JP2006057025A - Active energy ray-curable urethane (meth)acrylate composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an active energy ray-curable urethane (meth)acrylate having low viscosity and excellent storage stability and giving a cured product having excellent light resistance, transparency and colorlessness in contrast with a urethane (meth)acrylate produced by using conventional urethanization catalyst having developed color and poor storage stability and giving a cured product having poor light resistance, etc. <P>SOLUTION: The active energy ray-curable urethane (meth)acrylate composition is composed of (A) a urethane (meth)acrylate and (B) an organic bismuth compound. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

The present invention relates to a urethane (meth) acrylate composition. More specifically, the present invention relates to a urethane (meth) acrylate composition that gives a cured product having a relatively low viscosity, excellent storage stability, and excellent light resistance, transparency, and non-colorability.

Conventionally, urethane (meth) acrylate is cured by radiation, and the resulting cured product has excellent elasticity. Therefore, optical members (plastic lenses, prisms, optical fibers, etc.), electrical / electronic members (solder resist for flexible printed wiring boards) , Plating resist, interlayer insulation film for multilayer printed wiring boards, photosensitive optical waveguides, etc.), widely used as coating agents for sealing materials, adhesives, paper, plastics, etc. (see, for example, Patent Documents 1 and 2)
. Since the urethane (meth) acrylate has a reactive (meth) acrylate group, there is a problem that polymerization occurs due to heat or the like during synthesis, and it is necessary to lower the reaction temperature and shorten the reaction time. Therefore, in the production of urethane (meth) acrylate, urethanization catalysts such as organotin compounds, organotitanium compounds, amines, and quaternary ammonium salts are usually used.

Japanese Unexamined Patent Publication No. 07-330858 Japanese Patent Laid-Open No. 11-12340

However, in these catalysts, the reaction between the isocyanate and the water in the system proceeds, so that urea is generated and the molecular weight increases, so that the viscosity increases and the viscosity changes depending on the water content in the system. is there. In addition, since organotin compounds (such as tributyltin) are regarded as environmental hormones, there is a demand for changes to other catalysts. The organic titanium compound not only has a slow urethanation reaction rate, but also has a colored urethane (meth) acrylate,
In addition, the cured product has the disadvantage of poor light resistance. Similarly to amine and quaternary ammonium salts, in addition to coloring of urethane (meth) acrylate and deterioration of light resistance of the cured product, urethane (
There is a problem that the storage stability of the (meth) acrylate is poor.
An object of the present invention is to provide an active energy ray-curable urethane (meth) acrylate composition having a relatively low viscosity and excellent storage stability, and a cured product excellent in light resistance, transparency and non-colorability. .

The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems. That is, the present invention is an active energy ray-curable urethane (meth) acrylate composition comprising a urethane (meth) acrylate (A) and an organic bismuth compound (B); a cured product obtained by curing the composition And a method for producing a cured product, wherein the composition is applied to at least a part of at least one surface of a substrate and cured by irradiation with active energy rays.

The urethane (meth) acrylate composition of the present invention has the following effects.
(1) Relatively low viscosity and excellent storage stability.
(2) A cured product obtained by curing the composition is excellent in light resistance, transparency and non-coloring property.

The active energy ray-curable urethane (meth) acrylate composition of the present invention is urethane (
It consists of a (meth) acrylate (A) and an organic bismuth compound (B).
(A) is formed from a polyol component (a) and a polyisocyanate component (b), and (B)
Is used in that case. Before using (B), (a) and (b) are reacted in advance (
a) and / or (b) a method of containing, (a), (b) and (B) are used in a batch, and (a) and (b) are partially reacted. After the rest (
A method of adding and using (B) with a) and / or (b) is included.
Among the compositions of the present invention, it is preferable that (A) is a urethane (meta) formed from a polyol component (a) comprising a compound (a1) having a hydroxyl group and a (meth) acryloyl group and a polyisocyanate component (b). ) A composition that is an acrylate.

Examples of (a1) include the following.
(A11) alkylene oxide of (meth) acrylic acid [carbon number (hereinafter abbreviated as C) 2-4
), Hereinafter abbreviated as AO] adduct (meth) acrylic acid-2-hydroxyethyl, -2-hydroxypropyl, -2-hydroxybutyl and these AO adducts [molecular weight 160 to number average molecular weight [hereinafter abbreviated as Mn, The measurement is based on a gel permeation chromatography (GPC) method. ] 5,000]
Ε-caprolactone adduct of (a12) and (a11) etc. (molecular weight 230 to Mn5,000)
(Meth) acrylic acid-2-hydroxyethyl-ε-caprolactone 2-mole adduct, etc. (a13) (Meth) acrylic acid ester diol of diol (Mn300 to 5,000) [Mn300 to 5,000, which will be described later (a16) Other than the polyols constituting the above, for example, polycarbonate diol, polytetraethylene glycol, polyester diol] mono (meth) acrylate (a14) epoxide and (meth) acrylic acid reaction product 3-phenoxy-2-hydroxypropyl (meta Acrylate, 3-biphenoxy
2-hydroxypropyl (meth) acrylate and the like (a15) (meth) acrylic acid and a tri- or higher functional polyol (molecular weight 92 to Mn5,000)
) Reaction products of glycerol mono- and di (meth) acrylate, trimethylolpropane mono- and di (meth) acrylate, pentaerythritol mono-, di- and tri (meth) acrylate, ditrimethylolpropane mono-, di- and (A16) (meth) acrylic acid such as tri (meth) acrylate, dipentaerythritol mono-, di-, tri-, tetra- and penta (meth) acrylate and their AO adducts (addition mole number 1 to 100) Reaction product with at least one polyol (Mn 300 to 5,000) selected from the group consisting of butadiene polyol, isoprene polyol, hydrogenated butadiene polyol and hydrogenated isoprene polyol. Of these, reactivity with (b) described later From the viewpoint of (a14) , And more preferred is (a11) and (a15).

Polyisocyanate (hereinafter sometimes abbreviated as PI) component (b) in the present invention
As, for example, the following are included, and a mixture of two or more thereof.
(B1) C (excluding C in the NCO group, the same shall apply hereinafter) 6 to 20 aromatic polyisocyanate diisocyanate (hereinafter abbreviated as DI), such as 1,3- and / or 1,4-phenylene DI, 2, 4- and / or 2,6-tolylene DI (TDI), 4, 4'- and / or 2,4'-diphenylmethane DI (MDI), m- and p-isocyanatophenylsulfonyl isocyanate, 4,4'- Diisocyanatobiphenyl, 3,3'-
Dimethyl-4,4′-diisocyanatobiphenyl, 3,3′-dimethyl-4,4′-diisocyanatodiphenylmethane, 1,5-naphthylene DI, and m- and p-isocyanatophenylsulfonyl isocyanate; and Trifunctional or higher-functional PI (such as triisocyanate), such as crude TDI, crude MDI (polymethylene polyphenylene polyisocyanate) and 4,4 ′, 4 ″ -triphenylmethane triisocyanate

(B2) C2-18 aliphatic polyisocyanate DI, such as ethylene DI, tetramethylene DI, hexamethylene DI (HDI), heptamethylene DI, octamethylene DI, nonamethylene DI, decamethylene DI, dodecamethylene DI, 2,2, 4- and / or 2,4,4-trimethylhexamethylene D
I, lysine DI, 2,6-diisocyanatomethylcaproate, 2,6-diisocyanatoethylcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate and trimethylhexamethylene Diisocyanate (TMDI
And tri- or higher functional PI (such as triisocyanate), such as 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate and lysine ester Triisocyanates (phosgenates of the reaction product of lysine and alkanolamine, such as 2-isocyanatoethyl-2,6-diisocyanatohexanoate, 2- and / or 3-isocyanatopropyl-2,6-diisocyanate Natohexanoate)

(B3) C4-45 cycloaliphatic polyisocyanates DI, such as isophorone DI (IPDI), 2,4- and / or 2,6-methylcyclohexane DI (hydrogenated TDI), dicyclohexylmethane-4,4′-DI (Hydrogenated MD
I), cyclohexylene DI, methylcyclohexylene DI, bis (2-isocyanatoethyl) -4-cyclohexylene-1,2-dicarboxylate and 2,5- and / or 2,6-norbornane DI, dimer acid DI (DDI); and a trifunctional or higher functional PI (
Triisocyanates and the like), for example bicycloheptane triisocyanate (b4) C8-15 araliphatic polyisocyanates m- and / or p-xylylene DI (XDI), diethylbenzene DI and α,
α, α ', α'-Tetramethylxylylene DI (TMXDI)
(B5) Nurateated products of (b1) to (b4) Among these, preferred from the viewpoint of light resistance are (b2) and (b3), and (b5)
Among them, it is a urelate of aliphatic PI.

The polyol component (a) in the present invention further includes polyols (a13), (a15) and (a16) included in the polyol (a2) [(a2) from the viewpoint of toughness of the cured product. ] May be included.
(A2) includes dihydric alcohol (C2-20 or higher), for example, C2-12 aliphatic dihydric alcohol [(di) alkylene glycol (ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1, 2 -, 2,3-, 1,
3- and 1,4-butanediol, 1,6-hexanediol, neopentyl glycol and 3-methylpentanediol (hereinafter referred to as EG, DEG, PG, DPG, BD, respectively)
, HD, NPG and MPD), dodecanediol, etc.]], dihydric alcohols having C6-10 alicyclic skeleton [1,3- and 1,4-cyclohexanediol, cyclohexanedimethanol, etc.], C8 ~ 20 araliphatic dihydric alcohols [xylylene glycol, bis (hydroxyethyl) benzene, etc.];
Trihydric to octahydric or higher polyhydric alcohols such as (cyclo) alkane polyols and their intramolecular or intermolecular dehydrates [glycerin, trimethylolpropane, pentaerythritol, sorbitol and dipentaerythritol (hereinafter, respectively) GR
, TMP, PE, SO and DPE), 1,2,6-hexanetriol, erythritol, cyclohexanetriol, mannitol, xylitol, sorbitan, diglycerin and other polyglycerins, etc.], sugars and their derivatives [sucrose, glucose ,
Fructose, mannose, lactose, glucoside (methyl glucoside, etc.)];
Polyether polyol [the above-mentioned dihydric alcohol, or AO adduct of trihydric to octahydric or higher polyhydric alcohol (molecular weight 150 to Mn 20,000), polytetramethylene glycol (Mn 400 to 10,000), etc.], polyester Polyol (Mn200-2)
0.00), Mn200-10,000, polycaprolactone, polycarbonate,
Polybutadiene, hydrogenated polybutadiene, polyisoprene polyol and hydrogenated polyisoprene polyol, and AO1 to 300 mol adducts of these polyester polyols, polycaprolactone, polycarbonate, polybutadiene, hydrogenated polybutadiene, polyisoprene polyol and hydrogenated polyisoprene polyol. included.

Of these, polyether polyol, polyester polyol, hydrogenated polybutadiene polyol, and polyisoprene polyol are preferable from the viewpoint of light resistance, and polyether polyol and polyester polyol are more preferable.

In the production of urethane (meth) acrylate (A) by urethanization reaction, the equivalent ratio of isocyanate group to hydroxyl group is not particularly limited, but preferably 1 from the viewpoint of storage stability.
: 10 to 10: 1, more preferably 1: 5 to 2: 1, particularly preferably 1: 4 to 1: 1.
It is.

The organic bismuth compound (B) includes the following.
(B1) Organic bismuth carboxylate represented by the general formula Bi (OCOR) ₃ , wherein R is a monovalent aliphatic group [C1-20, such as alkyl (methyl, ethyl, n- and i-propyl, n-, i-, sec- and t
-Butyl, octyl, 2-ethylhexyl, decyl and dodecyl) and alkenyl (1-, 2- and i-propenyl, 1-, 2- and 3-butenyl) groups], aromatic (aliphatic) (C6-20, Examples include phenyl, toluyl, xylenyl, benzyl, phenethyl and hexylphenyl) groups and alicyclic (C3-10, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cyclooctyl) groups.
Among these R, a C2-12 aliphatic group and a C5-10 alicyclic group are preferable from the viewpoint of hydrolysis resistance.

(B2) Organic bismuth alkoxide The organic bismuth alkoxide is represented by the general formula Bi (OR) ₃ , R is the same as above, and R which is preferable from the viewpoint of hydrolysis resistance is the same as above.

(B3) Compound having dicarbonyl group and Bi chelate compound The compound having dicarbonyl group includes C4-15, for example, acetylacetone, acetylacetic acid, acetoacetoxyethyl (meth) acrylate, and the chelate compound includes these Bi chelate compounds are included.

Of these (B), (B1) and (B3) are preferable from the viewpoint of the reaction rate and the stability of (B) as a catalyst, and (B1) is more preferable from the viewpoint of coloring.

The amount of (B) used is preferably from the viewpoint of reactivity and transparency based on the weight of (A), and is preferably 0.00.
001 to 0.5%, more preferably 0.05 to 0.2%.

You may make the composition of this invention contain the catalyst used for urethanation reaction other than (B) in the range which does not inhibit the effect of this invention. Such other urethanization catalysts include organotin compounds, organotitanium compounds, tertiary amines and quaternary ammonium salts.
Examples of organotin compounds include trimethyltin laurate, trimethyltin hydroxide, dimethyltin dilaurate, dibutyltin diacetate, dibutyltin dilaurate,
Stanous octoate and dibutyltin maleate are listed.
Examples of the organic titanium compound include tetraalkyl (C = 2 to 12) titanate and alkylene dicarboxylic acid (C = 2 to 12) titanium.
As the tertiary amine, triethylenediamine, tetraalkyl (C = 1-3) alkylene (C = 2-6) diamine (for example, tetramethylethylenediamine, tetramethylhexylenediamine), diazabicycloalkenes {for example, 1, 8-diazabicyclo [5,4
, 0] Undecene-7 [DBU [manufactured by Sun Apro Co., Ltd., registered trademark]]}.
Examples of the quaternary ammonium salt include tetraalkyl (C = 1-4) ammonium bromide and tetraalkyl (C = 1-4) ammonium perchlorate.
The amount of the other urethanization catalyst used is usually 1% or less, preferably 0.0001 to 0.1% based on the weight of (A).

The composition of the present invention may further contain an organic acid (c) from the viewpoint of the stability of (B). Examples of (c) include aliphatic carboxylic acids (C2 to C20 such as acetic acid, propionic acid, isopropionic acid, butanoic acid, isovaric acid, octanoic acid, 2-ethylhexanoic acid and dodecanoic acid), and alicyclic carboxylic acids. (C4-10, such as cyclobutanecarboxylic acid, cyclopentanecarboxylic acid and cyclohexanecarboxylic acid), aromatic carboxylic acid (C7-
20, eg benzoic acid, terephthalic acid, phthalic acid and trimellitic acid), α-unsaturated carboxylic acids [C3-10, eg (meth) acrylic acid, cinnamic acid and maleic acid] and 2
Examples include monoesterified products of hydroxyethyl (meth) acrylate and polybasic acids (C2-15, such as oxalic acid, succinic acid, adipic acid, phthalic acid, trimellitic acid and acid anhydrides thereof).
Of these, aliphatic carboxylic acid and alicyclic carboxylic acid are preferable from the viewpoint of hydrolysis resistance, and preferable from the viewpoint of reactivity between (c) and urethane (meth) acrylate (A) at the time of active energy ray irradiation. Is a monoesterified product of (meth) acrylic acid and 2-hydroxyethyl (meth) acrylate and a polybasic acid.

The amount of (c) used is usually 20% or less based on the weight of (A), preferably 0.005 from the viewpoint of the stability of (B) and the other urethanization catalyst and the transparency of the cured product described below.
1 to 10%, more preferably 0.05 to 5%.

The weight ratio of (B) to (c) is preferably 0.001 / 1 to 9 from the viewpoint of the stability of (B).
/ 1, more preferably 0.01 / 1 to 4/1.

The conditions for the urethanization reaction of (a) and (b) are not particularly limited. For example, (a) and (b)
From the viewpoint of reactivity and stability of the mixture, preferably 6 to 100 ° C.
(A) can be manufactured by making it react at 0-95 degreeC for 2 to 20 hours. Further, if necessary, the reaction may be carried out by diluting with a solvent (ethyl acetate, methyl ethyl ketone, toluene, etc.). The amount of the solvent used is usually 5,000% or less based on the total weight of (a) and (b). The upper limit is preferably 1,000% from the viewpoint of the reaction rate, and the handling of the mixture of (a) and (b) From the viewpoint of properties, the preferred lower limit is 10%.

The urethanization reaction can be carried out at normal pressure, reduced pressure or increased pressure. The progress of the urethanization reaction can be judged, for example, by measuring the NCO% and hydroxyl value of the reaction system.

The composition of the present invention may further contain (meth) acrylate (X) other than (A). (X) includes the following, which may be used alone or in combination of two or more.

(1) Mono (meth) acrylate (1-1) C1-30 aliphatic monohydric alcohol (meth) acrylate Lauryl (meth) acrylate, stearyl (meth) acrylate, etc. (1-2) C1-30 aliphatic (Meth) acrylate of monohydric alcohol AO 1-30 mol adduct (meth) of lauryl alcohol ethylene oxide (hereinafter abbreviated as EO) 2 mol adduct (meth)
Acrylate, propylene oxide of lauryl alcohol (hereinafter abbreviated as PO) 3 mol adduct (meth) acrylate, etc. (1-3) C6-30 [alkyl (C1-20)] phenol AO 1-30 mol adduct (Meth) acrylate (meth) acrylate of PO3 mol adduct of phenol, (meth) acrylate of EO1 mol adduct of nonylphenol, etc. (1-4) (meth) acrylate of C6-30 alicyclic monohydric alcohol cyclohexyl ( (Meth) acrylate, isobornyl (meth) acrylate, etc.

(2) di (meth) acrylate (2-1) (poly) oxyalkylene (C2-4) (molecular weight 62 to Mn3,000) di (meth) acrylate polyethylene glycol (hereinafter abbreviated as PEG) (Mn400), Polypropylene glycol (hereinafter abbreviated as PPG) (Mn200) and polytetramethylene glycol (hereinafter abbreviated as PTMG) (Mn650), each di (meth) acrylate, etc. (2-2) AO 2-30 mol adduct of bisphenol compound Di (meth) acrylate Di (meth) acrylates of bisphenol A, -F and -S, EO2 mol and PO4 mol adducts (2-3) C2-30 aliphatic dihydric alcohol di (meth) acrylate NPG and HD di (meth) acrylates etc. (2-4) C6-30 alicyclic skeleton Dihydric alcohol di (meth) acrylate dimethylol tricyclodecane di (meth) acrylate, cyclohexane dimethanol di (meth) acrylates and di (meth) acrylate of hydrogenated bisphenol A with

(3) Poly (n = 3-6 or more) (meth) acrylate (3-1) C3-40 polyvalent (trivalent to hexavalent or more) alcohol poly (meth) acrylate TMP tri (meta ) Acrylate, GR tri (meth) acrylate, tri (meth) acrylate of TMP PO3 mol adduct, tri (meth) acrylate of EO3 mol adduct of TMP, tri (meth) acrylate of PE, tetra (meth) of PE Acrylate, tetra (meth) acrylate of PE EO4 mole adduct, dipentaerythritol (DP)
Hexa (meth) acrylate etc.

(4) Polyester (meth) acrylates Multivalent (2-4) carboxylic acids, polyvalent (2-8 or more) alcohols and (meth)
Polyester (meth) acrylate having a molecular weight of 150 to Mn4,000 having a plurality of ester bonds and a plurality of (meth) acryloyl groups obtained by esterification of an acryloyl group-containing compound. Polyhydric carboxylic acids [C3-20, such as malonic acid, maleic acid (anhydride), adipic acid, sebacic acid, succinic acid, a reaction product of acid anhydride (such as a reaction product of diPE and maleic anhydride), fat Cyclic polycarboxylic acids [C5-30, such as cyclohexanedicarboxylic acid, tetrahydro (anhydride) phthalic acid and methyltetrahydro (anhydride) phthalic acid] and aromatic polycarboxylic acids [C8-30, such as isophthalic acid,
Terephthalic acid, phthalic acid (anhydride) and trimellitic acid (anhydride)].

Examples of the polyvalent (2 to 8 or more) alcohols include the polyols exemplified as the above (a2).
Examples of the (meth) acryloyl group-containing compound include C2-30, such as (meth) acrylic acid and hydroxymethyl (meth) acrylate.

(5) A butadiene polymer having a (meth) acryloyl group in the main chain and / or side chain [for example, polybutadiene di (meth) acrylate (Mn 500 to 500,000)]
(6) A siloxane polymer having a (meth) acryloyl group in the main chain and / or side chain of dimethylpolysiloxane [Mn 300 to 20,000, such as dimethylpolysiloxane di (
(Meth) acrylate]
Among these, (2), (3) and (4) are preferable from the viewpoint of toughness of the cured product.

The amount of (X) used is usually 2,000% from the viewpoint of the elasticity of the cured product based on the weight of (A).
Hereinafter, it is further preferably 20 to 1,000%, particularly preferably 30 to 300%.
Among (X), those having an active hydrogen atom may be added after completion of the urethanization reaction, and those having no active hydrogen atom may be added at any stage during and / or after the urethanization reaction.

If necessary, the composition of the present invention may further contain various additives (D) used for paints and inks as long as the effects of the present invention are not impaired. (D) includes inorganic fine particles (D1)
, Organic pigment (D2), dispersant (D3), antifoaming agent (D4), leveling agent (D5), silane coupling agent (D6), thixotropic agent (thickener) (D7), slip agent ( D
8) Antioxidant (D9) and UV absorber (D10) are included.
The total amount of (D) used is usually 60% or less, preferably 0.005 to 50%, based on the total weight of the composition of the present invention.

(D1) includes alumina [aluminum oxide, aluminum hydroxide, alumina white (alumina hydrate), silica alumina (a fused material of alumina and silica, alumina surface coated with silica, etc.]], zirconia, carbonized Tungsten, titanium carbide,
Silicon carbide, boron carbide, diamond, carbon black (channel black, furnace black, thermal black, acetylene black, etc.), silica (fine silicate, hydrous silicate, diatom, colloidal silica, etc.), silicate (fine silicate) Magnesium, talc, soapstone, stearite, calcium silicate, magnesium aluminosilicate, sodium aluminosilicate, etc.), carbonate [precipitate (active, dry, heavy or light) calcium carbonate, magnesium carbonate, etc.], clay (kaolin) Clay, sericite clay, vilophyllite clay, montmorillonite clay, bentonite, acid clay, etc.), sulfate [
Aluminum sulfate (sulfate band, satin white, etc.), barium sulfate (barite powder, precipitated barium sulfate, lithopone, etc.), magnesium sulfate, calcium sulfate (stone koji) (anhydrous koji, hemihydrate koji, etc.)], lead white Mica powder, zinc white, titanium oxide, activated calcium fluoride, cement, lime, calcium sulfite, molybdenum disulfide, asbestos, glass fiber, lock fiber, and microballoon.

Among these, from the viewpoint of scratch resistance and composition of the cured product, and suppression of coloring of the cured product, alumina, silica, silicate, carbonate, sulfate and titanium oxide are preferable, and silica, calcium carbonate, Barium sulfate and titanium oxide.
(D1) may be used in combination of two or more, or two or more may be combined (for example, titanium oxide is fused to silica). The shape of (D1) is not particularly limited, and may be, for example, an indefinite shape, a spherical shape, a hollow shape, a porous shape, a petal shape, an aggregated shape, or a granular shape. The amount of (D1) used is usually 50% or less based on the total weight of the composition of the present invention, preferably 30% or less, more preferably 3 to 25% from the viewpoint of the flexibility of the cured product.

Examples of (D2) include the following.
(1) Azo pigments Insoluble monoazo pigments (toluidine red, permanent carmine FB, fast yellow G, etc.), insoluble disazo pigments (disazo yellow AAA, disazo orange PMP, etc.),
Azo lakes (soluble azo pigments) (lake red C, brilliant carmine 6B, etc.), condensed azo pigments, chelate azo pigments, etc. (2) polycyclic pigments phthalocyanine blue, indanthrone blue, quinacridone red, dioxazine violet, etc. (3) dyeing Lakes Basic dyes (Victoria Pure Blue BO Lake, etc.), Acid Dyes (Alkali Blue Toner, etc.), etc. (4) Other Azine pigments (Aniline Black, etc.), Daylight fluorescent pigments, Nitroso pigments, Nitro pigments,
The amount of the natural pigment or the like (D2) used is usually 50% or less based on the total weight of the composition, preferably 40% or less, more preferably 30% or less, from the viewpoint of the flexibility of the cured product.

Examples of (D3) include organic dispersants [polymer dispersants (Mn 2,000 to 500,000) and low molecular dispersants (molecular weight 100 to less than Mn 2,000)] and inorganic dispersants.

As the polymer dispersant, naphthalene sulfonate [alkali metal (Na and K etc.) salt, ammonium salt etc.] formalin condensate, polystyrene sulfonate (same as above),
Polyacrylate (same as above), poly (2-4) carboxylic acid (maleic acid / glycerin / monoallyl ether copolymer etc.) salt (same as above), carboxymethylcellulose (M
n1,000 to 10,000) and polyvinyl alcohol (Mn 1,000 to 100,
000) and the like.

The following are mentioned as a low molecular weight dispersing agent.
(1) Polyoxyalkylene type aliphatic alcohol (C4-30), [alkyl (C1-30)] phenol, aliphatic (
AO (C2-4) 1-30 mol adduct of C4-30) amine and aliphatic (C4-30) amide As aliphatic alcohol, n-, i-, sec- and t-butanol, octanol, dodecanol, etc. The (alkyl) phenol includes phenol, methylphenol and nonylphenol; the aliphatic amine includes laurylamine and methylstearylamine; and the aliphatic amide includes stearamide.
(2) Polyhydric alcohol type C4-30 fatty acid (lauric acid, stearic acid, etc.) and polyvalent (2-6 or more)
Monoester compounds of alcohols (eg GR, PE, SO and sorbitan) (3) Carboxylate type Alkali metal (same as above) salts of fatty acids of C4-30 (same as above) (4) Sulfate ester types C4-30 Aliphatic alcohols (same as above) and aliphatic alcohols AO (C2-
4) 1-30 mol adduct sulfate alkali metal (same as above) salts, etc.

(5) Sulfonate type [Alkyl (C1-30)] Phenol (same as above) sulfonic acid alkali metal salt (same as above) (6) Phosphate ester type C4-30 aliphatic alcohol (same as above) ) And AO of aliphatic alcohols (C2-
4) 1-30 mol adduct mono- or diphosphate salt [alkali metal (same as above) salt, quaternary ammonium salt, etc.]
(7) C1-30 aliphatic amines [primary (laurylamine, etc.), secondary (dibutylamine, etc.) and tertiary amine (dimethylstearylamine, etc.) hydrochloride, triethanolamine And C4
Inorganic acid (hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, etc.) salt of monoester of -30 fatty acids (same as above) (8) Quaternary ammonium salt type C4-30 quaternary ammonium (butyltrimethylammonium, diethyllaurylmethyl) Inorganic acid (same as above) salts of ammonium, dimethyl distearyl ammonium and the like.

Examples of the inorganic dispersant include alkali metal (same as above) salts of polyphosphoric acid and phosphoric acid-based dispersants (phosphoric acid, monoalkyl phosphoric acid ester, dialkyl phosphoric acid ester and the like).
The amount of (D3) used is usually 10% or less, preferably 0.05 to 5%, based on the total weight of the composition of the present invention.

As (D4), lower alcohol (C1-6) (methanol, butanol, etc.), higher alcohol (C8-18) (octyl alcohol, hexadecyl alcohol, etc.), higher fatty acid (C10-20) (oleic acid, stearic acid) Etc.), higher fatty acid esters (C11-
30) (glycerin monolaurate), phosphate ester (tributyl phosphate, etc.)
, Metal soap (calcium stearate, aluminum stearate, etc.), polyether [PEG (Mn 200-10,000), PPG (Mn 200-10,000), etc.], silicone (dimethyl silicone oil, alkyl-modified silicone oil, fluorosilicone oil) Etc.) and mineral oil type (silica powder dispersed in mineral oil).
The amount of (D4) used is usually 3% or less, preferably 0.01-2%, based on the total weight of the composition of the present invention.

(D5) includes PEG type nonionic surfactant (nonylphenol EO 1-40 mol adduct, stearic acid EO 1-40 mol adduct, etc.), polyhydric alcohol type nonionic surfactant (sorbitan palmitic acid monoester, sorbitan) Stearic acid monoester, sorbitan stearic acid triester, etc.), fluorosurfactant (perfluoroalkyl EO)
1-50 mol adducts, perfluoroalkyl carboxylates, perfluoroalkyl betaines, etc.), modified silicone oils [other than (■ 4), such as polyether-modified silicone

And (meth) acrylate-modified silicone oil].
The amount of (D5) used is usually 3% or less, preferably 0.1 to 2%, based on the total weight of the composition of the present invention.

Examples of (D6) include amino group-containing silane coupling agents (γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-phenylaminopropyltrimethoxysilane, etc.), ureido group-containing silane coupling agents ( Ureidopropyltriethoxysilane, etc.), vinyl group-containing silane coupling agents [vinylethoxysilane, vinylmethoxysilane, vinyltris (β-methoxyethoxy) silane, etc.], methacrylate groups-containing silane coupling agents (γ-methacryloxypropyltrimethoxy) Silane, γ-methacryloxypropylmethyldimethoxysilane, etc.), epoxy group-containing silane coupling agent (
γ-glycidoxypropyltrimethoxysilane etc.), isocyanate group-containing silane coupling agent (γ-isocyanatopropyltriethoxysilane etc.), polymer type silane coupling agent (polyethoxydimethylsiloxane, polyethoxydimethylsiloxane etc.),
And cationic type silane coupling agents [N- (N-benzyl-β-aminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride and the like].
The amount of (D6) used is usually 10% or less, preferably 0.5 to 7%, based on the total weight of the composition of the present invention.

Examples of (D7) include inorganic thixotropy imparting agents [bentonite, organically treated bentonite (surface wax coating treated bentonite, etc.) and ultrafine surface treated calcium carbonate (colloidal calcium carbonate, etc.)] and organic thixotropic property imparters (hydrogenated castor). Oil wax, calcium stearate, aluminum oleate, polymerized linseed oil, etc.).
The amount of (D7) used is usually 20% or less, preferably 0.5 to 10%, based on the total weight of the composition of the present invention.

(D8) includes higher fatty acid esters (such as butyl stearate), higher fatty acid amides (such as ethylene bis stearic acid amide and oleic acid amide), metal soaps (such as calcium stearate and aluminum oleate), and wax [paraffin wax, polyolefin And wax (polyethylene wax, polypropylene wax, carboxyl group-containing polyethylene wax, etc.) and silicone (for example, dimethyl silicone oil, alkyl-modified silicone oil and fluorosilicone oil).
The amount of (D8) used is usually 5% or less, preferably 0.01-2%, based on the total weight of the composition of the present invention.

(D9) is a hindered phenol compound [triethylene glycol-bis- [
3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,
6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 3,5-di-t-butyl-4-hydroxybenzylphosphonate diethyl ester] and amine compounds (n-butylamine, triethylamine, diethylaminomethyl methacrylate, etc.).
The amount of (D9) used is usually 3% or less, preferably 0.005 to 2%, based on the total weight of the composition of the present invention.

(D10) includes benzotriazole compounds [2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole, 2- (3 , 5-Di-t-butyl-2-hydroxyphenyl)-
5-chlorobenzotriazole, 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, etc.], triazine compound [2- (4,6-diphenyl-1,3,
5-triazin-2-yl) -5-[(hexyl) oxy] -phenol], benzophenone (such as 2-hydroxy-4-n-octyloxybenzophenone), oxalic acid anilide compound (2-ethoxy-2′-ethyl) Oxalic acid bisanilide and the like).
The amount of (D10) used is usually 3% or less, preferably 0.005 to 2%, based on the total weight of the composition of the present invention.

When the additives are the same and overlap between (D1) to (D10) above, the amount of each additive exerting the corresponding additive effect is not used regardless of the effect as the other additive, Considering that the effects as other additives can be obtained at the same time, the amount used is adjusted according to the purpose of use.

The composition of the present invention can further contain a thermosetting catalyst and / or a photopolymerization initiator as necessary as long as the effects of the present invention are not impaired. Those added with a thermosetting catalyst and / or a photopolymerization initiator can be cured with heat and / or ultraviolet rays in addition to the electron beam, and a cured product having excellent chemical resistance and scratch resistance can be obtained. When curing by heat, it is usually desirable to heat-treat in an oven at 50 to 200 ° C., preferably 80 to 180 ° C. for 1 minute to 20 hours. In the case of curing by ultraviolet rays, the irradiation amount of ultraviolet rays is usually 10 to 10
1,000 mJ / cm ² .

Examples of the thermosetting catalyst include peroxides (t-butyl peroxybenzoate, benzoyl peroxide, methyl ethyl ketone peroxide, etc.) and azo compounds (azobisisobutyronitrile, azobisisovaleronitrile, etc.). Of these, t-butyl peroxybenzoate and methyl ethyl ketone peroxide are preferable from the viewpoint of stability and reactivity of the composition.

As the photopolymerization initiator, a hydroxybenzoyl compound (2-hydroxy-2-methyl-
1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, benzoin alkyl ether, etc.), benzoylformate compound (methylbenzoylformate, etc.), thioxanthone compound (isopropylthioxanthone, etc.), benzophenone (benzophenone, etc.), phosphoric acid Examples include ester compounds (1,3,5-trimethylbenzoyldiphenylphosphine oxide and the like), benzyldimethyl ketal and the like. Among these, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone and 1,3,5-trimethylbenzoyldiphenylphosphine oxide are preferable from the viewpoint of preventing coloring of the cured product. is there.

The usage-amount of a thermosetting catalyst and a photoinitiator is 20% or less normally based on the total weight of the composition of this invention, respectively, Preferably it is 0.1 to 10%.

In order to adjust the viscosity of the composition of the present invention to a viscosity suitable for coating, a coating diluted with a solvent as necessary can be used. The amount of the solvent used is usually 2,000% or less, preferably 10 to 500%, based on the weight of the composition. Further, the viscosity of the coating is usually 5 to 500,000 mPa · s at the temperature during use (usually 5 to 60 ° C.), and preferably 50 to 10,000 mPa · s from the viewpoint of stable coating.

The solvent is not particularly limited as long as it dissolves the resin component in the composition of the present invention. Specifically, aromatic hydrocarbons (C7-10, such as toluene, xylene and ethylbenzene), esters or ether esters (C4-10, such as ethyl acetate, butyl acetate and methoxybutyl acetate), ethers (C4-10, such as Diethyl ether, tetrahydrofuran, monoethyl ether of EG, monobutyl ether of EG, monomethyl ether of PG and monoethyl ether of DEG), ketones (C3-10, eg acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone and cyclohexanone) ), Alcohols (C1-10, such as methanol, ethanol, n- and i-propanol, n-, i-, sec- and t-butanol, 2-ethylhexyl alcohol and benzyl alcohol). Call), an amide (C3-6, such as dimethylformamide, dimethylacetamide, N- methylpyrrolidone), sulfoxides (C2-4, such as dimethyl sulfoxide), water, and combinations of two or more mixed solvents thereof.
Of these solvents, esters, ketones and alcohols having a boiling point of 70 to 100 ° C. are preferred, and ethyl acetate, methyl ethyl ketone, i-propanol and mixtures thereof are more preferred.

The composition of the present invention is diluted with a solvent if necessary, applied to at least a part of at least one side of the substrate, and dried if necessary, and then irradiated with active energy rays (ultraviolet rays, electron beams, X-rays, etc.). Thus, a coating having a cured product on at least a part of the front surface and / or the back surface of the substrate can be obtained.
In the coating, a commonly used apparatus such as a coating machine [bar coater, gravure coater, roll coater (size press roll coater, gate roll coater, etc.), air knife coater, spin coater, blade coater, etc.] can be used. The coating film thickness is usually 0.5 to 300 μm as the film thickness after curing and drying, and the preferable upper limit is 250 μm from the viewpoint of drying property and curability, and the preferable lower limit is from the viewpoint of wear resistance, solvent resistance, and contamination resistance. Is 1 μm.

When the composition of the present invention is used after being diluted with a solvent, it is preferably dried after coating. Examples of the drying method include hot air drying (such as a dryer). The drying temperature is usually 10
The upper limit is preferably 150 ° C. from the viewpoint of ~ 200 ° C., the smoothness and the appearance of the coating film, and the lower limit is preferably 30 ° C. from the viewpoint of the drying speed.

When the composition of the present invention is cured by ultraviolet irradiation, a known ultraviolet irradiation device [for example, Eye Grandage, manufactured by Eye Graphic Co., Ltd.] can be used. The dose of the ultraviolet radiation is typically 10~10,000mJ / cm ^2, a preferred upper limit of a flexible point of view of the cured product, 5,000J / cm ^2, preferably lower from the viewpoint of curability of the composition, 100 mJ / cm ²
It is.

When the composition of the present invention is cured by electron beam irradiation, a known electron beam irradiation apparatus [for example, Electron Beam, manufactured by Iwasaki Electric Co., Ltd.] can be used. The electron beam dose is
Usually, 0.5 to 20 Mrad, and the preferable lower limit from the viewpoint of curability of the composition is 1 Mrad, flexibility of the cured product, and from the viewpoint of avoiding damage to the cured product (coating film) or the substrate,
A preferred upper limit is 15 Mrad.

The composition of the present invention is usually cured by active energy rays (ultraviolet rays, electron beams, X-rays, etc.), but can be cured by heat when a thermosetting catalyst is contained if necessary.

The composition of the present invention can be used as a coating agent such as a substrate, an adhesive, a sealing material and the like. Although it does not specifically limit as a base material applied, For example, paper, a plastics, glass, and a metal are mentioned. Specifically, paper (for example, thin paper, inter-paper reinforced paper, titanium paper, latex-impregnated paper and base paper for gypsum board), plastic [plastic film (film of vinyl chloride, polyester, polypropylene, polymethyl methacrylate, etc.), plastic plate (Plates of polymethyl methacrylate, polycarbonate and methyl methacrylate / styrene copolymer, etc.)], glass plates, copper plates, iron plates and the like.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by this.

Example 1
In a four-necked flask equipped with a stirrer, a condenser tube and a thermometer, 100 parts of pentaerythritol triacrylate [trade name: Light acrylate PE-3A, manufactured by Kyoeisha Chemical Co., Ltd.], H
29.8 parts of DI trimer [trade name: Tronate HDT-LV, manufactured by Rhodia Co., Ltd.] and 0.05 part of bismuth tri (2-ethylhexanoate) (2-ethylhexanoic acid 50% solution) as an organic bismuth compound It mix | blended and was made to react at 70 degreeC for 8 hours, and the urethane acrylate composition (U-1) was obtained.

Example 2
PTMG [trade names: PTMG-1000, Mn 1,000,
Mitsubishi Chemical Co., Ltd.] 100 parts and hydrogenated MDI 39.3 parts were mixed and reacted at 110 ° C. for 4 hours, then 11.6 parts of 2-hydroxyethyl acrylate and bismuth tri (cyclohexanecarboxylate) as an organic bismuth compound (Cyclohexanecarboxylic acid 20% solution) 0.03 part was added and reacted at 80 ° C. for 6 hours to obtain a urethane acrylate composition (U-2
)

Example 3
Polycarbonate diol [trade name: Plaxel PC-22 was added to the same reactor as in Example 1.
0, Mn 2,000, manufactured by Daicel Chemical Industries, Ltd.] 100 parts, IPDI 22.2 parts and 2-
11.6 parts of hydroxyethyl acrylate was added, 0.05 parts of bismuth tris (2,2,6,6-tetramethyl-3-5-heptanedionate) was added as an organic bismuth compound, and the reaction was carried out at 80 ° C. for 6 hours. To obtain a urethane acrylate composition (U-3).

Example 4
A glycerin PO adduct [trade name: New Pole GP-10] was added to the same reactor as in Example 1.
00, Mn 1,000, Sanyo Chemical Industries, Ltd.] 100 parts, HDI 50.4 parts and 2-
34.8 parts of hydroxyethyl acrylate was blended, 0.03 part of bismuth tributoxide was added as an organic bismuth compound, and the mixture was reacted at 70 ° C. for 12 hours to obtain a urethane acrylate composition (U-4) of the present invention.

Comparative Example 1
In Example 1, it replaces with bismuth tri (2-ethylhexanoate) (2-ethylhexanoic acid 50% solution), and is 70 degreeC by the same composition as Example 1 except using 0.05 part of tetramethylethylenediamine. When the reaction was carried out, gelation occurred at 2 hours, and the urethane acrylate composition (U-5) was not obtained.

Comparative Example 2
In Example 2, the reaction was carried out at 70 ° C. for 4 hours with the same composition as in Example 2 except that 0.02 part of dibutyltin dilaurate was used instead of bismuth tri (cyclohexanecarboxylate) (cyclohexanecarboxylic acid 20% solution). , Urethane acrylate composition (
U-6) was obtained.
Comparative Example 3
In Example 2, the reaction was carried out at 80 ° C. for 48 hours with the same composition as in Example 2 except that 0.3 parts of titanium tetrabutoxide was used instead of bismuth tri (cyclohexanecarboxylate) (cyclohexanecarboxylic acid 20% solution). The urethane acrylate composition (U-7) was obtained.

Table 1 shows the NCO%, Mn, viscosity, and color number (Hazen) of (U-1) to (U-4) and (U-6) to (U-7).
Table 1 also shows the results of the viscosity and the number of colors after storage under the following conditions.
[Storage conditions]
Temperature x period: dark in the thermostatic chamber 40 ° C x 3 months Container: Cylindrical type with hermetic lid with inner diameter 7.4cm, height 8.8cm, capacity 220ml
Brown glass container Sample volume: 200ml

Each urethane acrylate composition 1 of (U-1) to (U-4), (U-6) to (U-7)
To 00 parts, 50 parts of isobornyl acrylate, 3 parts of 2-hydroxy-2-methyl-1-phenylpropan-1-one and 50 parts of methyl ethyl ketone were blended. Next, it was coated on a polycarbonate plate (thickness 5 mm) with a bar coater so that the thickness after drying was about 5 μm, dried with a dryer, and then irradiated with 1,000 mJ / cm ² UV. And cured.
The yellow index (YI) of the obtained cured product was measured with a colorimeter [multiple light source spectrocolorimeter [manufactured by Suga Test Instruments Co., Ltd.]]. The results are shown in Table 1.

The cured product obtained by curing the composition of the present invention is excellent in light resistance, transparency, and non-coloring properties, and therefore uses that require transparency and non-coloring properties [coating agents, adhesives, sealing materials, optical materials. Widely used as a member (the above), an electric / electronic member (the above).

Claims (17)

An active energy ray-curable urethane (meth) acrylate composition comprising a urethane (meth) acrylate (A) and an organic bismuth compound (B). The composition according to claim 1, wherein (A) is a urethane (meth) acrylate formed from a polyol component (a) comprising a compound (a1) having a hydroxyl group and a (meth) acryloyl group and a polyisocyanate component (b). object. The composition according to claim 2, wherein (b) is an aliphatic or alicyclic polyisocyanate. Furthermore, the other polyol (a2) is contained in (a), The composition of Claim 2 or 3. The composition according to claim 4, wherein (a2) is a polyether and / or a polyester polyol. The composition according to any one of claims 1 to 4, wherein (B) is at least one selected from the group consisting of organic bismuth carboxylates, organic bismuth alkoxides and chelating products of organic bismuth and compounds having a dicarbonyl group. The composition according to any one of claims 1 to 5, wherein the proportion of (B) based on the weight of (A) is 0.001 to 0.5%. Furthermore, the organic acid (c) is contained, The composition in any one of Claims 1-6. The composition according to claim 8, wherein the proportion of (c) based on the weight of (A) is 0.001 to 10%. The weight ratio of (B) to (c) is 0.001 / 1 to 9/1.
Or the composition of 9. Furthermore, other (meth) acrylates (X) other than (A) are contained, The composition in any one of Claims 1-10. Furthermore, the composition in any one of Claims 1-11 made to contain a thermosetting catalyst and / or a photoinitiator. In the manufacturing method of the composition in any one of Claims 2-12, the polyol component (a) and polyisocyanate component (b) which consist of a compound (a1) which has a hydroxyl group and a (meth) acryloyl group are made into an organic bismuth compound ( The urethanization reaction is carried out at 40 to 100 ° C. in the presence of B), or (a) and (b) are partially reacted in the absence of (B) and then 40 to 100 in the presence of (B). A process for producing an active energy ray-curable urethane (meth) acrylate composition, wherein the urethane-forming reaction is carried out at a temperature of ° C. A coating agent comprising the composition according to any one of claims 1 to 12,
Adhesive or sealant. Hardened | cured material formed by hardening | curing the composition in any one of Claims 1-12. An optical member or an electric / electronic member comprising the cured product according to claim 15. The manufacturing method of the hardened | cured material characterized by apply | coating the composition in any one of Claims 1-12 to at least one part of at least one side of a base material, and irradiating an active energy ray and hardening.