.05 g of dibutyltin dilaurate, and the temperature was raised to 40 ° C. Next, as (a2), 6.8 g of hexamethylene diisocyanate (Duranate 50M-HDI: manufactured by Asahi Kasei Chemicals Co., Ltd., hereinafter referred to as “HDI”) was added dropwise over 2 hours while paying attention to heat generation. At this time, the isocyanate group of HDI is 0.5 equivalent to 1 equivalent of the hydroxyl group of (a1-1). After completion of the dropping, the reaction was carried out at 60 ° C. for 2 hours until the isocyanate group content was 0.1% or less by the method described in JIS K7301 to obtain a urethane compound (A-1).

(Synthesis Example 4: Synthesis of Urethane Compound (A-2))
324 g of (a1-2) and 0.05 g of dibutyltin dilaurate were placed in a flask equipped with a stirrer, a gas introduction pipe, a cooling pipe and a thermometer, and the temperature was raised to 40 ° C. Next, 4.6 g of isophorone diisocyanate as (a2) was added dropwise over 2 hours, paying attention to heat generation. At this time, the isocyanate group of isophorone diisocyanate is 0.5 equivalent to 1 equivalent of the hydroxyl group of (a1-2). After completion of the dropping, the reaction was carried out at 60 ° C. for 2 hours until the isocyanate group content was 0.1% or less by the method described in JIS K7301 to obtain a urethane compound (A-2).

(Synthesis Example 5: Synthesis of Urethane Compound (A'-1))
A flask equipped with a stirrer, a gas introduction pipe, a cooling pipe and a thermometer was charged with 319 g of (a'1-1) and 0.05 g of dibutyltin dilaurate, and the temperature was raised to 40 ° C. Next, as (a2), 13.4 g of HDI was added dropwise over 2 hours, paying attention to heat generation. At this time, the isocyanate group of HDI is 0.5 equivalent to 1 equivalent of the hydroxyl group of (a'1-1). After completion of the dropping, the reaction was carried out at 60 ° C. for 2 hours until the isocyanate group content was 0.1% or less by the method described in JIS K7301 to obtain a urethane compound (A'-1).

(Synthesis Example 6; Synthesis of Urethane (Meta) Acrylate (B-1))
A mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (Viscoat 300 manufactured by Osaka Organic Chemical Industry Co., Ltd., hydroxyl value: 130 mgKOH / g, pentaerythritol) in a flask equipped with a stirrer, a gas introduction tube, a cooling tube and a thermometer. 258 g of triacrylate / pentaerythritol tetraacrylate = 70/30 (mass%), 0.05 g of hydroquinone monomethyl ether, and 0.05 g of dibutyltin dilaurate were charged, and the temperature was raised to 40 ° C. while blowing air. Next, 50.5 g of HDI was added dropwise over 2 hours, paying attention to heat generation. After completion of the dropping, the reaction was carried out at 60 ° C. for 2 hours until the isocyanate group content was 0.1% or less by the method described in JIS K7301 to obtain a hexafunctional urethane acrylate (B-1) (number average molecular weight). A 765) / pentaerythritol tetraacrylate mixture (75/25 by mass ratio mixture) was obtained.

<Synthesis Example 7; Synthesis of Urethane (Meta) Acrylate (B-2)>
A mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (Viscoat 300 manufactured by Osaka Organic Chemical Industry Co., Ltd., hydroxyl value: 130 mgKOH / g, pentaerythritol) in a flask equipped with a stirrer, a gas introduction tube, a cooling tube and a thermometer. 221 g of triacrylate / pentaerythritol tetraacrylate = 70/30 (mass%), 0.05 g of hydroquinone monomethyl ether, and 0.05 g of dibutyltin dilaurate were charged, and the temperature was raised to 40 ° C. while blowing air. Next, 87.3 g of a modified isocyanurate of hexamethylene diisocyanate (Duranate TPA-100: manufactured by Asahi Kasei Chemicals Co., Ltd.) was added dropwise over 2 hours while paying attention to heat generation. After completion of the dropping, the reaction was carried out at 60 ° C. for 2 hours until the isocyanate group content was 0.1% or less by the method described in JIS K7301 to obtain a 9-functional urethane acrylate (B-2) (number average molecular weight). 1398) / pentaerythritol tetraacrylate mixture (mixture of 78/22 by mass ratio) was obtained.

<Example 1>
1.0 g of the urethane compound (A-1) obtained in Synthesis Example 3 is weighed into a 30 ml brown screw tube, and 9.0 g of urethane (meth) acrylate (B-1) is added to the mixture of Synthesis Example 6. As a photopolymerization initiator, 0.3 g of 1-hydroxycyclohexylphenyl-ton (Irgacure 184 manufactured by BASF) was weighed. This was mixed with a vortex mixer for 1 minute to obtain an active energy ray-curable resin composition. The obtained active energy ray-curable resin composition is coated on a predetermined substrate so that the dry film thickness is 25 μm, and an integrated light amount of 500 mJ / using an 80 W / cm electrodeless UV lamp (H valve). A cured product test piece was obtained by irradiating with an energy amount of ^{cm 2.} The following evaluation was performed using this cured product test piece.

<Transparency>
For a cured film test piece using a polycarbonate plate (manufactured by Nippon Test Panel Co., Ltd., thickness 1 mm, 70 x 150 mm) as a base material, the total light transmittance (%) is set according to the following criteria in accordance with JIS K7361. evaluated.

Total light transmittance is 92% or more (evaluation: ◎)
Total light transmittance is 90% or more (evaluation: ○)
Total light transmittance is less than 90% (evaluation: ×)

<Surface hardness>
A hardened film test piece using a polycarbonate plate (manufactured by Nippon Test Panel Co., Ltd., thickness 1 mm, 70 x 150 mm) as a base material has a scratch hardness (pencil method) under the condition of a load of 750 g in accordance with JIS K5600. It was measured and evaluated according to the following criteria.


Pencil hardness is 2H or more (evaluation: ◎)

Pencil hardness is F to H (evaluation: ○)

Pencil hardness is 2B or less (evaluation: ×)

<Impact resistance>
For a cured film test piece using a glass plate (manufactured by Matsunami Glass Co., Ltd., thickness 1 mm, 40 × 75 mm) as a base material, a steel ball (diameter 16 mm, weight 16 g) was dropped under the conditions of 25 ° C. and 60 RH%. The maximum height at which there was no trace on the surface of the cured film and the glass substrate was not cracked was determined according to the following criteria.


⊚: The maximum height is 45 cm or more.

◯: The maximum height is 35 to 44 cm.
X: The maximum height is 34 cm or less.

<Examples 2 and 3, Comparative Examples 1 and 2>
An active energy ray-curable resin composition was prepared with the compounding ratios shown in Table 3, and the same evaluation as in Example 1 was performed. The evaluation results are shown in Table 3.

From the evaluation results in Table 3, the cured product of the active energy ray-curable resin composition of Examples 1 to 3 according to the present invention is excellent in transparency, surface hardness, and impact resistance.

As shown in Comparative Example 1 of Table 3, it does not contain the component (A) and is excellent in transparency and surface hardness, but inferior in impact resistance. _{Further, as in Comparative Example 2, the ML} / _MH calculated from the GPC chart of the component (A) is out of the scope of the present invention, resulting in inferior impact resistance.

Claims (1)

It contains the following component (A) and component (B), and the mass ratio ((A) / (B)) of the mass of the component (A) to the mass of the component (B) is 1/99 to 30/70. An active energy ray-curable resin composition characterized by being present.

Ingredient (A):
Urethane, which is a reaction product of an alkyloxylane derivative (a1) represented by the following formula (1) and satisfying the relationship of the following formula (2) and an isocyanate (a2) containing two or more isocyanate groups in the molecule. Compound

Z- [O- (AO) _n- H] _x ... (1)

(In equation (1),
Z indicates a residue having 1 to 6 carbon atoms and 2 or 3 hydroxyl groups excluding all hydroxyl groups.
x is 2 or 3
AO represents an oxyalkylene group having 3 carbon atoms.
n represents a number of 25 or more and 120 or less. )

_{0.35 ≦ M L / M H ≦} 0.75 ··· (2)

(On a chromatogram in which the length of the perpendicular line from the maximum point K to the baseline B, which maximizes the refractive index intensity on the chromatogram obtained by gel permeation chromatography measurement, is L, and the refractive index intensity is L / 2. Of the two points, the one with the earlier dissolution time is designated as the point O, the one with the slower dissolution time is designated as the point Q, and the intersection of the straight line G connecting the points O and the point Q and the perpendicular line drawn from the maximum point K to the baseline is defined as the intersection. when is P, a distance between the point O and the intersection P and M _H, the distance between the point Q and the point of intersection P and M _L.)

Ingredient (B):
Urethane (meth) acrylate compound having 6 or more and 9 or less ethylenically unsaturated groups

Images