CN1814674A - Activity energy-line solidifying type resin composition - Google Patents
Activity energy-line solidifying type resin composition Download PDFInfo
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- CN1814674A CN1814674A CN 200510007358 CN200510007358A CN1814674A CN 1814674 A CN1814674 A CN 1814674A CN 200510007358 CN200510007358 CN 200510007358 CN 200510007358 A CN200510007358 A CN 200510007358A CN 1814674 A CN1814674 A CN 1814674A
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Abstract
This invention is aimed to provide a resin composite with solidified useful active energy lines when forming a coating with excellent anti-static under low humidity including amido-methyl crylic acid ester compound with quaternary ammonium salt and a polymer with quaternary ammonium salt.
Description
Technical field
The present invention relates to contain the activity energy-line solidifying type resin composition of carbamate (methyl) acrylic ester compound, relate to useful activity energy-line solidifying type resin composition in forming outstanding coating in more detail, described outstanding coating is in hardness of film, scuff resistance, static resistance, particularly there are not humidity interdependence, the static resistance under low humidity very outstanding, even and then cooperate ethylene unsaturated monomer and make static resistance reduce seldom coating yet.
Background technology
Plastic molded article is except that in light weight, the transparency is outstanding, and forming process is easy, economical, so be widely used, still, its disadvantageous one side is soft, scratch easily, in addition, because electroconductibility is low, so make accumulation of static electricity easily, adsorbs dust easily.For this reason, adopt to go into plastics or to be coated on the method for frosting static inhibitor is directly mixing as applying agent.
But; in mixing method of going into plastics with static inhibitor; the transparency reduces, the high problem of processing charges because exist; so in actual applications; what adopt is the method that coating applies agent,, though can give to a certain degree static resistance; but because the function of frosting is not almost mechanically protected in this coating agent, so the result is the easy problem that scratches in surface that exists in plastics.Thereby, also there is not all outstanding coating agent of static resistance and scuff resistance two aspects.
Under such situation; as applying agent; the polyalkylene glycol compounds that has proposed to contain at an end hydroxyl is the coating agent composition that contains urethane acrylate oligomer (for example consult the spy and open the 2000-264939 communique) that raw material is made; and active energy ray-curable material; this material contains (methyl) acrylate (A) with 1 carboxyl and 1 or its above acryl and has N, the polymerizable compound of N-dialkyl amido and quaternary ammonium salt base (B) (for example consult the spy and open the 2002-121208 communique).
But, after the present inventor discusses in detail, find that above-mentioned spy opens in the disclosed technology of 2000-264939 communique, coating agent composition can not satisfy antistatic property separately fully, in the practical application, have to and static inhibitor and usefulness, and, along with the influence of humidity, under the low-humidity environment in the winter that more is difficult to bring into play static resistance, static resistance can further reduce.In addition, above-mentioned spy opens the disclosed cured coating film of 2000-264939 communique, from the viewpoint of scuff resistance, can not satisfy the requirements at the higher level that propose along with technology heightization in recent years.
On the other hand; open in the disclosed technology of 2002-121208 communique the spy; comprise (methyl) acrylate (A) and have N with 1 carboxyl and 1 or its above acryl; the resin combination of the polymerizable compound of N-dialkyl amido and quaternary ammonium salt base (B); the phenomenons of the cured coating film generation albefaction that obtains etc. etc. are as the poor practicability that applies agent.
Disclosure of an invention
Under such background, the object of the present invention is to provide activity energy-line solidifying type resin composition useful when forming coating, described coating is in hardness of film, scuff resistance, static resistance, particularly there are not humidity interdependence, the static resistance under low humidity very outstanding, even and then cooperate ethylene unsaturated monomer and make static resistance reduce seldom coating yet.
What the present inventor furtherd investigate repeatedly in view of such situation found that, contain the activity energy-line solidifying type resin composition that carbamate (methyl) acrylic ester compound [I] with quaternary ammonium salt base and the polymkeric substance [II] with quaternary ammonium salt base are formed, conform with above-mentioned purpose, and finished the present invention.
Among the present invention, carbamate (methyl) acrylic ester compound [I] that particularly has quaternary ammonium salt base be make polyisocyanates compounds (a1) with the quaternary ammonium salt (a2) of following general formula (1) expression and contain (methyl) acrylic ester compound (a3) reaction of hydroxyl and during carbamate (methyl) acrylic ester compound (A) that obtains, or make polyisocyanates compounds (b1) with the quaternary ammonium salt (b2) of following general formula (3) expression and contain (methyl) acrylic ester compound (b3) reaction of hydroxyl and during carbamate (methyl) acrylic ester compound (B) that obtains, will bring into play effect of the present invention significantly.
Here, R
1, R
2, R
3Be alkyl, the X of carbonatoms 1～50
1Be Cl, Br, R
4SO
3(R
4Be alkyl, alkyl oxide or alkylbenzene), n is 1～200 integer.
Here, R
8, R
9Be any one in the alkyl of carbonatoms 1～50, X
2Be Cl, Br, RSO
3(R is alkyl, alkyl oxide or alkylbenzene), m, n are 1 or its above integer, m+n is 2～500.
In addition, have the polymkeric substance [II] of quaternary ammonium salt base among the present invention, preferably will contain the multipolymer of the unsaturated monomer of quaternary ammonium salt base, or will contain the quaternized thing of amino unsaturated monomer as the multipolymer of copolymer composition as copolymer composition.
And then, in the present invention, from making static resistance not reduce, make the viewpoint of raisings such as hardness of film, scuff resistance preferably to contain carbamate (methyl) acrylic ester compound [IV], this compound by the isocyanate group in the polyisocyanates compounds (c1) with form amino-formate bond respectively with the hydroxyl of the polyalkylene derivative (c2) of following general formula (6) expression and the hydroxyl that contains (methyl) acrylic ester compound (c3) of hydroxyl and constitute.
Here, Y is an alkylene, and Z is any one in alkyl, (methyl) acryl, allyl group, the acyl group, and p is 1 or its above integer.
In the present invention, more preferably also contain ethylene unsaturated monomer [V] from hardness of film, scuff resistance aspect.
The optimal morphology that carries out an invention
Below, explain the present invention.
Activity energy-line solidifying type resin composition of the present invention, be to contain carbamate (methyl) acrylic ester compound [I] with quaternary ammonium salt base and the formation of the polymkeric substance [II] with quaternary ammonium salt base, by import quaternary ammonium salt base in the molecule of carbamate (methyl) acrylic ester compound and polymkeric substance, balance is brought into play static resistance and scuff resistance etc. well simultaneously.
At first, carbamate (methyl) acrylic ester compound [I] is described.
As carbamate (methyl) acrylic ester compound [I], if have just having no particular limits of quaternary ammonium salt base, but wherein, from hardness of film, scuff resistance, static resistance aspect, more preferably make polyisocyanates compounds (a1) and react carbamate (methyl) acrylic ester compound (A) that obtains with the quaternary ammonium salt (a2) of following general formula (1) expression and (methyl) acrylic ester compound (a3) of containing hydroxyl.
Here, R
1, R
2, R
3Be the alkyl of carbonatoms 1～50, X
1Be Cl, Br, R
4SO
3(R4 is alkyl, alkyl oxide or alkylbenzene), n is 1～200 integer.
(a1) has no particular limits as the polyisocyanates compounds, for example can enumerate, the fragrance same clan, aliphatics, the polyisocyanates of the alicyclic ring same clan etc., wherein, can enumerate, tolylene diisocyanate, diphenylmethanediisocyanate, hydrogenated diphenyl methane diisocyanate, polyphenyl methane polyisocyanates, modified diphenylmethane diisocyanate, the hydrogenation xylylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, the tetramethyl-xylylene diisocyanate, isophorone diisocyanate, the norbornylene vulcabond, 1, two (isocyanato-methyl) hexanaphthenes of 3-, phenylene vulcabond, lysinediisocyanate, Lysine triisocyanate, 3 aggressiveness compound or polymer compounds of the polyisocyanates of naphthalene diisocyanate etc. or these polyisocyanates, biuret type polyisocyanates, water dispersive polyisocyanate (for example, " ア Network ア ネ one ト 100 " of Japan's Port リ ウ レ Application industry (strain), " ア Network ア ネ one ト 110 ", " ア Network ア ネ one ト 200 ", " ア Network ア ネ one ト 210 " etc.), in addition, can enumerate the reaction product etc. of these polyisocyanates and polyvalent alcohol.
As such polyvalent alcohol, have no particular limits, can enumerate for example ethylene glycol, glycol ether, triglycol, Tetraglycol 99, polyoxyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butyleneglycol, polytetramethylene glycol, 1, the polyvalent alcohol of 6-hexylene glycol, neopentyl glycol, cyclohexanedimethanol, Hydrogenated Bisphenol A, polycaprolactone, trimethylolethane, TriMethylolPropane(TMP), poly-TriMethylolPropane(TMP), tetramethylolmethane, polypentaerythritol, Sorbitol Powder, mannitol, glycerine, Polyglycerine, polytetramethylene glycol etc.; The polyether glycol of at least a kind of structure of polyethylene oxide, poly(propylene oxide), the block with ethylene oxide/propylene oxide or random copolymerization is as polybutadiene polyvalent alcohol of the caprolactone modification polyvalent alcohol of the polyester polyol of the condenses of polyprotonic acids such as this polyvalent alcohol or polyether glycol and maleic anhydride, toxilic acid, fumaric acid, itaconic anhydride, methylene-succinic acid, hexanodioic acid, m-phthalic acid, polytetramethylene polyvalent alcohol of caprolactone modification etc., polyolefins polyvalent alcohol, hydrogenated butadiene polymer polyvalent alcohol etc. etc.
Further, as such polyvalent alcohol, also for example can enumerate, 2, two (methylol) butyric acid of 2-, tartrate, 2,4-resorcylic acid, 3,5-resorcylic acid, 2, two (methylol) propionic acid, 2 of 2-, two (hydroxyethyl) propionic acid, 2 of 2-, two (hydroxypropyl) propionic acid of 2-, dihydroxyl methyl acetic acid, two (4-hydroxy phenyl) acetate, 4, the polyvalent alcohol that contains carboxyl of two (4-hydroxy phenyl) valeric acids of 4-, homogentisic acid etc., or contain 1, the sulfonic group of 4-butyleneglycol sodium sulfonate etc. or contain polyvalent alcohol of sulphonate-base etc.
When using the reaction product of polyisocyanates and polyvalent alcohol, for example can be used as, the polyisocyanates that contains terminal isocyanate group that the reaction of above-mentioned many Yuans alcohol and above-mentioned polyisocyanates is obtained uses.In the reaction of polyisocyanates and polyvalent alcohol,, also preferably use the such metal catalyst of dibutyl tin laurate, 1, the amines catalyst that 8-diazabicyclo [5.4.0] undecylene-7 is such etc. to promote that reaction is a purpose.
As with the quaternary ammonium salt (a2) of above-mentioned polyisocyanates compounds (a1) reaction, can enumerate the quaternary ammonium salt of structure shown in the above-mentioned general formula (1).
In above-mentioned, R
1, R
2, R
3, X
1, n is same as described above, the preferable range of oxyethane addition mole number n is 1～100, is more preferably 1～50.
Object lesson as the quaternary ammonium salt (a2) of general formula (1) expression, can enumerate dimethyl alkyl hydroxyethylsulfonic acid ammonium, polyoxyethylene dimethyl alkylsulphonic acid ammonium, diethyl alkyl hydroxyethylsulfonic acid ammonium, polyoxyethylene diethyl alkylsulphonic acid ammonium, triethyl hydroxyethylsulfonic acid ammonium, polyoxyethylene three ethyl sulfonic acid ammoniums or these R
4SO
3(R
4Be alkyl, alkyl oxide or alkylbenzene) product that replaced by chlorine or bromine etc.
In addition, as the weight-average molecular weight of the quaternary ammonium salt (a2) of above-mentioned general formula (1) expression, preferably 130～9000, more preferably 180～5000, be more preferably 200～2000.Weight-average molecular weight is less than 130 o'clock, the decreased solubility in solvent, the tendency of handling the difficulty that becomes arranged, in case greater than 9000, then the hardness of cured coating film, scuff resistance etc. have the tendency of remarkable variation, thereby not preferred.
As with (methyl) acrylic ester compound (a3) that contains hydroxyl of above-mentioned polyisocyanates compounds (a1) reaction; have no particular limits; for example can enumerate 2-hydroxyethyl (methyl) acrylate; 2-hydroxypropyl (methyl) acrylate; 2-hydroxyl butyl (methyl) acrylate; 4-hydroxyl butyl (methyl) acrylate; 2-hydroxyethyl acryl phosphoric acid ester; 2-(methyl) acryloxy-2-hydroxypropyl phthalic acid ester; 2-hydroxyl-3-(methyl) acryloxy propyl group (methyl) acrylate; caprolactone modification 2-hydroxyethyl (methyl) acrylate; tetramethylolmethane three (methyl) acrylate; Dipentaerythritol five (methyl) acrylate; caprolactone modification Dipentaerythritol five (methyl) acrylate; caprolactone modification tetramethylolmethane three (methyl) acrylate; oxyethane modification Dipentaerythritol five (methyl) acrylate; oxyethane modification tetramethylolmethane three (methyl) acrylate etc.
Among the present invention, when obtaining carbamate (methyl) acrylic ester compound [I], its preparation method is had no particular limits, can enumerate following method:
(i) with the quaternary ammonium salt (a2) of polyisocyanates compounds (a1), above-mentioned general formula (1) expression, contain the method that (methyl) acrylic ester compound (a3) of hydroxyl once adds and makes it to react.
After polyisocyanates compounds (a1) and (methyl) acrylic ester compound (a3) that contains hydroxyl are reacted, make the method for quaternary ammonium salt (a2) reaction of above-mentioned general formula (1) expression.
After the quaternary ammonium salt (a2) that polyisocyanates compounds (a1) and above-mentioned general formula (1) are represented reacts, make the method for (methyl) acrylic ester compound (a3) reaction that contains hydroxyl.But, from the stability and the angle of shortening production time of reaction control, preferred method (ii).
When using method (ii), the hydroxyl of the isocyanate group that preferably makes polyisocyanates compounds (a1) and (methyl) acrylic ester compound (a3) that contains hydroxyl is after making it reaction under the condition of residual isocyanate base, then, make this residual isocyanate group of polyisocyanates compounds (a1) and the hydroxyl reaction of the quaternary ammonium salt (a2) that above-mentioned general formula (1) is represented.
In addition, in this reaction, to promote that reaction is a purpose, the preferred such metal catalyst or 1 of dibutyl tin laurate that uses, the amines catalyst that 8-diazabicyclo [5.4.0] undecylene-7 is such etc., further, preferred 30～90 ℃ of temperature of reaction, more preferably 40～70 ℃ scope.
For the carbamate that obtains like this (methyl) acrylic ester compound (A), carbamate (methyl) acrylic ester compound of especially preferably following general formula (2) expression structure aspect hardness, static resistance, scuff resistance.
Here, R
5Be the residual groups of the amino-formate bond of polyisocyanates compounds (a1), R
6Be residual groups, the R of amino-formate bond of the quaternary ammonium salt (a2) of above-mentioned general formula (1) expression
7Be that residual groups, a of amino-formate bond that contain (methyl) acrylic ester compound (a3) of hydroxyl is that 1～50, preferred 1～5 integer, b are 1～50, preferred 1～5 integers.
Carbamate (methyl) acrylic ester compound of above-mentioned general formula (2) expression structure can prepare by the quaternary ammonium salt (a2) of adjusting polyisocyanates compounds (a1), general formula (1) expression, the reinforced ratio that contains (methyl) acrylic ester compound (a3) of hydroxyl.
Can obtain carbamate (methyl) acrylic ester compound (A) like this, as the weight-average molecular weight of the carbamate that obtains (methyl) acrylic ester compound (A), preferably 500～30000, more preferably 500～15000.Weight-average molecular weight had the tendency of film-forming properties decline less than 500 o'clock, in case greater than 30000, then viscosity is difficult to regard to uprising handle, and in addition, the hardness of cured coating film, scuff resistance etc. have the tendency of remarkable decline, thereby not preferred.
In addition, the weight-average molecular weight of above-mentioned carbamate (methyl) acrylic ester compound (A), it is the weight-average molecular weight that converts and obtain with the polystyrene standard molecular weight, in high-speed liquid chromatography (the Shodex GPC system-11 type that clear and electrician's (strain) makes), 3 pillars of connecting are measured pillar: Shodex GPC KF-806L (eliminating boundary molecular weight: 2 * 10
7, separating ranges: 100～2 * 10
7, number of theoretical plates: 10000 sections/root, filling agent material: styrene diethylene benzene copoly mer, filling agent particle diameter: 10 μ m).
Below, the mensuration of the weight-average molecular weight of carbamate described later (methyl) acrylic ester compound is measured according to the method described above.
In addition, among the present invention, from hardness of film, scuff resistance, static resistance aspect, carbamate (methyl) acrylic ester compound [I] with quaternary ammonium salt base also preferably makes the quaternary ammonium salt (b2) of polyisocyanates compounds (b1) and following general formula (3) expression and contains (methyl) acrylic ester compound (b3) reaction of hydroxyl and carbamate (methyl) acrylic ester compound (B) that obtains.
Here, R
8, R
9Be the alkyl of carbonatoms 1～50, X
2Be Cl, Br, RSO
3(R is alkyl, alkyl oxide, alkylbenzene), m, n be 1 or its above integer, m+n be 2～500.
As above-mentioned polyisocyanates compounds (b1), can enumerate and the identical material of above-mentioned polyisocyanates compounds (a1).
As with the quaternary ammonium salt (b2) of above-mentioned polyisocyanates compounds (b1) reaction, can be the material of structure shown in the above-mentioned general formula (3).
Object lesson as the quaternary ammonium salt (b2) of above-mentioned general formula (3) expression, can enumerate, polyoxyethylene alkyl dimethyl ammonium chloride, polyoxyethylene diethyl ammonium chloride, polyoxyethylene dodecyl methyl ammonium chloride, polyoxyethylene hexadecyl ammonio methacrylate, polyoxyethylene octadecyl methyl ammonium chloride, or these chlorine are by bromine or RSO
3The material that (R is alkyl, alkyl oxide or alkylbenzene) replaces etc.
In above-mentioned, mole number m, the n of oxyethane addition be 1 or it is above, preferably 1～300, m+n is 2～500, preferably 2～100, is more preferably 2～50.
In addition, the weight-average molecular weight of the quaternary ammonium salt (b2) of above-mentioned general formula (3) expression, preferably 100～23000, to be more preferably 100～10000, to be more preferably be 100～4000.Molecular weight is less than 100 o'clock, the decreased solubility in solvent, the tendency of handling the difficulty that becomes arranged, in case greater than 23000, then the hardness of cured coating film, scuff resistance etc. have the tendency of remarkable variation, thereby not preferred.
As with (methyl) acrylic ester compound (b3) that contains hydroxyl of above-mentioned isocyanate ester compound (b1) reaction, can enumerate and the above-mentioned same material of (methyl) acrylic ester compound (a3) that contains hydroxyl.
In carbamate (methyl) acrylic ester compound (B), 1 hydroxyl of the quaternary ammonium salt (b2) that the isocyanate group in the preferred polyisocyanates compounds (b1) and general formula (3) are represented and the hydroxyl that contains (methyl) acrylic ester compound (b3) of hydroxyl form amino-formate bond respectively and the material that forms.
Wherein, preferred especially carbamate (methyl) acrylic ester compound (B) is carbamate (methyl) acrylic ester compound (B1) of structure shown in the following general formula (4) from aspects such as hardness, scuff resistances, in general formula (4), a is that 1～50 integer, preferred 1～5 integer, b are 1～50 integer, preferred 1～5 integer.
Here, R
10Be residual groups, the R of the amino-formate bond of polyisocyanates compounds (b1)
11Be residual groups, the R of carbamate groups of the quaternary ammonium salt (b2) of general formula (3) expression
12Be that residual groups, a of amino-formate bond that contain (methyl) acrylic ester compound (b3) of hydroxyl is that 1～50 integer, b are 1～50 integers.
For example, when polyisocyanates compounds (b1) has 2 isocyanate group, 1 hydroxyl that forms 1 isocyanate group and quaternary ammonium salt (b2) forms amino-formate bond, remaining 1 isocyanate group and the hydroxyl of (methyl) acrylic ester compound (b3) that contains hydroxyl form carbamate (methyl) acrylic ester compound (B1) of amino-formate bond, when polyisocyanates compounds (b1) has 3 isocyanate group, the hydroxyl that forms 1 isocyanate group and quaternary ammonium salt (b2) [or contain hydroxyl (methyl) acrylic ester compound (b3)] forms amino-formate bond, and remaining 2 isocyanate group and the hydroxyl of (methyl) acrylic ester compound (b3) [or quaternary ammonium salt (b2)] that contains hydroxyl form carbamate (methyl) acrylic ester compound (B1) of amino-formate bond.
Form the reaction of above-mentioned amino-formate bond, have no particular limits, can enumerate following method:
(i) polyisocyanates compounds (b1), quaternary ammonium salt (b2), (methyl) acrylic ester compound (b3) of containing hydroxyl are once added the method that makes it to react.
(ii) make polyisocyanates compounds (b1) and (methyl) acrylic ester compound (b3) reaction back of containing hydroxyl, the method that quaternary ammonium salt (b2) is reacted.
After polyisocyanates compounds (b1) and quaternary ammonium salt (b2) are reacted, make the method for (methyl) acrylic ester compound (b3) reaction that contains hydroxyl.
From the stability and the viewpoint that shortens manufacturing time of reaction control, preferred method (ii).
In addition, in such reaction, to promote that reaction is a purpose, the preferred such metal catalyst or 1 of dibutyl tin laurate that uses, the such amines catalyst of 8-diazabicyclo [5.4.0] undecylene-7, further, preferred 30～90 ℃ of temperature of reaction, more preferably at 40～70 ℃.
Can obtain carbamate (methyl) acrylic ester compound (B1) like this, as the weight-average molecular weight of the carbamate that obtains (methyl) acrylic ester compound (B1), preferably 100～100000, more preferably 100～50000.Weight-average molecular weight had the tendency of film-forming properties decline less than 100 o'clock, in case greater than 100000, viscosity just uprises, is difficult to handle, and in addition, the hardness of cured coating film, scuff resistance etc. have the tendency of remarkable decline, thereby not preferred.
In addition, weight-average molecular weight and above-mentioned mensuration similarly.
In carbamate (methyl) acrylic ester compound (B), aspect static resistance, scuff resistance, introduced carbamate (methyl) acrylic ester compound (B2) of structure shown in the following general formula (5) of specific quaternary ammonium salt base in the also preferred molecular skeleton.
Here, R
13Be the residual groups of the amino-formate bond of polyisocyanates compounds (b1), R
14, R
14' be the residual groups (R of amino-formate bond of the quaternary ammonium salt (b2) of above-mentioned general formula (3) expression
14, R
14' can be identical also can be inequality), R
15Be residual groups, the R of amino-formate bond that contains (methyl) acrylic ester compound (b3) of hydroxyl
16Be R
14Or R
15Any one, a is that 1～50 integer, b are that 0～50 integer, c are that 0～50 integer, d are that 0～50 integer, e are 1～30 integers.
Further, in carbamate (methyl) acrylic ester compound (B2) shown in the above-mentioned general formula (5), at carbamate (methyl) acrylic ester compound of structure shown in the more preferably particularly following general formula in aspects such as hardness, scuff resistance (5-1)～(5-4).
When obtaining carbamate (methyl) acrylic ester compound (B2) of general formula (5) expression, have no particular limits, can enumerate following method:
(i) polyisocyanates compounds (b1), quaternary ammonium salt (b2), (methyl) acrylic ester compound (b3) of containing hydroxyl are once added the method that makes it to react.
After polyisocyanates compounds (b1) and (methyl) acrylic ester compound (b3) that contains hydroxyl are reacted, make the method for quaternary ammonium salt (b2) reaction.
After polyisocyanates compounds (b1) and quaternary ammonium salt (b2) are reacted, make the method for (methyl) acrylic ester compound (b3) reaction that contains hydroxyl.
But from the stability and the viewpoint that shortens manufacturing time of reaction control, preferred method (ii).
In addition, in such reaction, to promote that reaction is a purpose, the preferred such metal catalyst or 1 of dibutyl tin laurate that uses, the such amines catalyst of 8-diazabicyclo [5.4.0] undecylene-7, further, preferred 30～90 ℃ of temperature of reaction, more preferably at 40～70 ℃.
Can obtain carbamate (methyl) acrylic ester compound (B2) like this, as the weight-average molecular weight of the carbamate that obtains (methyl) acrylic ester compound (B2), preferably 500～100000, more preferably 500～50000.Weight-average molecular weight had the tendency of film-forming properties decline less than 500 o'clock, in case greater than 100000, then viscosity just uprises, is difficult to handle, and in addition, the hardness of cured coating film or scuff resistance etc. have the tendency of remarkable decline, thereby not preferred.
In addition, weight-average molecular weight and above-mentioned mensuration similarly.
Below, the polymkeric substance [II] with quaternary ammonium salt base is described.
As the polymkeric substance with quaternary ammonium salt base [II], so long as have just having no particular limits of quaternary ammonium salt base, but wherein can enumerate with the unsaturated monomer that contains quaternary ammonium salt base as the multipolymer of copolymer composition, to contain the quaternary ammonium compound of amino unsaturated monomer as the multipolymer of copolymer composition.
As with the unsaturated monomer that contains quaternary ammonium salt base multipolymer as copolymer composition, for example can enumerate the multipolymer that unsaturated monomer that contains quaternary ammonium salt base that is obtained by the quaterisation of (methyl) acrylate of amino alcohol and other copolymerization unsaturated monomer constitute etc.Object lesson as (methyl) acrylate of amino alcohol, can enumerate, N, N-dimethyl aminoethyl (methyl) acrylate, N, N-diethylamino ethyl (methyl) acrylate, N, N-dimethylaminopropyl (methyl) acrylate, N, N-diethylamino propyl group (methyl) acrylate, N, N-dimethylamino butyl (methyl) acrylate, N, N-diethylamino butyl (methyl) acrylate, N, N-dihydroxy ethyl amino-ethyl (methyl) acrylate etc. are particularly suitable for using N, N-dimethyl aminoethyl (methyl) acrylate.
As other copolymerization unsaturated monomer, have no particular limits, can enumerate for example methyl (methyl) acrylate, ethyl (methyl) acrylate, sec.-propyl (methyl) acrylate, normal-butyl (methyl) acrylate, isobutyl-(methyl) acrylate, 2-ethylhexyl (methyl) acrylate, n-hexyl (methyl) acrylate, dodecyl (methyl) acrylate, tridecyl (methyl) acrylate, octadecyl (methyl) acrylate, cyclohexyl (methyl) acrylate, octyl group (methyl) acrylate, isobornyl (methyl) acrylate, two cyclopentyl (methyl) acrylate, allyl chloride, vinylbenzene, alpha-methyl styrene, vinyl acetate, propionate, vinylchlorid, ethene, alkyl vinyl ether, (methyl) vinyl cyanide, the methylene-succinic acid dialkyl, dialkyl fumarate, outside the dialkyl maleate etc., also can use monomer with functional group, as monomer with functional group, have no particular limits, can enumerate the monomer that contains carboxyl that for example in 1 molecule, contains 2 or its above ethene unsaturated group, the monomer that contains hydroxyl, the monomer that contains ehter bond, the monomer that contains epoxy group(ing), contain amide group or methylol, the monomer that contains carbonyl, contain amino monomer etc.
As the monomer that contains carboxyl, for example vinylformic acid, acrylic acid dimer, methacrylic acid, butenoic acid, methylene-succinic acid or its monoesters, fumaric acid or its monoesters, toxilic acid (acid anhydride) or its monoesters, methyl-maleic acid, ricinolic acid or its salt (amine salt, sodium salt, sylvite) can be enumerated, a kind or 2 kinds can be used or more than it.
As the monomer that contains hydroxyl; can enumerate for example 2-hydroxyethyl (methyl) acrylate; 2-hydroxypropyl (methyl) acrylate; the ethyl carbitol acrylate; triglycol (methyl) acrylate; 1; 4-butyleneglycol list (methyl) acrylate; 2-hydroxyl-3-chloropropyl (methyl) acrylate; glycerine list (methyl) acrylate; 2-hydroxyethyl acryl phosphoric acid ester; 4-butylhydroxy acrylate; caprolactone modification 2-hydroxy ethyl methacrylate; polyethyleneglycol (methyl) acrylate; polypropylene glycol list (methyl) acrylate; 2-hydroxyl-3-phenoxy propyl acrylate; 2-acryloxy ethyl succsinic acid; vinylcarbinols etc. can use a kind or 2 kinds or more than it.
As the monomer that contains ehter bond, for example 2-methoxy ethyl (methyl) acrylate, 2-ethoxyethyl group (methyl) acrylate, 2-butoxyethyl group (methyl) acrylate, methoxyl group glycol ether (methyl) acrylate, methoxy poly (ethylene glycol) (methyl) acrylate etc. can be enumerated, a kind or 2 kinds can be used or more than it.
As the monomer that contains epoxy group(ing), for example can enumerate glycidyl (methyl) acrylate, allyl glycidyl ether, (4-(2 for N-, the 3-glycidoxy) 3, the 5-dimethyl benzyl) single (methyl) acrylate of acrylamide, dihydroxyphenyl propane diglycidyl ether etc. can use a kind or 2 kinds or more than it.
As the monomer that contains amide group or methylol, carbonyl, for example acrylamide, Methacrylamide, N-methylol (methyl) acrylamide, butoxy N hydroxymethyl acrylamide, diacetone-acryloamide(DAA), 2-(acetoacetoxy groups) ethyl (methyl) acrylate, allyl group acetylacetic ester etc. can be enumerated, a kind or 2 kinds can be used or more than it.
As containing amino monomer, can enumerate for example N, N-dimethyl aminoethyl (methyl) acrylate, N, N-diethylamino ethyl (methyl) acrylate, N, N-dimethylaminopropyl (methyl) acrylate, N, N-diethylamino propyl group (methyl) acrylate, N, N-dimethylamino butyl (methyl) acrylate, N, N-diethylamino butyl (methyl) acrylate, N, N-dihydroxy ethyl amino-ethyl (methyl) acrylate, dimethylaminopropyl (methyl) acrylamide, diethylamino propyl group (methyl) acrylamide etc. has the vinyl monomer of uncle's amino etc., can use a kind or 2 kinds or more than it.
Among the present invention, to contain the ratio of the unsaturated monomer of quaternary ammonium salt base as the unsaturated monomer that contains quaternary ammonium salt base in the multipolymer of copolymer composition, be 5～95 weight %, preferred especially 20～70 weight %, static resistance deficiency during less than 5 weight %, in case it is not greater than 95 weight %, the tendency of the transparent variation of filming is arranged, thereby preferred.
In addition, the quaternized thing that contains amino unsaturated monomer as the multipolymer of copolymer composition of the present invention can enumerate that the multipolymer that for example will contain amino unsaturated monomer and other copolymerization unsaturated monomer composition carries out quaterisation and the material that forms etc.As containing amino unsaturated monomer, can enumerate (methyl) acrylate of above-mentioned amino alcohol etc., as other copolymerization unsaturated monomer, can enumerate above-mentioned copolymerization unsaturated monomer (containing except the amino unsaturated monomer).
To contain amino unsaturated monomer as the ratio that contains amino unsaturated monomer in the quaternized thing of the multipolymer of copolymer composition, be 5～95 weight %, preferred especially 20～70 weight %, in case it is not static resistance deficiency during less than 5 weight %, greater than 95 weight % then the transparency of filming has the tendency of variation, thereby preferred.
Further, in the above-mentioned in the present invention polymkeric substance [II] with quaternary ammonium salt base, the preferred multipolymer that forms by (methyl) acrylate of amino alcohol and its quaternary ammonium salt and other copolymerization unsaturated monomer.
With the above-mentioned unsaturated monomer that contains quaternary ammonium salt base as the multipolymer of copolymer composition or to contain in the amino preparation of unsaturated monomer as the multipolymers such as multipolymer of copolymer composition, can be according to known polymerization process, water, vinyl acetic monomer, methylethylketone, Virahol etc. separately or mixed solution in the presence of, use the radical polymerization initiator of azobis isobutyronitrile etc. to carry out.
In addition, the number-average molecular weight of the polymkeric substance with quaternary ammonium salt base [II] that obtains is 200～200000, further preferably 1000～100000, number-average molecular weight was less than 200 o'clock, through after a while, static resistance just descends, in case greater than 100000, with the intermiscibility variation of resin, thereby not preferred.
Like this, certainly obtain containing the activity energy-line solidifying type resin composition that carbamate (methyl) acrylic ester compound [I] with above-mentioned quaternary ammonium salt base and the polymkeric substance [II] with quaternary ammonium salt base form among the present invention, content with polymkeric substance [II] of quaternary ammonium salt base, with respect to the carbamate with quaternary ammonium salt base (methyl) acrylic ester compound [I] of 100 weight parts, preferably 0.1～300 weight part, to be more preferably 0.5～100 weight part, to be more preferably be 1～50 weight part.The content of polymkeric substance [II] less than 0.1 weight part, the insufficient tendency of static resistance is arranged, in case greater than 300 weight parts, the transparency of then filming has the tendency of variation, thereby not preferred.
In addition, when obtaining activity energy-line solidifying type resin composition of the present invention, preferably further contain Photoepolymerizationinitiater initiater [III] and form.
As Photoepolymerizationinitiater initiater [III]; just can so long as under the effect of light, produce the material of free radical; have no particular limits; can enumerate for example 4-phenoxy group dichloroacetophenone; the 4-tertiary butyl-dichloroacetophenone; diethoxy acetophenone; 2-hydroxy-2-methyl-1-phenyl propyl-1-ketone; 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl propane-1-ketone; 1-(4-dodecylphenyl)-2-hydroxy-2-methyl propane-1-ketone; 4-(2-hydroxyl-oxethyl)-phenyl (2-hydroxyl-2-propyl group) ketone; the 1-hydroxycyclohexylphenylketone; 2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholino propane-1; benzoin; the benzoin methyl ether; the benzoin ethyl ether; the benzoin isopropyl ether; the benzoin isobutyl ether; benzyldimethylketal; benzophenone; diphenylketone formic acid; the diphenylketone methyl-formiate; the 4-phenyl benzophenone; dihydroxy benaophenonel; 4-benzyl-4 '-dimethyl diphenyl sulfide; 3; 3 '-dimethyl-4-methoxy benzophenone; thioxanthone; the 2-chlorothiaxanthenone; 2-methyl thioxanthone; 2; 4-dimethyl thia anthrone; isopropyl thioxanthone; camphorquinone; dibenzosuberone; 2-ethyl-anthraquinone alcohol; 4 '; 4 "-diethyl isophthaloyl benzene; 3; 3 '; 4; 4 '-four (t-butyl peroxy carbonyl) benzophenone; the alpha-acyloxy ester; acylphosphine oxide; the aminomethyl phenyl glyoxylic ester; benzil; 9, the 10-phenanthrenequione; 4-(2-hydroxyl-oxethyl) phenyl-(2-hydroxyl-2-propyl group) ketone etc.; benzyldimethylketal wherein; the 1-hydroxycyclohexylphenylketone; the benzoyl isopropyl ether; 4-(2-hydroxyl-oxethyl)-phenyl (2-hydroxyl-2-propyl group) ketone; 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone can use suitably.
Further, auxiliary agent as Photoepolymerizationinitiater initiater, also can and use trolamine, tri-isopropanolamine, 4,4 '-dimethylamino benzophenone (Michler's keton), 4,4 '-diethylamino benzophenone, 2-dimethyl aminoethyl phenylformic acid, 4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid (n-butoxy) ethyl ester, 4-dimethylaminobenzoic acid isopentyl ester, 4-dimethylaminobenzoic acid-2-ethylhexyl, 2,4-diethyl thioxanthone, 2,4-di-isopropyl thioxanthone etc.
Among the present invention, except carbamate (methyl) acrylic ester compound [I] with quaternary ammonium salt base with have the polymkeric substance [II] and Photoepolymerizationinitiater initiater [III] of quaternary ammonium salt base, contain carbamate (methyl) acrylic ester compound [IV] different with [I] structure, this is preferred making static resistance not descend, make aspect the hardness, scuff resistance raising of cured coating film.
Carbamate (methyl) acrylic ester compound [IV], be in the polyisocyanates compounds (c1) isocyanate group with the hydroxyl of the polyalkylene derivative (c2) of following general formula (6) expression and the hydroxyl that contains (methyl) acrylate (c3) of hydroxyl, form amino-formate bond respectively and carbamate (methyl) acrylic ester compound that forms.
Here, Y is that alkylidene group, Z are any one in alkyl, (methyl) acryl, allyl group, the acyl group, and p is 1 or its above integer.
Above-mentioned polyisocyanates compounds (c1) is identical with above-mentioned polyisocyanates compounds (a1).
In addition, as the object lesson of the polylalkylene glycol derivatives (c2) of above-mentioned general formula (6) expression, can enumerate
[Z: when being alkyl]
For example, poly glycol monomethyl ether, polyoxyethylene glycol lauryl ether, polyoxyethylene glycol cetyl ether, polyoxyethylene glycol octadecyl ether, polyethylene glycol nonylphenyl ether, polyoxyethylene glycol tridecyl ether, polyoxyethylene glycol oleyl ether, Triton X-100, polyoxyethylene oil base cetyl ether, polypropylene glycol monomethyl ether etc.
[Z: when being (methyl) acryl]
For example, polyethyleneglycol (methyl) acrylate, polypropylene glycol list (methyl) acrylate, polyoxyethylene glycol polypropylene glycol list (methyl) acrylate, poly-(ethylene glycol-tetramethylene glycol) single (methyl) acrylate, poly-(propylene glycol-tetramethylene glycol) single (methyl) acrylate etc.
[Z: when being allyl group]
For example, polyoxyethylene glycol mono allyl ether, polypropylene glycol mono allyl ether, poly-(ethylene glycol and 1,2-propylene glycol) monoallyl ether etc.
[Z: when being acyl group]
For example, polyethylene glycol monolaurate, polypropylene glycol mono-laurate, poly-(ethylene glycol and 1,2-propylene glycol) mono-laurate, polyethylene glycol mono stearate, polyethyleneglycol n-Hexadecane acid esters etc.
In above-mentioned, preferred polyethyleneglycol derivative, oxyethane addition mole number n is 5～500, preferred 5～100, more preferably 5～50.
In addition, with polylalkylene glycol derivatives (c2) weight-average molecular weight of above-mentioned general formula (6) expression, preferred 100～20000, more preferably 200～10000, be more preferably 400～4000.Weight-average molecular weight was less than 100 o'clock, and the surface resistivity of cured coating film has the tendency of increase, in case greater than 20000, hardness of cured coating film, scuff resistance etc. has the tendency of remarkable variation, thereby not preferred.
The hydroxyl value of the polylalkylene glycol derivatives (c2) of above-mentioned general formula (6) expression, preferred 2～560mgKOH/g, more preferably 5.5～280mgKOH/g, be more preferably 14～145mgKOH/g.Hydroxyl value is during less than 2mgKOH/g, and the hardness of cured coating film, scuff resistance etc. have the tendency of remarkable variation, in case greater than 560mgKOH/g, the surface resistivity of cured coating film just has the tendency that becomes big, thereby not preferred.
Form (methyl) acrylic ester compound (c3) that contains hydroxyl of amino-formate bond with isocyanate group in the above-mentioned polyisocyanates compounds (c1), identical with above-mentioned (methyl) acrylic ester compound (a3) that contains hydroxyl.
Carbamate (methyl) acrylic ester compound [IV], by the polylalkylene glycol derivatives (c2) that makes polyisocyanates compounds (c1), general formula (6) expression, (methyl) acrylic ester compound (c3) reaction that contains hydroxyl, isocyanate group in the polyisocyanates compounds (c1) forms amino-formate bond respectively with the hydroxyl of polylalkylene glycol derivatives (c2) and the hydroxyl that contains (methyl) acrylic ester compound (c3) of hydroxyl and obtains.
Carbamate (methyl) acrylic ester compound [IV] can be used with the same reaction method of above-mentioned carbamate (methyl) acrylic ester compound (A) to obtain.
The weight-average molecular weight of the carbamate that obtains like this (methyl) acrylic ester compound [IV], preferably 100～100000, be more preferably 100～50000.Weight-average molecular weight is less than 100 o'clock, and the surface resistivity of cured coating film has the tendency that becomes big, in case greater than 100000, then become high viscosity and be difficult to handle, not preferred at aspects such as the hardness of cured coating film, scuff resistances in addition yet.
The mensuration of weight-average molecular weight is identical with above-mentioned carbamate (methyl) acrylic ester compound [I].
Among the present invention, except carbamate (methyl) acrylic ester compound [I] with quaternary ammonium salt base, polymkeric substance [II] and Photoepolymerizationinitiater initiater [III] with quaternary ammonium salt base so that carbamate (methyl) acrylic ester compound [IV], preferably also contain ethylene unsaturated monomer [V] aspect the raisings such as hardness of film, scuff resistance making.
In addition, the wet fastness that requires when being used for optical applications in the past, though by cooperating ethylene unsaturated monomer to improve, the tendency that has the static resistance of making to descend on the contrary is so exist suitable restriction in the cooperation of ethylene unsaturated monomer.And in the present invention,, static resistance is descended even cooperate ethylene unsaturated monomer, also can become resin combination with the outstanding effect of wet fastness.
As ethylene unsaturated monomer [V], can be the monomer that in 1 molecule, has 1 or the ethene unsaturated group more than it, can enumerate monofunctional monomer, 2 functional monomers, 3 officials can or its above monomer.
As monofunctional monomer, can enumerate for example vinylbenzene; Vinyl toluene; chlorostyrene; alpha-methyl styrene; (methyl) methyl acrylate; (methyl) ethyl propenoate; vinyl cyanide; vinyl acetate; 2-hydroxyethyl (methyl) acrylate; 2-hydroxypropyl (methyl) acrylate; 2-hydroxyl butyl (methyl) acrylate; phenoxy group ethyl (methyl) acrylate; 2-phenoxy group-2-hydroxypropyl (methyl) acrylate; 2-hydroxyl-3-phenoxy propyl (methyl) acrylate; 3-chloro-2-hydroxypropyl (methyl) acrylate; glycerine list (methyl) acrylate; glycidyl (methyl) acrylate; dodecyl (methyl) acrylate; cyclohexyl (methyl) acrylate; isobornyl (methyl) acrylate; three ring decyl (methyl) acrylate; dicyclopentenyl (methyl) acrylate; normal-butyl (methyl) acrylate; hexyl (methyl) acrylate; heptyl (methyl) acrylate; octyl group (methyl) acrylate; nonyl (methyl) acrylate; decyl (methyl) acrylate; isodecyl (methyl) acrylate; dodecyl (methyl) acrylate; Octadecane base (methyl) acrylate; benzyl (methyl) acrylate; phenyl ethylene oxide modification (n=2) (methyl) acrylate; nonyl phenol epoxy pronane modification (n=2.5) (methyl) acrylate; half (methyl) acrylate of the phthalic acid derivative of 2-(methyl) acryl oxygen base-2-hydroxypropyl phthalic acid ester etc.; furfuryl group (methyl) acrylate; Trivalin SF (methyl) acrylate; benzyl (methyl) acrylate; butoxyethyl group (methyl) acrylate; allyl group (methyl) acrylate; acryloyl morpholine; 2-hydroxyethyl acrylamide; N-methylol (methyl) acrylamide; the N-vinyl pyrrolidone; the 2-vinyl pyridine; 2-(methyl) acryl oxygen ethyl acid phosphoric acid ester monoesters etc.
As 2 functional monomers; can enumerate for example ethylene glycol bisthioglycolate (methyl) acrylate; glycol ether two (methyl) acrylate; Tetraglycol 99 two (methyl) acrylate; polyoxyethylene glycol two (methyl) acrylate; propylene glycol two (methyl) acrylate; dipropylene glycol two (methyl) acrylate; polypropylene glycol two (methyl) acrylate; butyleneglycol two (methyl) acrylate; neopentyl glycol two (methyl) acrylate; oxyethane modified bisphenol A type (methyl) acrylate; epoxy pronane modification bisphenol A-type (methyl) acrylate; 1,6-hexylene glycol two (methyl) acrylate; glycerine two (methyl) acrylate; tetramethylolmethane two (methyl) acrylate; ethylene glycol bisthioglycolate glycidyl ether two (methyl) acrylate; glycol ether diglycidyl ether two (methyl) acrylate; phthalic acid diglycidyl ester two (methyl) acrylate; hydroxyl trimethylacetic acid modification neopentyl glycol two (methyl) acrylate; cyamelide oxyethane modification (methyl) acrylate; 2-(methyl) acryl oxygen ethyl acid phosphoric acid ester diester etc.
As 3 officials can or monomer more than it, can enumerate for example trimethylolpropane tris (methyl) acrylate; tetramethylolmethane three (methyl) acrylate; tetramethylolmethane four (methyl) acrylate; Dipentaerythritol five (methyl) acrylate; Dipentaerythritol six (methyl) acrylate; three (methyl) acryl oxygen oxyethyl group TriMethylolPropane(TMP); glycerine poly epihydric alcohol base ether gathers (methyl) acrylate; cyamelide oxyethane modification triacrylate; oxyethane modification Dipentaerythritol five (methyl) acrylate; oxyethane modification Dipentaerythritol six (methyl) acrylate; oxyethane modification tetramethylolmethane three (methyl) acrylate; oxyethane modification tetramethylolmethane four (methyl) acrylate etc.
Also can enumerate other acrylic acid Mick that affixture or 2-acryl oxygen ethyl dicarboxylic acid monoesters; as acrylic acid Mick that affixture, can enumerate for example acrylic acid dimer, methacrylic acid dimer, vinylformic acid tripolymer, methacrylic acid tripolymer, the vinylformic acid tetramer, the methacrylic acid tetramer etc.In addition; as 2-acryl oxygen ethyl dicarboxylic acid monoesters; be carboxylic acid with specified substituent, for example 2-acryl oxygen ethyl monomester succinate, 2-methacryloyl oxygen ethyl monomester succinate, 2-acryl oxygen ethylbenzene dioctyl phthalate monoesters, 2-methacryloyl oxygen ethylbenzene dioctyl phthalate monoesters, 2-acryl oxygen ethyl hexahydro-phthalic acid monoesters, 2-methacryloyl oxygen ethyl hexahydro-phthalic acid monoesters etc.And then, also can enumerate other oligomer ester acrylate etc.
Can use above-mentioned these ethylene unsaturated monomers [V] individually, also can be also with 2 kinds or more than it.
Among the present invention, except carbamate (methyl) acrylic ester compound [I] with quaternary ammonium salt base, polymkeric substance [II] and Photoepolymerizationinitiater initiater [III], carbamate (methyl) acrylic ester compound [IV], ethylene unsaturated monomer [V] with quaternary ammonium salt base, for further improving the static resistance effect, also can cooperate static inhibitor [VI].
As static inhibitor [VI], can enumerate anionic antistatic agent, higher alcohols alkylene oxide affixture, polyalkylene glycol fatty acid ester of the cationic static inhibitor, aliphatic sulfonate, higher alcohol sulfate salt, higher alcohols alkylene oxide affixture sulfuric acid, high alcohol phosphate salt, higher alcohols alkylene oxide affixture phosphate ester salt etc. of quaternary ammonium salt for example etc.
Among the present invention, the use level of above-mentioned Photoepolymerizationinitiater initiater [III], has carbamate (methyl) acrylic ester compound [I] of quaternary ammonium salt base (when cooperating carbamate (methyl) acrylic ester compound [IV] or ethylene unsaturated monomer [V] with respect to 100 weight parts, be total 100 weight parts of [I] and [IV] and/or [V]), preferably 1～10 weight part, to be more preferably 1～8 weight part, to be more preferably be 1～5 weight part.Use level is during less than 1 weight part, the tendency extremely slowly that becomes of the curing speed during ultraviolet curing, in case even greater than 10 weight parts add can not improve solidified nature, be waste.
In addition, use level as carbamate (methyl) acrylic ester compound [IV], have carbamate (methyl) acrylic ester compound [I] of quaternary ammonium salt base with respect to 100 weight parts, preferably 1～500 weight part, to be more preferably 1～200 weight part, to be more preferably be 5～100 weight parts.Use level is during less than 1 weight part, and the interpolation that is difficult to obtain hardness of film, scuff resistance etc. improves effect, in case become big greater than the surface resistivity of 500 weight parts, cured coating film, thus not preferred.
In addition, use level as ethylene unsaturated monomer [V], with respect to carbamate (methyl) acrylic ester compound [I] of 100 weight part quaternary ammonium salt bases, preferably 1～500 weight part, to be more preferably 1～200 weight part, to be more preferably be 5～100 weight parts.Use level is during less than 1 weight part, and the interpolation that is difficult to obtain hardness of film improves effect, in case greater than 500 weight parts, then the surface resistivity of cured coating film has the tendency that becomes big, thereby not preferred.
Use level as static inhibitor [VI], the total amount that has carbamate (methyl) acrylic ester compound [I] with the polymkeric substance with quaternary ammonium salt base [II] of quaternary ammonium salt base with respect to 100 weight parts (and then is cooperating carbamate (methyl) acrylic ester compound [IV], during ethylene unsaturated monomer [V], be the total amount of [I], [II], [IV], [V]), preferably 1～100 weight part, to be more preferably 1～50 weight part, to be more preferably be 2～20 weight parts.Use level is difficult to obtain anlistatig interpolation and improves effect during less than 1 weight part, in case greater than 100 weight parts, filming becomes embrittlement or static resistance through descending after a while, thereby not preferred.
In addition, remove above-mentioned carbamate (methyl) acrylic ester compound [I] with quaternary ammonium salt base, polymkeric substance [II] with quaternary ammonium salt base, Photoepolymerizationinitiater initiater [III], carbamate (methyl) acrylic ester compound [IV], ethylene unsaturated monomer [V], static inhibitor [VI] also can cooperate in addition, electrolytic salt, dyestuff, pigment, oil, softening agent, the wax class, siccative, dispersion agent, wetting agent, emulsifying agent, gelating agent, stablizer, defoamer, flow agent, thixotropy gives agent, antioxidant, fire retardant, weighting agent, toughener, matting agent, linking agent etc.
Can obtain the activity energy-line solidifying type resin composition that contains carbamate (methyl) acrylic ester compound [I] with above-mentioned quaternary ammonium salt base and the formation of the polymkeric substance [II] with quaternary ammonium salt base of the present invention like this.As required, said composition also can cooperate organic solvent, adjustment viscosity to use.As organic solvent, can enumerate for example cellosolve class of vinyl acetic monomer, N-BUTYL ACETATE, toluene, dimethylbenzene, methyl alcohol, ethanol, propyl alcohol, butanols, acetone, mibk, methylethylketone, pimelinketone, ethyl cellosolve etc.The propylene glycol ethers of propylene glycol monomethyl ether etc., Pyranton etc.
Activity energy-line solidifying type resin composition of the present invention, be applied to object after, by the irradiation active energy ray make its curing.
As such object, have no particular limits, can enumerate the such polyolefin resin of polyethylene for example, polypropylene, polycyclopentadiene, polycarbonate, polyester, ABS resin, acrylic resin etc. and moulding product (film, sheet, cup etc.) thereof, metal, glass etc.
As active energy ray, can utilize the hertzian wave of the light, X line, γ line etc. of far ultraviolet rays yue, ultraviolet ray, near-ultraviolet ray, infrared rays etc., in addition, can utilize electronics line, proton line, neutron line etc., but from considerations such as the degree of purchasing easily of curing speed, irradiating unit, prices, it is favourable being cured with uviolizing.In addition, when carrying out electron irradiation, even also can solidify without Photoepolymerizationinitiater initiater [III].
As making it the solidified method by irradiation ultraviolet radiation, use the high voltage mercury lamp that sends 150～450nm wavelength region light, ultrahigh pressure mercury lamp, carbon arc lamp, metal halide lamp, xenon lamp, chemical lamp etc., with 100～3000mJ/cm
2Degree irradiation just can.
After the uviolizing, as required, heat, can realize that solidified is complete.
Activity energy-line solidifying type resin composition of the present invention; because contain carbamate (methyl) acrylic ester compound [I] with quaternary ammonium salt base and polymkeric substance [II] with quaternary ammonium salt base; so at hardness of film; scuff resistance; static resistance; particularly there is not the humidity interdependence; static resistance under low humidity also shows very outstanding; further; even cooperation ethylene unsaturated monomer; also form the activity energy-line solidifying type resin composition of the coat that makes the few excellent of static resistance decline; at coating; tackiness agent; caking agent; tackiness agent; ink; protection applies agent; tackify applies agent; the magnetic application of adhesive; the sand spraying device mulch film; plates etc. use as the material that forms various mulch films.Wherein, it is very useful using as the coating agent of optical thin film.
Embodiment
Below, enumerate embodiment and be described more specifically the present invention.
In addition, " % " among the embodiment, " part ", unless stated otherwise, the expression weight standard.
The synthesis example of carbamate (methyl) acrylic ester compound [I]
(carbamate (methyl) acrylic ester compound (A-1))
Thermometer is being housed, stirrer, water-cooled condenser, in the four-hole boiling flask of nitrogen access tube, 3 aggressiveness (a1) (isocyanate group content 21.3%) that add the hexamethylene diisocyanate of 128.1g (0.22 mole), 0.56g 2, the 6-di-tertiary butyl methyl phenol, 0.12g dibutyl tin laurate, 507.5g (0.44 mole) Dipentaerythritol five acrylate (mixture (hydroxyl value 48mgKOH/g) with Dipentaerythritol five acrylate and dipentaerythritol acrylate adds) (a3), 300.0g methylethylketone, under 60 ℃, make it to react 2 hours, become at 1.0% o'clock at the residual isocyanate base, be cooled to 45 ℃, in the time of 45 ℃, in reaction system, add 64.4g (0.22 mole) dimethyl alkyl hydroxyethylsulfonic acid ammonium (a2) again [with compound (this grease of bamboo (strain) system of following structural formula (7) expression, (molecular weight 297.0))], make at 60 ℃ and reacted 3 hours down, the residual isocyanate base becomes at 0.1% o'clock and finishes reaction, obtains carbamate (methyl) acrylic ester compound (A-1) (resin concentration 70%).
Here, R is the alkyl of carbonatoms 8.
The weight-average molecular weight of the carbamate that obtains (methyl) acrylic ester compound (A-1) is 1730.
(carbamate (methyl) acrylic ester compound (A-2))
Thermometer is being housed, stirrer, water-cooled condenser, in the four-hole boiling flask of nitrogen access tube, 3 aggressiveness (a1) (isocyanate group content 21.1%) that add the hexamethylene diisocyanate of 145.6g (0.24 mole), 0.56g 2, the 6-di-tertiary butyl methyl phenol, 0.12g dibutyl tin laurate, 445.9g (0.36 mole) Dipentaerythritol five acrylate (mixture (hydroxyl value 46mgKOH/g) with Dipentaerythritol five acrylate and dipentaerythritol acrylate adds) (a3), 300.0g methylethylketone, under 60 ℃, make it to react 2 hours, become at 1.7% o'clock at the residual isocyanate base, be cooled to 45 ℃, in the time of 45 ℃, in reaction system, add 108.5g dimethyl alkyl hydroxyethylsulfonic acid ammonium (0.36 mole) again (a2) [with compound (this grease of bamboo (strain) system of following structural formula (7) expression, (molecular weight 297.0))], it was reacted 3 hours down at 60 ℃, the residual isocyanate base becomes at 0.1% o'clock and finishes reaction, obtains carbamate (methyl) acrylic ester compound (A-2) (resin concentration 70%).
The weight-average molecular weight of the carbamate that obtains (methyl) acrylic ester compound (A-2) is 1310.
(carbamate (methyl) acrylic ester compound (B1-1))
Thermometer is being housed, stirrer, water-cooled condenser, in the four-hole boiling flask of nitrogen access tube, 3 aggressiveness (b1) (isocyanate group content 21.3%) that add the hexamethylene diisocyanate of 105.1g (0.18 mole), 1.4g 2, the 6-di-tertiary butyl methyl phenol, 0.02g dibutyl tin laurate, 433.3g (0.44 mole) Dipentaerythritol five acrylate (mixture (hydroxyl value 46mgKOH/g) with Dipentaerythritol five acrylate and dipentaerythritol acrylate adds) (b3), 300.0g methylethylketone, under 60 ℃, make it to react 3 hours, become at 0.9% o'clock at the residual isocyanate base, be cooled to 45 ℃, in the time of 45 ℃, in reaction system, add 161.60g (0.18 mole) polyxyethylated methyl ammonium salt (b2) [ラ イ オ Application (strain) system again, " エ ソ カ one De C/25 "] (weight-average molecular weight 910.50, oxyethane addition mole number 15), under 50 ℃, make its reaction 3 hours, the residual isocyanate base becomes at 0.1% o'clock and finishes reaction, obtains carbamate (methyl) acrylic ester compound (B1-1) (resin concentration 70%).
The weight-average molecular weight of the carbamate that obtains (methyl) acrylic ester compound (B1-1) is 2170.
(carbamate (methyl) acrylic ester compound (B2-1))
Thermometer is being housed, stirrer, water-cooled condenser, in the four-hole boiling flask of nitrogen access tube, 3 aggressiveness (b1) (isocyanate group content 21.3%) that add the hexamethylene diisocyanate of 204.9g (0.35 mole), 1.4g 2, the 6-di-tertiary butyl methyl phenol, 0.02g dibutyl tin laurate, 337.4g pentaerythritol triacrylate (0.69 mole) (weight-average molecular weight 465.64, hydroxyl value 120.5mgKOH/g) (Osaka organic chemistry industry (strain) system, " PVC ス コ one ト #300 ") (b3), 300.0g methylethylketone, under 60 ℃, make it to react 3 hours, become at 1.9% o'clock at the residual isocyanate base, be cooled to 45 ℃, in the time of 45 ℃, in reaction system, add the polyxyethylated methyl ammonium salt of 157.68g (0.17 mole) (ラ イ オ Application (strain) system again, " エ ソ カ one De C/25 ") (weight-average molecular weight 910.50, oxyethane addition mole number 15) (b2), under 50 ℃, make its reaction 3 hours, the residual isocyanate base becomes at 0.1% o'clock and finishes reaction, obtains carbamate (methyl) acrylic ester compound (B2-1) (resin concentration 70%).
The weight-average molecular weight of the carbamate that obtains (methyl) acrylic ester compound (B2-1) is 1800.
(carbamate (methyl) acrylic ester compound [I '])
Thermometer is being housed, stirrer, water-cooled condenser, in the four-hole boiling flask of nitrogen access tube, 3 aggressiveness (isocyanate group content 21.1%) that add the hexamethylene diisocyanate of 239.4g (0.40 mole), 2.0g 2, the 6-di-tertiary butyl methyl phenol, 0.02g dibutyl tin laurate, below 60 ℃, with the pentaerythritol triacrylate (hydroxyl value 125.4mgKOH/g) that dripped 713.9g (1.47 moles) in about 1 hour (Osaka organic chemistry industry (strain) system, " PVC ス コ one ト #300 "), make it to react 8 hours at 60 ℃, become at 0.3% o'clock at the residual isocyanate base, finish reaction, obtain carbamate (methyl) acrylic ester compound [I '] (resin concentration 100%).
The weight-average molecular weight of the carbamate that obtains (methyl) acrylic ester compound [I '] is 6800.
Synthesis example with polymkeric substance [II] of quaternary ammonium salt base
(polymkeric substance [II-1]) with quaternary ammonium salt base
Thermometer is being housed, stirrer, water-cooled condenser, in the four-hole boiling flask of nitrogen access tube, add 48.1g (0.34 mole) N, N-dimethyl amino ethyl methacrylate (common prosperity society chemistry (strain) system, " ラ イ ト エ ス テ Le DM ") and 158.6g (0.48 mole) N, the quaternized thing of N-dimethyl amino ethyl methacrylate (common prosperity society chemistry (strain) system, " ラ イ ト エ ス テ Le DQ-100 ")), the 2-ethylhexyl methacrylic ester of (72.1g 0.39 mole), 2.38g azobis isobutyronitrile, 480.8g Virahol, 240.4g methylethylketone, carry out nitrogen replacement after stirring beginning, be warmed up under 80 ℃, make it to react 8 hours, obtain polymkeric substance [II-1] (resin concentration 28%).
(polymkeric substance [II-2]) with quaternary ammonium salt base
Use [go one セ Off ア イ マ one C-670 (acrylic resin contains quaternary ammonium salt)] (water dilution product, resinous principle concentration 30%) of Japanese synthetic chemistry (strain) system.
The synthesis example of carbamate (methyl) acrylic ester compound [IV]
(carbamate (methyl) acrylic ester compound [IV-1])
Thermometer is being housed, stirrer, water-cooled condenser, in the four-hole boiling flask of nitrogen access tube, 3 aggressiveness (c1) (isocyanate group content 21.3%) of the hexamethylene diisocyanate of adding 147.3g (0.25 mole) and Dipentaerythritol five acrylate (0.50 mole) (adding with Dipentaerythritol five acrylate of 607.2g and the mixture (hydroxyl value 46mgKOH/g) of dipentaerythritol acrylate) are (c3), 2.0g 2, the 6-di-tertiary butyl methyl phenol, 0.10g dibutyl tin laurate, under 60 ℃, make it to react 5 hours, become at 1.4% o'clock at the residual isocyanate base, be cooled to 50 ℃, in the time of 55 ℃ in reaction system with being added dropwise to 245.5g (0.26 mole) poly glycol monomethyl ether (c2) (weight-average molecular weight 957.51 in about 1 hour, oxyethane addition mole number 22, hydroxyl value 58.6mgKOH/g), it was reacted 3 hours down at 60 ℃, the residual isocyanate base becomes at 0.1% o'clock and finishes reaction, obtains carbamate (methyl) acrylic ester compound [IV-1] (resin concentration 100%).
The weight-average molecular weight of the carbamate that obtains (methyl) acrylic ester compound [IV-1] is 4000.
The example of ethylene unsaturated monomer [V]
(ethylene unsaturated monomer [V-1])
Use tetramethylol methane tetraacrylate (common prosperity society chemistry (strain) system, " ラ イ ト ア Network リ レ one ト PE-4A ").
Embodiment 1～20 and comparative example 1～5.
(activity energy-line solidifying type resin composition)
With above-mentioned carbamate (methyl) acrylic ester compound [I] ((A-1), (A-2), (B1-1) (B2-1)) or [I '], polymkeric substance [II] ([II-1] with quaternary ammonium salt base, [II-2]), carbamate (methyl) acrylic ester compound [IV-1], ethylene unsaturated monomer [V-1] and Photoepolymerizationinitiater initiater [III] (1-hydroxycyclohexylphenylketone (チ バ ス ペ シ ヤ リ テ イ ケ ミ カ Le ズ (strain) system, " イ Le ガ キ ユ ア 184 ")) convert with solids component, the ratio represented with table 1～3 cooperates, being diluted to the resinous principle of removing Photoepolymerizationinitiater initiater with propylene glycol monomethyl ether is 20%, obtains activity energy-line solidifying type resin composition.
With the activity energy-line solidifying type resin composition that obtains, on bonding easily polyethylene terephthalate film, with No.8 bar varnishing machine, making dried thickness become 5 μ m is coated with like that, 90 ℃ of dryings after 3 minutes, with the high voltage mercury lamp of 1 80W, from the height of 18cm, with the transfer rate of 1m/min, 2 (cumulative exposure 450mJ/cm of uviolizing
2), form cured coating film, carry out following evaluation.
(appearance of film)
The outward appearance of the cured coating film that visual observations obtains (degree of spot, albefaction).Outward appearance is estimated on 2 stages ground, good be evaluated as zero, spottiness and albefaction be *.
(hardness of film)
For cured coating film, be benchmark with JIS K 5400, measure pencil hardness.
(scuff resistance)
For cured coating film, visual observations is with the surface of the steel wool #0000 that has applied the 1Kg load behind reciprocal 40 times of cured coating film, and metewand is as follows
◎ ... do not hinder fully or almost do not hinder
Zero ... a little a bit hinder
△ ... more or less hinder
* ... film and turn white due to wound
(surface resistivity)
For cured coating film, use the resistrivity meter " Ha イ レ ス one UP " of Mitsubishi Chemical's (strain) system, use the URS detector, measure the following surface resistivity of (1) 20 ℃ * 65%RH the environment ((Ω/) of the surface resistivity under Ω/) and (2) 20 ℃ * 65%RH environment.
The evaluation result of embodiment and comparative example is shown in table 1～3.
Table 1
| [I] | [II] | [III] | [IV] | [V] | Appearance of film | Hardness of film | Scuff resistance | Surface resistivity (Ω/) | ||
| (1) | (2) | |||||||||
| Embodiment 1 | (A-1) (92.0) | [II-1] (8.0) | (2.6) | - | - | ○ | 2H | ○ | 5.0×10 8 | 1.5×10 9 |
| Embodiment 2 | (A-1) (97.0) | [II-2] (3.0) | (2.7) | - | - | ○ | 2H | ○ | 4.0×10 8 | 3.0×10 9 |
| Embodiment 3 | (A-1) (36.8) | [II-1] (3.2) | (3.4) | [IV-1] (60.0) | - | ○ | 3H | ◎ | 8.0×10 8 | 1.0×10 9 |
| Embodiment 4 | (A-1) (36.8) | [II-1] (3.2) | (3.4) | - | [V-1] (60.0) | ○ | 3H | ◎ | 1.0×10 9 | 3.5×10 9 |
| Embodiment 5 | (A-1) (36.8) | [II-1] (3.2) | (3.4) | [IV-1] (20.0) | [V-1] (40.0) | ○ | 3H | ◎ | 9.0×10 8 | 1.5×10 9 |
| Embodiment 6 | (A-2) (92.0) | [II-1] (8.0) | (2.6) | - | - | ○ | H | △ | 1.0×108 | 4.0×108 |
| Embodiment 7 | (A-2) (97.0) | [II-2] (3.0) | (2.7) | - | - | ○ | H | △ | 9.0×10 7 | 5.0×10 8 |
| Embodiment 8 | (A-2) (36.8) | [II-1] (3.2) | (3.4) | [IV-1] (60.0) | - | ○ | 2H | ○ | 4.0×10 8 | 6.5×10 8 |
| Embodiment 9 | (A-2) (36.8) | [II-1] (3.2) | (3.4) | - | [V-1] (60.0) | ○ | 2H | ◎ | 7.0×10 8 | 1.0×10 9 |
| Embodiment 10 | (A-2) (36.8) | [II-1] (3.2) | (3.4) | [IV-1] (20.0) | [V-1] (40.0) | ○ | 2H | ◎ | 5.0×10 8 | 7.5×10 8 |
Numeric representation solids component ratio, "-" expression in () are not added.
Table 2
| [I] | [II] | [III] | [IV] | [V ] | Appearance of film | Hardness of film | Scuff resistance | Surface resistivity (Ω/) | ||
| (1) | (2) | |||||||||
| Embodiment 11 | (B1-1) (92.0) | [II-1] (8.0) | (2.6) | - | - | ○ | H | △ | 1.5×10 8 | 5.0×10 8 |
| Embodiment 12 | (B1-1) (97.0) | [II-2] (3.0) | (2.7) | - | - | ○ | H | △ | 9.0×10 7 | 5.0×10 8 |
| Embodiment 13 | (B1-1) (36.8) | [II-1] (3.2) | (3.4) | [IV-1] (60.0) | - | ○ | 2H | ○ | 5.0×10 8 | 8.0×10 8 |
| Embodiment 14 embodiment 15 | (B1-1) (36.8) | [II-1] (3.2) | (3.4) | - | [V-1] (60.0) | ○ | 2H | ◎ | 8.0×10 8 | 1.0×10 9 |
| (B1-1) (36.8) | [II-1] (3.2) | (3.4) | [IV-1] (20.0) | [V-1] (40.0) | ○ | 2H | ◎ | 7.0×10 8 | 9.5×10 8 | |
| Embodiment 16 | (B2-1) (92.0) | [II-1] (8.0) | (2.6) | - | - | ○ | HB | △ | 5.0×10 9 | 8.0×10 9 |
| Embodiment 17 | (B2-1) (97.0) | [II-2] (3.0) | (2.7) | - | - | ○ | HB | △ | 3.0×10 9 | 9.0×10 9 |
| Embodiment 18 | (B2-1) (36.8) | [II-1] (3.2) | (3.4) | [IV-1] (60.0) | - | ○ | H | ○ | 7.0×10 9 | 9.0×10 9 |
| Embodiment 19 | (B2-1) (36.8) | [II-1] (3.2) | (3.4) | - | [V-1] (60.0) | ○ | H | ◎ | 8.0×10 9 | 1.0×10 10 |
| Embodiment 20 | (B2-1) (36.8) | [II-1] (3.2) | (3.4) | [IV-1] (20.0) | [V-1] (40.0) | ○ | H | ◎ | 8.0×10 9 | 9.5×10 9 |
Numeric representation solids component ratio, "-" expression in () are not added.
Table 3
| [I] | [II] | [III] | [IV] | [V] | Appearance of film | Hardness of film | Scuff resistance | Surface resistivity (Ω/) | ||
| (1) | (2) | |||||||||
| Comparative example 1 | (A-1) (100.0) | - | (2.8) | - | - | ○ | 2H | ○ | 8.0×10 10 | 6.0×10 13 |
| Comparative example 2 | (B1-1) (100.0) | - | (2.8) | - | - | ○ | H | ○ | 2.0×10 8 | 4.0×10 12 |
| Comparative example 3 | (B2-1) (100.0) | - | (2.8) | - | - | ○ | HB | ◎ | 1.0×10 11 | 8.0×10 13 |
| Comparative example 4 | (I’) (95.0) | [II-1] (5.0) | (2.7) | - | - | × | 3H | ◎ | 5.0×10 8 | 5.0×10 9 |
| Comparative example 5 | - | [II-1] (5.0) | (2.7) | - | [V-1] (95.0) | × | 4H | ◎ | 8.0×10 8 | 3.0×10 9 |
Numeric representation solids component ratio, "-" expression in () are not added.
Utilizability on the industry
Activity energy-line solidifying type resin composition of the present invention; because containing carbamate (methyl) acrylic ester compound [I] with quaternary ammonium salt base and the polymer [II] with quaternary ammonium salt base forms; so show very outstanding effect in hardness of film, marresistance, antistatic behaviour, special antistatic behaviour under low humidity; make the few effect of antistatic behaviour decline even further cooperate ethylene unsaturated monomer also to show; at coating, adhesive, bonding agent, adhesive, ink, protection coating agent, tackify coating agent, magnetic application of adhesive, sanding machine coverlay, plate etc., be useful as the material that forms various coverlays. Wherein, the plastics that is used as blooming is very useful.
Claims (13)
1. an activity energy-line solidifying type resin composition is characterized in that, contains carbamate (methyl) acrylic ester compound [I] with quaternary ammonium salt base and the polymkeric substance [II] with quaternary ammonium salt base and forms.
2. activity energy-line solidifying type resin composition as claimed in claim 1, it is characterized in that, carbamate (methyl) acrylic ester compound [I] with quaternary ammonium salt base, be to make the quaternary ammonium salt (a2) of polyisocyanates compounds (a1) and following general formula (1) expression and contain carbamate (methyl) acrylic ester compound (a3) reaction of hydroxyl and carbamate (methyl) acrylic ester compound (A) that obtains
Here, R
1, R
2, R
3Be alkyl, the X of carbonatoms 1～50
1Be Cl, Br, R
4SO
3(R
4Be alkyl, alkyl oxide, alkylbenzene), n is 1～200 integer.
3. activity energy-line solidifying type resin composition as claimed in claim 2, it is characterized in that, carbamate (methyl) acrylic ester compound (A) is that the hydroxyl of the isocyanate group that makes polyisocyanates compounds (a1) and (methyl) acrylic ester compound (a3) that contains hydroxyl makes under the residual condition of carbamate groups after the reaction, then, this residual isocyanate base that makes polyisocyanates compounds (a1) obtains with hydroxyl reaction with the quaternary ammonium salt (a2) of above-mentioned general formula (1) expression.
4. as claim 2 or 3 described activity energy-line solidifying type resin compositions, it is characterized in that carbamate (methyl) acrylic ester compound (A) is carbamate (methyl) acrylic ester compound with following general formula (2) expression,
Here, R
5Be the residual groups of the amino-formate bond of polyisocyanates compounds (a1), R
6Be residual groups, the R of amino-formate bond of the quaternary ammonium salt (a2) of above-mentioned general formula (1) expression
7Be that residual groups, a of amino-formate bond that contain (methyl) acrylic ester compound (a3) of hydroxyl is that 1～50 integer, b are 1～50 integers.
5. activity energy-line solidifying type resin composition as claimed in claim 1, it is characterized in that, carbamate (methyl) acrylic ester compound [I] that contains quaternary ammonium salt base is to make the quaternary ammonium salt (b2) of polyisocyanates compounds (b1) and following general formula (3) expression and contain (methyl) acrylic ester compound (b3) reaction of hydroxyl and carbamate (methyl) acrylic ester compound (B) that obtains
Here, R
8, R
9Be the alkyl of carbonatoms 1～50, X
2Be Cl, Br, RSO
3(R is alkyl, alkyl oxide, alkylbenzene), m, n be 1 or its above integer, m+n be 2～500.
6. activity energy-line solidifying type resin composition as claimed in claim 5 is characterized in that, carbamate (methyl) acrylic ester compound (B) is carbamate (methyl) acrylic ester compound (B1) of following general formula (4) expression,
Here, R
10Be residual groups, the R of the amino-formate bond of polyisocyanates compounds (b1)
11Be residual groups, the R of carbamate groups of the quaternary ammonium salt (b2) of general formula (3) expression
12Residual groups, a of amino-formate bond that contains (methyl) acrylic ester compound (b3) of hydroxyl is that 1～50 integer, b are 1～50 integers.
7. activity energy-line solidifying type resin composition as claimed in claim 5 is characterized in that, carbamate (methyl) acrylic ester compound (B) is carbamate (methyl) acrylic ester compound (B2) of following general formula (5) expression,
Here, R
13Be the residual groups of the amino-formate bond of polyisocyanates compounds (b1), R
14, R
14Be the residual groups (R of amino-formate bond of the quaternary ammonium salt (b2) of above-mentioned general formula (3) expression
14, R
14' can be identical also can be inequality), R
15Be residual groups, the R of amino-formate bond that contains (methyl) acrylic ester compound (b3) of hydroxyl
16Be R
14Or R
15Any one, a is that 1～50 integer, b are that 0～50 integer, c are that 0～50 integer, d are that 0～50 integer, e are 1～30 integers.
8. as any described activity energy-line solidifying type resin composition of claim 1～7, it is characterized in that to be the unsaturated monomer that will contain quaternary ammonium salt base maybe will contain the quaternized thing of amino unsaturated monomer as the multipolymer of copolymer composition as the multipolymer of copolymer composition to the polymkeric substance [II] with quaternary ammonium salt base.
9. as any described activity energy-line solidifying type resin composition of claim 1～8, it is characterized in that, also contain Photoepolymerizationinitiater initiater [III].
10. as any described activity energy-line solidifying type resin composition of claim 1～9, it is characterized in that, contain also that the hydroxyl of polyalkylene derivative (c2) of isocyanate group in the polyisocyanates compounds (c1) and following general formula (6) expression and the hydroxyl that contains (methyl) acrylic ester compound (c3) of hydroxyl form amino-formate bond respectively and carbamate (methyl) acrylic ester compound [IV] that forms and forming
Here, Y is an alkylidene group, and Z is any one in alkyl, (methyl) acryl, allyl group, the acyl group, and p is 1 or its above integer.
11. as any described activity energy-line solidifying type resin composition of claim 1～10, it is characterized in that, further contain ethylene unsaturated monomer [V].
12. as any described activity energy-line solidifying type resin composition of claim 1～11, it is characterized in that, further contain static inhibitor [VI]
13. as any described activity energy-line solidifying type resin composition of claim 1～12, it is characterized in that, be used to apply agent.
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| CN103314024A (en) * | 2011-04-13 | 2013-09-18 | 日本合成化学工业株式会社 | Resin molding, and laminate produced using same |
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| CN106459329A (en) * | 2014-06-13 | 2017-02-22 | 东亚合成株式会社 | Curable composition |
| CN110028622A (en) * | 2017-12-22 | 2019-07-19 | 荒川化学工业株式会社 | Actinic energy ray curable resion composition antistatic agent, actinic energy ray curable resion composition, solidfied material and film |
| CN112300358A (en) * | 2020-05-27 | 2021-02-02 | 南京山维新材料科技有限公司 | Solvent-free ultraviolet curing quaternary ammonium salt resin and preparation method thereof |
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2005
- 2005-02-04 CN CN 200510007358 patent/CN1814674A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103314024A (en) * | 2011-04-13 | 2013-09-18 | 日本合成化学工业株式会社 | Resin molding, and laminate produced using same |
| CN104017138A (en) * | 2013-02-04 | 2014-09-03 | 荒川化学工业株式会社 | Active energy ray gel-type resin composition, antistatic agent used for composition, solidified membrane, and anti-static processing optical film |
| CN104017138B (en) * | 2013-02-04 | 2018-06-22 | 荒川化学工业株式会社 | Active energy ray-curable resin composition, the composition antistatic agent, cured film and antistatic treatment optical film |
| CN104710771A (en) * | 2013-12-16 | 2015-06-17 | 陶氏环球技术有限公司 | Crosslinkable composition, a method of making the same and a crosslinked composition produced therefrom |
| CN104710771B (en) * | 2013-12-16 | 2017-12-05 | 陶氏环球技术有限公司 | The composition of crosslinkable composition, its preparation method and crosslinking prepared therefrom |
| CN106459329A (en) * | 2014-06-13 | 2017-02-22 | 东亚合成株式会社 | Curable composition |
| CN106459329B (en) * | 2014-06-13 | 2019-12-10 | 东亚合成株式会社 | Curable composition |
| CN110028622A (en) * | 2017-12-22 | 2019-07-19 | 荒川化学工业株式会社 | Actinic energy ray curable resion composition antistatic agent, actinic energy ray curable resion composition, solidfied material and film |
| CN110028622B (en) * | 2017-12-22 | 2022-05-10 | 荒川化学工业株式会社 | Antistatic agent for active energy ray-curable resin composition, cured product, and film |
| CN112300358A (en) * | 2020-05-27 | 2021-02-02 | 南京山维新材料科技有限公司 | Solvent-free ultraviolet curing quaternary ammonium salt resin and preparation method thereof |
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