CN1673250A

CN1673250A - Polyester (methyl) propenoic acid ester

Info

Publication number: CN1673250A
Application number: CN 200410008888
Authority: CN
Inventors: 吉宗壮基
Original assignee: Nippon Shokubai Co Ltd
Current assignee: Nippon Shokubai Co Ltd
Priority date: 2004-03-25
Filing date: 2004-03-25
Publication date: 2005-09-28
Anticipated expiration: 2024-03-25
Also published as: CN100418998C

Abstract

The present invention provides polyester (methyl) acrylate, which has low viscosity, excellent operation performance, fast curing, capacity of form coating with high hot water resistance, proper hardness, excellent toughness and elasticity, and excellent hot color change resistance. The polyester (methyl) acrylate of the present invention features that it is prepared through reaction of aliphatic polybasic carboxylic acid with 12 or more carbon atoms, polyol with alicyclic skeleton, polybasic carboxylic acid with 11 or less carbon atoms and functionality not smaller than 3 and (methyl) acrylic acid as essential components.

Description

Polyester (methyl) acrylate

Technical field

The present invention relates to polyester (methyl) acrylate.Specifically, relate to polyester (methyl) acrylate with solidified nature, described polyester (methyl) acrylate can be used for printing ink, coating, tackiness agent, resin concrete, FRP (fibre reinforced plastics), inner lining material etc.

Background technology

Polyester (methyl) acrylate has the polymerizability unsaturated link(age), therefore have peroxide cure and ultraviolet isoreactivity energy ray-curable, thereby can form the coating of fundamental property excellence, in addition, with other the oligopolymer of polymerizability unsaturated link(age) with epoxy (methyl) acrylate or carbamate (methyl) acrylate etc. or polymkeric substance relatively, therefore polyester (methyl) acrylate can be used for printing ink, coating, tackiness agent, resin concrete, FRP (fibre reinforced plastics), inner lining material etc. because of the low easy handling of viscosity.In such polyester (methyl) vinylformic acid, the material with excellent characteristics such as rapidly-curable, hot water resistance and toughness is suitable for such use very much.

About polyester (methyl) acrylate, disclosed the Photocurable coating composition (opening clear 56-159260 communique (1-2 page or leaf)) that contains following compositions (A) and composition (B) referring to for example spy in the past.

Composition (A) is polymerization or oligomeric acrylate, it is that wherein polyvalent alcohol is to be selected from following (a) polyvalent alcohol with alicyclic ring skeleton to (c) with polyprotonic acid, polyvalent alcohol and the acrylic or methacrylic acid polymerization or the oligomeric acrylic acid class ester that obtain of esterification together.

(a) tristane dimethanol

(b) give 1～8 mole of alcohol of 1 mole of cyclohexanedimethanol addition with olefin oxide of 2～3 carbon atoms

(c) give 1～8 mole of alcohol of 1 mole of cyclohexanediol addition with olefin oxide of 2～3 carbon atoms

Composition (B) is a Photoepolymerizationinitiater initiater.

Also disclose polymer resin composition (opening clear 58-29814 communique (page 1)) referring to for example spy; it must composition be; (A) contain the vibrin (a-1) of (methyl) acryl and/or contain the polyester type urethane resin (a-2) of (methyl) acryl and (B) polymerisation reactivity thinner.Described vibrin (a-1) is that the polyester polyol (a-1-1) with the dimeracid residue that contains 9 weight %～70 weight % is that initiator obtains.

Also disclose polyester (methyl) acrylate (opening 2002-20468 communique (1-2 page or leaf) referring to for example spy) that the following compositions reaction is obtained, described polyester (methyl) acrylate is the electron(beam)curing type coating-forming agent that is used for the building materials and ornaments cardboard.

(A) one or more are selected from the material in the group of being made up of 2～4 yuan polycarboxylic acid, its acid anhydrides and its alkyl ester with alicyclic ring skeleton

(B) 3～6 yuan polyvalent alcohol and/or have 2 yuan of alcohol of alicyclic ring skeleton

(C) one or more are selected from the material in the group of being made up of (methyl) vinylformic acid, (methyl) acrylic acid hydroxy alkyl ester and polyalkylene glycol mono (methyl) acrylate

And inner lining material is disclosed with resin combination (opening flat 9-296032 communique (1-2 page or leaf) referring to for example spy); described inner lining material contains intramolecularly with resin combination and has 2 (methyl) acryls and the unsaturated ester that has more than or equal to the non-aromatic alkyl of 12 carbon atoms at least; and in this unsaturated ester; remove in the carbon atom carbon outward of formation (methyl) acryl, the ratio of the carbonatoms of formation non-aromatic alkyl is more than or equal to 60% of total carbon atom number.In addition, this inner lining material discloses the acrylic acid epoxy acrylate of use (methyl) with in the resin combination, but does not disclose polyester (methyl) acrylate.

But, in these existing polyester (methyl) acrylate, constituent for polyester (methyl) acrylate is still waiting research, so that it has the low advantage of viscosity, thereby go for printing ink, coating or tackiness agent, resin concrete, FRP (resin reinforced plastics) and inner lining material etc. also, make it become the material of solidified nature and coating performance excellence.

And, in the application purpose of polyester (methyl) acrylate, study characteristics such as elasticity, hot water resistance in addition, and improve the leeway of heat-resisting discolouration.That is, using pigment etc. painted and when forming coating etc., the variation that also needs to take place when coating is heated is studied, so that improve the quality of colored coating etc., and then can make polyester (methyl) acrylate be applicable to various uses.

Summary of the invention

In view of the foregoing, the purpose of this invention is to provide polyester (methyl) acrylate, it is because of the low operability excellence of viscosity, has rapidly-curable, fundamental property excellences such as hot water resistance as coating performance, and when having suitable hardness, toughness and elasticity excellence, and heat-resisting discolouration excellence.

To being suitable for printing ink, coating, tackiness agent, resin concrete, FRP (fibre reinforced plastics), the oligopolymer of inner lining material etc. or polymkeric substance carry out in the various researchs, the inventor etc. notice, polyester (methyl) acrylate is easy to because of viscosity is low handle, and low cost of manufacture, also find, the essential composition of such polyester (methyl) acrylate is a carbonatoms more than or equal to 12 aliphatics polycarboxylic acid (A-1), polyvalent alcohol (A-2) with alicyclic ring skeleton, carbonatoms smaller or equal to 11 and functionality more than or equal to polycarboxylic acid (A-3) and (methyl) vinylformic acid (A-4) of 3, and by behind these compositions formation polyester (methyl) acrylate, carbonatoms provides elasticity and has not damaged coating hardness more than or equal to 12 aliphatics polycarboxylic acid (A-1), polyvalent alcohol (A-2) with alicyclic ring skeleton provides toughness, (methyl) vinylformic acid (A-4) provides solidified nature, simultaneously by carbonatoms smaller or equal to 11 and functionality improved curing speed more than or equal to the molecular structure branching of 3 polycarboxylic acid (A-3), in addition, be embodied in fully in polyester (methyl) acrylate by these functions that become branch to give, the inventor expects that thus this can solve well about operability, solidified nature, hot water resistance, toughness, the above-mentioned problem of elasticity etc.In addition, the inventor has formed the more excellent material of solidified nature and coating performance, and then can perform well in such use etc. after also finding ratio specialization with these constituents.

Find also with described (A-1), (A-2) and (A-4) serve as to react in polyester (methyl) acrylate that obtains by composition that iodine number (A-1) also has excellent various characteristics smaller or equal to 100 material, and aspect heat-resisting discolouration excellence.When particularly using as (A-1), further improved the heat-resisting discolouration of cured coating film with the hydride of dimeracid.

The polyester that promptly the present invention relates to (methyl) acrylate (below be also referred to as polyester (methyl) acrylate (A-a)) be by with carbonatoms more than or equal to 12 aliphatics polycarboxylic acid (A-1), polyvalent alcohol (A-2), carbonatoms with alicyclic ring skeleton smaller or equal to 11 and functionality serve as must composition to react to obtain more than or equal to 3 polycarboxylic acid (A-3) and (methyl) vinylformic acid (A-4).

Another polyester (methyl) acrylate that the present invention relates to (below be also referred to as polyester (methyl) acrylate (A-b)) is by serving as must composition to react to obtain with carbonatoms more than or equal to 12 aliphatics polycarboxylic acid (A-1), the polyvalent alcohol (A-2) with alicyclic ring skeleton and (methyl) vinylformic acid (A-4), wherein said carbonatoms more than or equal to the iodine number of 12 aliphatics polycarboxylic acid (A-1) smaller or equal to 100.

Embodiment

Below be described in detail the present invention.

Polyester of the present invention (methyl) acrylate (A-a) by carbonatoms more than or equal to 12 aliphatics polycarboxylic acid (A-1), carbonatoms smaller or equal to 11 and functionality form the skeleton of polyester more than or equal to 3 polycarboxylic acid (A-3) and the carboxyl in (methyl) vinylformic acid (A-4) and the hydroxyl reaction in the polyvalent alcohol (A-2) with alicyclic ring skeleton, and (methyl) acryl that is had because of (methyl) vinylformic acid (A-4) makes this polyester (methyl) acrylate have peroxide cure or active energy ray-curable.For these constituents, each composition can use a kind of, also can share more than 2 kinds or 2 kinds.In addition, also can form polyester of the present invention (methyl) acrylate (A-a) by the composition that contains the material beyond these compositions be reacted, but preferably with described must composition be principal constituent.

In addition, in the present invention, it is as follows to be preferably formed the mass ratio of composition of described polyester (methyl) acrylate (A-a): carbonatoms is more than or equal to 12 aliphatics polycarboxylic acid (A-1): the polyvalent alcohol (A-2) with alicyclic ring skeleton: carbonatoms smaller or equal to 11 and functionality more than or equal to 3 polycarboxylic acid (A-3): (methyl) vinylformic acid (A-4) is 1: 0.1～5: 0.001～0.3: 0.01～2.

If the mass ratio of each composition not in described scope, then can not fully show the performance that respectively becomes branch to give polyester (methyl) acrylate, thereby can not perform well in described each purposes etc.For example, (A-1) be 1 and (A-2) during less than 0.1, may cause the hardness in the coating performance insufficient, if but (A-2) above 5 o'clock, then can not get the sufficient elasticity brought into play by the structural unit that carbonatoms forms more than or equal to 12 aliphatics polycarboxylic acid, and might be able to not form polyester (methyl) acrylate of tenacity excellent.In addition, (A-1) be 1 and (A-3) less than 0.001 or (A-4) during less than 0.01, may can not get solidified nature than the more excellent material of common polyester (methyl) acrylate, and, might cause insufficient as coating performances such as toughness (A-3) greater than 0.3 or (A-4) greater than 2 o'clock.Supposing that (A-1) is 1, (A-2) more preferably is 0.5～5, more preferably 0.75～5, be preferably 0.75～3 especially, and most preferably be 1～3.In addition, (A-3) more preferably be 0.01～0.3.(A-4) more preferably be 0.1～2, more preferably 0.1～1, be preferably 0.5～1 especially.

As carbonatoms among the present invention more than or equal to 12 aliphatics polycarboxylic acid (A-1), can enumerate as dodecanedicarboxylic acid, tetradecane dicarboxylic acid, hexadecane dicarboxylic acid, octadecane dicarboxylic acid, 1,16-(6-ethyl n-Hexadecane) dicarboxylic acid, 1,18-(7,12-18 diene) dicarboxylic acid, 1,12-(6-ethyl dodecane) dicarboxylic acid, 1,12-(6-ethynyl dodecane) dicarboxylic acid, 1,18-(7-ethynyl octadecane) dicarboxylic acid, 5-(7-carboxyl heptyl)-2-hexyl-3-cyclohexene carboxylate, dimeracid, hydrogenated dimer acids, trimer acid etc.

In addition, more than or equal to 12 aliphatics polycarboxylic acid (A-1), preferably use the dimer of unsaturated fatty acids, i.e. dimeracid as carbonatoms among the present invention.As dimeracid, can enumerate the natural monobasic unsaturated fatty acids polymeric material that ready denier oil acid, soya fatty acid etc. contain, these materials can contain monomer or trimerical single acid or the trimer acid as the monobasic unsaturated fatty acids of 5 weight %～40 quality %.Dimeracid can be the form of dicarboxylic acid, also can be forms such as acid anhydrides, ester, etheride.In addition, preferably use the dimeracid (hydrogenated dimer acids) of hydrogen addition and/or carbonatoms more than or equal to 30 dicarboxylic acid.Improved the heat-resisting discolouration of cured coating film by the dimeracid that uses the hydrogen addition.

Among the present invention, described carbonatoms can share less than 12 dicarboxylic acid with carbonatoms more than or equal to 12 aliphatics polycarboxylic acid (A-1)., can enumerate less than 12 dicarboxylic acid as carbonatoms as aliphatic dibasic acids such as hexanodioic acid, sebacic acid, fumaric acid, toxilic acid, maleic anhydride, furoate clothing and furoate clothing acid anhydrides; Phthalic acid, Tetra hydro Phthalic anhydride, m-phthalic acid, terephthalic acid etc. have the diprotic acid of aromatic nucleus; Hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, Tetra Hydro Phthalic Anhydride etc. have the diprotic acid of alicyclic ring skeleton.

Described carbonatoms more than or equal to 12 aliphatics polycarboxylic acid (A-1) and carbonatoms less than the preferred mass ratio of 12 dicarboxylic acid is, is 100 mass parts more than or equal to 12 aliphatics polycarboxylic acid (A-1) and carbonatoms less than the total amount of 12 dicarboxylic acid with carbonatoms, carbonatoms is 30～100 mass parts more than or equal to 12 aliphatics polycarboxylic acid, more preferably be 40～99 mass parts, 50～95 mass parts more preferably, be preferably 55～90 mass parts especially, most preferably be 55～80 mass parts.

As described dimeracid, can use commercially available product, can enumerate HARIDIMER 200,300 (trade(brand)names, Harry changes into corporate system), VERSADYME 228,216, EMPOL 1018,1019,1061,1062 (trade(brand)names, the COGNIS corporate system), TSUNODYME 216 (trade(brand)name is built food picked from the fields product industrial system) etc.In addition, as the commercially available product of hydrogenated dimer acids, can enumerate Pripol 1009 (trade(brand)name, UNICHEMA corporate system), EMPOL 1008 (trade(brand)name, COGNIS corporate system) etc.

As the polyvalent alcohol that has the alicyclic ring skeleton among the present invention (A-2), the carbonatoms of preferred alicyclic ring skeleton is 6～20.In addition, preferably have two hydroxyls.As polyvalent alcohol (A-2) with such alicyclic ring skeleton, preferred 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, cyclohexanedimethanol, tristane dimethanol, Hydrogenated Bisphenol A.In addition, it also is preferred for example giving the dibasic alcohol such as the formed compound of olefin oxide (carbonatoms 2～4) etc. of 3～30 moles of above-mentioned polyvalent alcohol additions.As the polyvalent alcohol (A-2) with such alicyclic ring skeleton, tristane dimethanol or Hydrogenated Bisphenol A are more suitable, and preferably having in the polyvalent alcohol of alicyclic ring skeleton more than or equal to 50 quality % is tristane dimethanol or Hydrogenated Bisphenol A.Mass ratio with tristane dimethanol in the polyvalent alcohol of alicyclic ring skeleton or Hydrogenated Bisphenol A is high more, and the toughness of polyester (methyl) acrylate is high more.

As carbonatoms among the present invention smaller or equal to 11 and functionality more than or equal to 3 polycarboxylic acid (A-3), so long as the compound that has more than or equal to 3 carboxyls gets final product, preferred carbonatoms smaller or equal to 11 and functionality more than or equal to being the compound that has more than or equal to 3 carboxyls more than or equal to 50 quality % in 3 the polycarboxylic acid.As the compound with 3 carboxyls, suitable have benzene tricarboxylic acid, hexanaphthene tricarboxylic acid, methylcyclohexane tricarboxylic acid, tetrahydrobenzene tricarboxylic acid, a tetrahydrotoluene tricarboxylic acid etc.As the compound with 4 carboxyls, suitable have hexanaphthene tetracarboxylic acid, methylcyclohexane tetracarboxylic acid, pyromellitic acid, 1,2,3, a 4-BTCA etc.Among the present invention, can use these sour acid anhydrides or alkyl ester etc.Wherein, preferably use 1,2, the 4-benzene tricarboxylic acid is the acid anhydrides of trimellitic acid, i.e. trimellitic acid 1,2-anhydride.

As the manufacture method of polyester of the present invention (methyl) acrylate (A-a), can enumerate following 2 kinds of methods.In the described essential composition, to (A-1), (A-2) and (A-3) carry out esterification after, add (A-4) and carry out esterification method (2 step synthesis method), or (A-1)～(A-4) carry out esterification method (1 goes on foot synthesis method) together.Wherein, from the angle of operability, the preferred 1 step synthesis method that adopts (A-1)～(A-4) to carry out esterification together is because this method can obtain low viscous polyester (methyl) acrylate.

The carrying out of described esterification can confirm by the generation of water, in each esterification, preferably proceed to no longer include water and generate till.

In the described 1 step synthesis method, can esterification be carried out, in the esterification,, preferably be blown into the gas of the oxygen that contains molecularity in order fully to prevent gelation by normal pressure or decompression.As the gas of the oxygen that contains molecularity, preferably use mixed gas of rare gas elementes such as air, nitrogen and air or oxygen etc.As the temperature of esterification, preferably be controlled at 50～140 ℃, more preferably at 70～120 ℃.

In the described 2 step synthesis methods, can esterification be carried out by normal pressure or decompression, be blown into nitrogen in the time of preferred (A-1), (A-2) and esterification (A-3), in addition, adding (A-4) carries out in the esterification process preferably being blown into the gas of the oxygen that contains molecularity in order fully to prevent gelation.As the gas of the oxygen that contains molecularity, can use mixed gas of rare gas elementes such as air, nitrogen and air or oxygen etc.In addition, add the viewpoint that (A-4) carries out the time of esterification, preferably add excessive (A-4),, use 1.01～1.5 normal (A-4) for example with respect to 1 normal terminal hydroxyl from shortening.Reaction finishes remaining (A-4) in back can remove by the following method, as the aqueous solution of water or alkali clean, by carry out filtering method after the neutralization reaction precipitating metal salt again, with the method for alkaline, inorganic salts such as MgO or anionite-exchange resin fractionation by adsorption etc.

As the temperature of esterification in the described 2 step synthesis methods, (A-1), (A-2) and esterification temperature (A-3) be preferably at 50～200 ℃.More preferably at 70～180 ℃.In addition, add (A-4) and carry out in the esterification, preferably at 50～140 ℃, more preferably at 70～120 ℃.

In the described esterification process,, preferably use catalysts from suppressing the angle of gelation and promotion esterification.Concerning catalysts, preferred acid catalyzer, for example sulfuric acid, hydrochloric acid, phosphoric acid, p-methyl benzenesulfonic acid, Phenylsulfonic acid, methylsulfonic acid, trifluoromethanesulfonic acid, Zeo-karb etc.These can use separately, also can share more than 2 kinds or 2 kinds.For usage quantity, be 100 mass parts with total addition level, be preferably 0.1～5 mass parts.Preferably finishing the back in reaction carries out aftertreatment or removes catalysts catalysts.As the method for aftertreatment, can enumerate by with basic cpds such as tertiary amine or NaOH neutralizations, perhaps make itself and epoxy compounds reaction etc.Can enumerate Racemic glycidol (methyl) acrylate, glycidyl allyl ether, bisphenol A type epoxy resin, bisphenol f type epoxy resin, cresol-novolac epoxy resin etc. as used epoxy compounds.As the method for removing catalysts, can enumerate following method, as the aqueous solution of water or alkali clean, by carry out filtering method after the neutralization reaction precipitating metal salt again, with the method for alkaline, inorganic salts such as MgO or anionite-exchange resin fractionation by adsorption etc.

In addition, in the described esterification process, can also use does not as required have active solvent to reaction.As solvent, preferred toluene, dimethylbenzene, hexanaphthene etc.In addition, preferably use stopper.As stopper, phenols such as preferred quinhydrones, Hydroquinone monomethylether; Quinoline such as benzoquinoline, phenylbenzene benzo quinoline; Thiodiphenylamine; Mantoquita etc.These can use separately, also can share more than 2 kinds or 2 kinds.

As the usage quantity of described stopper, be 0.0001 weight %～2 quality % with respect to the preferred usage quantity of total mass of the reaction raw materials that forms polyester (methyl) acrylate.More preferably be 0.005 weight %～0.5 quality %.

Polyester of the present invention (methyl) acrylate (A-b) is by serving as to react polyester (methyl) acrylate that obtains by composition with carbonatoms more than or equal to 12 aliphatics polycarboxylic acid (A-1), the polyvalent alcohol (A-2) with alicyclic ring skeleton and (methyl) vinylformic acid (A-4), wherein said carbonatoms more than or equal to the iodine number of 12 aliphatics polycarboxylic acid (A-1) smaller or equal to 100.

Described carbonatoms more than or equal to the iodine number of 12 aliphatics polycarboxylic acid (A-1) smaller or equal in 100 the compound, preferred hydrogenated dimer acids.Described hydrogenated dimer acids can be made dimer by the unsaturated fatty acids that iodine number is low, or by dimeracid hydrogenant method, iodine number is reduced to smaller or equal to 100 obtains.Iodine number by making aliphatics polycarboxylic acid (A-1) can fully improve the heat-resisting discolouration that polyester (methyl) acrylate solidifies the solidified coating that obtains smaller or equal to 100.More preferably described iodine number is smaller or equal to 80, is more preferably less than to equal 40, most preferably smaller or equal to 10.

Described iodine number is the index of amount of unsaturated hydrocarbons in the expression molecule, shows with the gram numerical table of the iodine of 100g material absorbing.Iodine number can be according to measuring as standard grease analytical test method 2341-96 etc.

As the commercially available product of described iodine number, can enumerate EMPOL 1062,1008 (trade(brand)name, COGNIS corporate system), Pripol 1009 (trade(brand)name, Unichema corporate system) etc. smaller or equal to 100 hydrogenated dimer acids.

Manufacture method as described polyester (methyl) acrylate (A-b), same with polyester (methyl) acrylate (A-a), can enumerate following 2 kinds of methods, in the described essential composition, after to (A-1) and (A-2) carrying out esterification, add (A-4) and carry out esterification method (2 step synthesis method), or (A-1)～(A-4) carry out esterification method (1 step synthesis method) together.Wherein, from the viewpoint of operability, the 1 step synthesis method of (A-1)～(A-4) carrying out esterification together is preferred because of obtaining low viscous polyester (methyl) acrylate.

The mass ratio of composition that is preferably formed described polyester (methyl) vinylformic acid (A-a), (A-b) is as follows: carbonatoms is more than or equal to 12 aliphatics polycarboxylic acid (A-1): the polyvalent alcohol (A-2) with alicyclic ring skeleton: (methyl) vinylformic acid (A-4) is 1: 0.1～5: 0.01～2.(A-2) more preferably be 0.5～5, more preferably 0.75～5, be preferably 0.75～3 especially, most preferably be 1～3.In addition, more preferably be 0.1～2 (A-4), more preferably 0.1～1, preferred especially 0.5～1.

As mentioned above, polyester among the present invention (methyl) acrylate can be with (A-1), (A-2), (A-3) and (A-4) to serve as polyester (methyl) acrylate (A-a) that must the composition reaction obtains, also can be with (A-1), (A-2) and (A-4) serve as must composition react obtain and iodine number (A-1) smaller or equal to 100 polyester (methyl) acrylate (A-b).And polyester (methyl) acrylate can also be these combination among the present invention.Promptly with (A-1), (A-2), (A-3) and (A-4) serve as must the composition reaction obtain and iodine number (A-1) smaller or equal to 100 polyester (methyl) acrylate.

Among the present invention, in order to improve the adaptation with base material, preferred polyester (methyl) acrylate intramolecularly imports carboxyl.As the method that imports carboxyl to polyester (methyl) acrylate intramolecularly, can use any method, preferably as use the carboxyl that surpasses with respect to the equivalence ratio of hydroxyl to carry out 1 step synthetic method.

The equivalence ratio of preferred carboxyl/hydroxyl is in 1.01～2.0 scope.More preferably in 1.1～1.8 scope, more preferably 1.2～1.5 scope.Under the situation of less than 1.01, can not effectively import carboxyl, and surpass at 2.0 o'clock, it is many that the amount of carboxyl can become, and causes hot water resistance to reduce.

Amount about the intramolecular carboxyl of preferred importing polyester (methyl) acrylate, the acid number of preferred polyester (methyl) acrylate is in the scope of 10mg KOH/g～60mg KOH/g, more preferably in the scope of 15mg KOH/g～50mg KOH/g, more preferably at 20mg KOH/g～40mgKOH/g.Under the situation of not enough 10mg KOH/g, the carboxyl of importing is low to the effect of adaptation, and when surpassing 60mg KOH/g, causes hot water resistance to reduce.

Polyester of the present invention (methyl) acrylate (A-a) or polyester (methyl) acrylate (A-b) can constitute curing composition with polymerizable monomer (B).Below, polyester of the present invention (methyl) acrylate (A-a) or polyester (methyl) acrylate (A-b) are also referred to as polyester (methyl) acrylate (A).

The curing composition that contains polyester of the present invention (methyl) acrylate (A) and polymerizable monomer (B) has peroxide cure and ultraviolet isoreactivity energy ray-curable, can form coating, thereby be fit to above-mentioned purposes etc. with excellent fundamental property.These compositions can use a kind of separately, also can share more than 2 kinds or 2 kinds.

As described polymerizable monomer (B), preferred functionality is more than or equal to 1 (methyl) acrylic monomer or vinyl monomer.As functionality is (methyl) acrylic monomer of 1, can enumerate as (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) vinylformic acid pentyl ester, (methyl) Ethyl acrylate, (methyl) vinylformic acid heptyl ester, (methyl) 2-EHA, (methyl) vinylformic acid n-octyl, (methyl) Isooctyl acrylate monomer, (methyl) vinylformic acid ester in the positive ninth of the ten Heavenly Stems, (methyl) vinylformic acid ester in the different ninth of the ten Heavenly Stems, (methyl) decyl acrylate, (methyl) dodecylacrylate, (methyl) tridecyl acrylate, (methyl) vinylformic acid stearyl, (methyl) cyclohexyl acrylate, (methyl) vinylformic acid benzene methyl, (methyl) vinylformic acid two cyclopentenes esters, (methyl) vinylformic acid 2-two cyclopentenes 2-ethoxyethyl acetates, (methyl) isobornyl acrylate, (methyl) vinylformic acid methoxyl group ethyl ester, (methyl) vinylformic acid ethoxy ethyl ester, (methyl) vinylformic acid butoxy ethyl ester, alkoxyl group polyalkylene glycol (methyl) acrylate, phenoxy group polyalkylene glycol (methyl) acrylate, alkyl phenoxy polyalkylene glycol (methyl) acrylate, (methyl) tetrahydrofurfuryl acrylate, (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinylformic acid 2-hydroxypropyl acrylate, (methyl) vinylformic acid 4-hydroxy butyl ester, (methyl) acryloyl morpholine, (methyl) vinylformic acid acetoacetoxy groups ethyl ester etc. contains (methyl) acrylate of acetoacetoxy groups, (methyl) vinylformic acid, (methyl) acrylamide etc.

As described functionality more than or equal to (methyl) acrylic monomer of 2, can enumerate as ethylene glycol bisthioglycolate (methyl) acrylate, 1, ammediol two (methyl) acrylate, 1,4-butyleneglycol two (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, glycerine two (methyl) acrylate, Diethylene Glycol two (methyl) acrylate, polyoxyethylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, polytetramethylene glycol two (methyl) acrylate, two (methyl) acrylate of dihydroxyphenyl propane ethylene oxide adduct, two (methyl) acrylate of dihydroxyphenyl propane propylene oxide adduct, (methyl) vinylformic acid affixture of bisphenol A diglycidyl ether, neopentyl glycol two (methyl) acrylate, 1,4 cyclohexane dimethanol two (methyl) acrylate, tristane dimethanol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, three (2-(methyl) acrylyl oxy-ethyl) chlorinated isocyanurates, tetramethylolmethane four (methyl) acrylate, Dipentaerythritol six (methyl) acrylate.

As described vinyl monomer, preferably just like vinylbenzene, Vinyl toluene, vinyl-acetic ester, N-ethene ethanamide, hexanodioic acid divinyl ester etc.

About the mass ratio of described polyester (methyl) acrylate (A) and polymerizable monomer (B), preferred 5/95～95/5, more preferably 20/80～95/5, more preferably 50/50～90/10.

The following of the not enough above-mentioned scope of the ratio of polymerizable monomer (B) may can not get sufficient solidified nature in limited time, and surpasses going up in limited time of above-mentioned scope, it is big that cure shrinkage becomes, filming to produce bending, perhaps may not reach both flexibles, the effect of the present invention that hot water resistance is good again.

Polyester of the present invention (methyl) acrylate (A-a) and solidifying agent (C) can constitute curing composition jointly.The curing composition that contains polyester (methyl) acrylate (A) and solidifying agent (C) of the present invention has peroxide cure or ultraviolet isoreactivity energy ray-curable, this composition can form the coating of fundamental property excellence, and therefore is fit to described purposes etc.When making composition, use superoxide, when making composition, use Photoepolymerizationinitiater initiater as solidifying agent (C) with active energy ray-curable as solidifying agent (C) with peroxide cure.These compositions can use a kind separately, also can share more than 2 kinds or 2 kinds.When using superoxide, can be cured by normal temperature or heating.When using ultraviolet homenergic dynamic rays, can be cured by the active energy beam projector.In addition, when using electron rays, do not use Photoepolymerizationinitiater initiater can be cured as energy-ray yet.In addition, can also share described polymerizable monomer (B) and solidifying agent (C).

As described superoxide, can enumerate preferred as organo-peroxides such as benzoyl peroxide, lauroyl peroxide, methylethyl ketone peroxide, the t-butyl peroxy-2 ethyl hexanoic acid tert-butyl ester, the Peroxycaprylic acid tert-butyl ester, t-butyl per(oxy)benzoate, cumene hydroperoxide, cyclohexanone peroxide, dicumyl peroxide, two (4-tert-butylcyclohexyl) peroxy dicarbonates; 2,2 '-Diisopropyl azodicarboxylate, 2-phenylazo-2,4-dimethyl-azo-compounds such as 4-methoxyl group valeronitrile etc.Wherein, organo-peroxide such as preferred benzoyl peroxide.Security in order to guarantee to operate in addition, for described organo-peroxide, preferably being diluted to concentration with inert liq is 50% pasty substance, or powdery substance.

When using described superoxide, preferably share curing catalyst.As curing catalyst, the described superoxide of preferably combination constitutes the compound of redox class solidifying agent, and suitable is amines such as thiourea derivative, dimethyl methyl aniline, diethyl Tolylamine, di-isopropyl Tolylamine, dihydroxy ethyl Tolylamine, xylidine, Diethyl Aniline, diisopropyl aniline, dihydroxy ethyl aniline; Organic acid such as naphthoic acid cobalt, cobalt octoate metal-salt; The condensation product of organic metal chelate complex, aldehyde and amine etc.Wherein, from the solidified nature aspect, preferred amine, organic acid metal-salt.

As described Photoepolymerizationinitiater initiater, can enumerate a compounds etc. that produces free radical as benzophenone, benzil, Michler's keton, thioxanthone, anthraquinone etc. by dehydrogenation.In addition, preferably tertiary amines such as these compounds and methylamine, diethanolamine, N-ethyldiethanolamine, Tributylamine use together.In addition, can also enumerate st-yrax, dialkoxy phenyl methyl ketone, acyl group oxime ester, benzil ketals, hydroxyalkyl phenyl ketone, halogenated ketone, Norleucyl benzene etc. produce free radical by intramolecularly division a compounds etc.

About the mass ratio of described polyester (methyl) acrylate (A) with solidifying agent (C), curing composition with polyester (methyl) acrylate (A) or polyester (methyl) acrylate (A) and polymerizable monomer (B) composition is 100 mass parts, preferred consolidation agent (C) is 0.1～20 mass parts, more preferably 1～10 mass parts.The ratio of solidifying agent (C) may not obtain sufficient solidified nature in limited time less than the following of described scope, and surpasses going up in limited time of described scope, may cause the cured coating film variable color, or increase the cost of curing composition.

Among the present invention, the preferred curing composition that contains tinting materials (D) such as pigment, dyestuff that uses.

As described pigment, can use mineral dye and pigment dyestuff.As mineral dye, can enumerate chrome yellow, zinc yellow, Prussian orchid, barium sulfate, cadmium red, titanium dioxide, zinc oxide, ferric oxide, white lake, lime carbonate, ultramarine, carbon black, graphite, aluminium powder, Indian red etc.; As pigment dyestuff, can enumerate the 2-Naphthol class, the β-Qiang Jinaijiasuan class, beta-hydroxy naphthanilide class, the alpha.-acetylacetanilide class, the solubility azo pigment of pyrazoline ketone etc., the 2-Naphthol class, beta-hydroxy naphthanilide class, alpha.-acetylacetanilide class Monoazo compound, alpha.-acetylacetanilide class tetrazo compound, the insoluble azo colour of pyrazoline ketone etc., copper phthalocyanine, halo (chloro or bromo) copper phthalocyanine, sulfonated copper phthalocyanine, phthalocyanine pigments such as no metallic copper phthalocyanine, quinoline a word used for translation ketone dioxazines, intellectual circle's class (golden yellow G of cloudy Shi Danlin, anthanthrone, indanthrone, anthrapyrimidine yellow, flavanthrene, thioindigo, anthraquinone, Naphtocyclinon, perylene), isoindoline ketone, metal complex, many rings pigment such as quinophthalone and heterocycle pigment etc.

As described dyestuff, preferably as various matching stains, substantive dyestuff and basic dyestuffs such as black cationic dyestuff, azo black class, turmeric yellow class, direct yellow class, basic yellow class, Xylene Red class, direct red class, alkaline red class, acid blue class, sun blue class, alkali blue classes.

About the content of the tinting material in the described curing composition (D), be 100 quality % with curing composition, preferred colorant content is at 1 quality %～80 quality %.More preferably at 5 quality %～60 quality %.More preferably at 10 quality %～50 quality %.Most preferably at 20 quality %～40 quality %.

During irradiation light (particularly ultraviolet ray), pigment or dyestuff absorb or have covered light (particularly ultraviolet ray), cause curing speed to reduce, and in order to prevent this phenomenon, can use sensitizer in the described curing composition.

As described sensitizer, sulphur compounds such as soluble salt, the N of urea compound, diethyl sulfide sodium phosphate or aromatic series-sulfinic acid such as cyclic amine compounds such as preferred fat amine, amine, piperidines, O-tolylthiourea with aromatic base, phosphorus compound, Michler's keton, the derivative of N-nitro oxyamine, oxazolidine compounds, tetrahydrochysenes-1 such as nitrile compounds such as N '-two replacement-p-aminophenyl formonitrile HCN, tri-n-butyl phosphine or diethyl sulfenyl sodium phosphate, the nitrogenous compounds such as condenses of 3-oxazine compounds, formaldehyde or acetaldehyde and diamines etc.These compounds can use more than a kind or a kind.

According to desired performance in the purposes of using, can also contain various additives in the described curing composition.As such additive, can enumerate as paraffinic hydrocarbons, natural and synthetic polymer substance, dispersion agent, silane coupling agent, slip(ping)agent, antioxidant, matting agent, softening agent, filling agent, viscosity modifier, uv-absorbing agent, solvent, tensio-active agent, levelling agent, defoamer, fire retardant, fiber reinforced material etc.These additives can use more than a kind or a kind separately.

The preferred paraffinic hydrocarbons that uses in the described additive, because when curing composition solidifies, paraffinic hydrocarbons is separated out on the surface of curing composition, the blocking curing composition contacts with air, thereby can improve surface cure, surface hardness, intensity, thermotolerance, glossiness and the stain resistance of curing composition.As paraffinics such as the preferred paraffin of paraffinic hydrocarbons, Microcrystalline Wax, polyethylene wax or wax class, stearic acid, 1, senior lipid acid such as 2-hydroxystearic acid.Preferred paraffin.The fusing point of paraffinic hydrocarbons is preferably at 30～130 ℃, and more preferably 50～80 ℃, more preferably 50～65 ℃.

As the using method of described curing composition, preferably after being coated on it on base material, be cured by the active energy beam irradiation.One of preferred implementation of the present invention is to adopt the active energy beam irradiation curing composition that contains polyester (methyl) acrylate of the present invention, thereby obtain cured article.As base material, preferred paper, metal, plastics, plastic film, pottery, glass, timber etc.As active energy beam, preferred hertzian wave, ultraviolet ray, visible light, infrared rays, electron rays, gamma ray etc.Wherein, preferred ultraviolet ray or electron rays.

Described when being cured by uviolizing, the preferred use comprises that wavelength is the light source of 150～450nm.As such light source, preferred solar source, low pressure mercury lamp, high voltage mercury lamp, ultrahigh pressure mercury lamp, metal halide lamp, gallium lamp, xenon lamp, carbon-point arc lamp etc.These light sources also can be used with the heat seal that infrared rays, far infrared rays, hot blast, ratio-frequency heating etc. produce.

The described irradiation by electron rays is cured in the process, and the acceleration voltage of preferred electron ray is in the scope of 10kv～500kv.20kv～300kv more preferably.More preferably 30kv～200kv.In addition, about irradiation dose, preferably at 2kGy (kilogray (kGy))～500kGy.3kGy～300kGy more preferably.More preferably 5kGy～200kGy.In addition, electron rays also can be used with the heat seal that infrared rays, far infrared rays, hot blast, ratio-frequency heating etc. produce.

Described curing composition can be used for printing ink, coating, tackiness agent, resin concrete, FRP (fibre reinforced plastics), inner lining material etc.Wherein, one of preferred embodiment of the present invention is that polyester (methyl) acrylate (A) is used for the printing ink of ultraviolet curing as oligopolymer.

In addition, when the curing composition that contains polyester of the present invention (methyl) acrylate (A) uses as printing ink, can well be used for mode of printings such as letterpress, photogravure, offset printing, silk screen printing, spray ink Printing.

Polyester of the present invention (methyl) acrylate with above-mentioned composition has excellent operation and rapidly-curable owing to its viscosity is low, it is as the fundamental property excellences such as hot water resistance of coating, and has the hardness of appropriateness and high toughness, so it can constitute the curing composition of various uses such as suitable printing ink, coating, tackiness agent, resin concrete, FRP (fibre reinforced plastics), inner lining material.

Enumerate embodiment below and illustrate in greater detail the present invention, single the present invention is not limited only to these embodiment.In addition, do not specify part, " part " expression " weight part ", " % " expression " quality % ".

Embodiment 1～3 and comparative example 1～3

(except that the vinylformic acid and the Epo-Tohto YDF-170) such as raw materials of the amount of Table 1 be added to be furnished with stirrer, in the flask of gas introduction tube, Dean-Rodney Stark (Dean-Stark) type water-and-oil separator and thermometer, be blown into nitrogen on one side, carry out esterification at 90～120 ℃ on one side, till reaction no longer includes the water generation.Then, add the vinylformic acid of the amount of Table 1, be blown into air, and meanwhile carry out esterification at 90～120 ℃, till reaction no longer includes the water generation.Add the Epo-Tohto YDF-170 (trade(brand)name of the amount of Table 1 again, Dongdu changes into the bisphenol f type epoxy resin of corporate system, and epoxy equivalent (weight) is 170g/eq (a gram/equivalent)), in 90 ℃ the reaction 30 minutes after, remove at 100 ℃, 13.3～40.0kPa and to desolvate, obtain polyester acrylate.

Comparative example 4

In the flask of being furnished with stirrer, gas introduction tube, reflux condensing tube and thermometer, add 440 parts of Epo-Tohto YD-128 (trade(brand)names, Dongdu changes into the bisphenol f type epoxy resin of corporate system, epoxy equivalent (weight) is 183g/eq), 346 parts of TSUNODYME 216 (trade(brand)names, build the dimeracid of food picked from the fields product industrial, acid number is 195mg KOH/g), 2.63 parts of chlorination triethylbenzene ammonium methyls, 0.09 part of quinhydrones, be blown into air on one side, carry out esterification at 105～120 ℃ on one side, till acid number drops to below the 5mgKOH/g.Then, add 91 parts of vinylformic acid,,, till acid number drops to below the 12mg KOH/g, thereby obtain epoxy acrylate Yi Bian carry out esterification at 105～120 ℃ Yi Bian be blown into air.

Table 1

	Embodiment 1	Embodiment 2	Embodiment 3	Comparative example 1	Comparative example 2	Comparative example 3
	Embodiment 1	Embodiment 2	Embodiment 3	Comparative example 1	Comparative example 2	Comparative example 3	TSUNODYME 216 (part)	??459	????-	????231	????530	????-	????474
EMPOL 1008 (part)	??-	????459	????-	????-	????-	????-	TSUNODYME 216 (part)	??459	????-	????231	????530	????-	????474
EMPOL 1008 (part)	??-	????459	????-	????-	????-	????-	Hexanodioic acid (part)	??-	????-	????88	????-	????239	????-
Trimellitic acid 1,2-anhydride (part)	??5.4	????5.4	????6.8	????6.2	????5.5	????-	Hexanodioic acid (part)	??-	????-	????88	????-	????239	????-
Trimellitic acid 1,2-anhydride (part)	??5.4	????5.4	????6.8	????6.2	????5.5	????-	Hydrogenated Bisphenol A (part)	??403	????403	????507	????-	????620	????396
1,9-nonanediol (part)	??-	????-	????-	????311	????-	????-	Hydrogenated Bisphenol A (part)	??403	????403	????507	????-	????620	????396
1,9-nonanediol (part)	??-	????-	????-	????311	????-	????-	Vinylformic acid (part)	??133	????133	????167	????154	????135	????130
Tosic acid monohydrate (part)	??10	????10	????10	????10	????10	????10	Vinylformic acid (part)	??133	????133	????167	????154	????135	????130
Tosic acid monohydrate (part)	??10	????10	????10	????10	????10	????10	Thiodiphenylamine (part)	??0.25	????0.25	????0.25	????0.25	????0.25	????0.25
Toluene (part)	??100	????100	????100	????100	????100	????100	Thiodiphenylamine (part)	??0.25	????0.25	????0.25	????0.25	????0.25	????0.25
Toluene (part)	??100	????100	????100	????100	????100	????100	Hexanaphthene (part)	??100	????100	????100	????100	????100	????100
Epo-Tphto YDF-170 (part)	??9	????9	????9	????9	????9	????9	Hexanaphthene (part)	??100	????100	????100	????100	????100	????100

In the table 1, TSUNODYME 216 (trade(brand)name) builds the dimeracid of food picked from the fields product industrial (acid number 195mg KOH/g), and EMPOL 1008 is hydrogenated dimer acids (acid number) 195mg KOH/g that COGNIS JAPAN company produces)

Embodiment 4～6, comparative example 5～8

Use according to described synthesis example synthetic polyester acrylate and epoxy acrylate and carry out following various evaluation test.The results are shown in table 2.

The evaluation method of peroxide cure

Composition shown in the mixture table 2, dissolve 0.2 part of paraffin 130 (trade(brand)name, the paraffin of Japanese smart wax corporate system) therein, then, mix 0.2 part of benzoyl peroxide (50% concentration) and 0.3 part of N, the N-dimethyl-p-toluidine as curing catalyst as solidifying agent.In 25 ℃ air, immediately the gained mixture is coated on the aluminium sheet of abundant degrease with spreader, form the film of thick 200 μ m, measure the used time of film hardening.

The evaluation method of active energy ray-curable

Composition shown in the mixture table 2 dissolves 5 parts of IRGACURE 907 as Photoepolymerizationinitiater initiater (trade(brand)name, the vapour Bart plants chemical company (Ciba Specialty ChemicalsK.K) system) therein.In 25 ℃ air, with spreader with this solution coat on the aluminium sheet of abundant degrease, form the film of thick 200 μ m.Then, in its uviolizing machine of packing into (USHIO motor corporate system, commodity are called " PM25C-100 ", use the 250w ultrahigh pressure mercury lamp, predominant wavelength is 365nm), irradiation per second energy is 43mJ/cm ²Ultraviolet ray, measure the used time of film hardening.

The measuring method of viscosity,

At room temperature composition shown in the mixture table 2 in 25 ℃ air, utilizes E type viscometer determining viscosity.

The evaluation method of pencil hardness

Utilize described peroxide cure evaluation method to make film hardening, measure the pencil hardness of cured article on the aluminium sheet according to JIS K 5400.

The evaluation method of anti-bending

Aluminium sheet behind the film hardening that will similarly make with described peroxide cure evaluation method, double flat around pencil, whether viewing film breaks.

Zero: crack-free

*: have and break

The evaluation method of hot water resistance

Use the aluminium sheet behind the film hardening that autoclave will similarly make with described peroxide cure evaluation method, contact 30 minutes with 120 ℃ water vapour, viewing film is at the degradation of test front and back.

Zero: no deterioration

*: deterioration is arranged

Table 2

	Embodiment 4	Embodiment 5	Embodiment 6	Comparative example 5	Comparative example 6	Comparative example 7	Comparative example 8
	Embodiment 4	Embodiment 5	Embodiment 6	Comparative example 5	Comparative example 6	Comparative example 7	Comparative example 8	The polyester acrylate of embodiment 1 (part)	????70	????-	????-	????-	????-	????-	????-
The polyester acrylate of embodiment 2 (part)	????-	????70	????-	????-	????-	????-	????-	The polyester acrylate of embodiment 1 (part)	????70	????-	????-	????-	????-	????-	????-
The polyester acrylate of embodiment 2 (part)	????-	????70	????-	????-	????-	????-	????-	The polyester acrylate of embodiment 3 (part)	????-	????-	????70	????-	????-	????-	????-
The polyester acrylate of comparative example 1 (part)	????-	????-	????-	????70	????-	????-	????-	The polyester acrylate of embodiment 3 (part)	????-	????-	????70	????-	????-	????-	????-
The polyester acrylate of comparative example 1 (part)	????-	????-	????-	????70	????-	????-	????-	The polyester acrylate of comparative example 2 (part)	????-	????-	????-	????-	????70	????-	????-
The polyester acrylate of comparative example 3 (part)	????-	????-	????-	????-	????-	????70	????-	The polyester acrylate of comparative example 2 (part)	????-	????-	????-	????-	????70	????-	????-
The polyester acrylate of comparative example 3 (part)	????-	????-	????-	????-	????-	????70	????-	The epoxy acrylate of comparative example 4 (part)	????-	????-	????-	????-	????-	????-	????70
Viscoat 295 (part)	????30	????30	????30	????30	????30	????30	????30	The epoxy acrylate of comparative example 4 (part)	????-	????-	????-	????-	????-	????-	????70
Viscoat 295 (part)	????30	????30	????30	????30	????30	????30	????30	Peroxide cure (minute)	????30	????30	????25	????35	????30	????60	????70
Active energy ray-curable (second)	????5	????5	????4	????5	????4	????15	????14	Peroxide cure (minute)	????30	????30	????25	????35	????30	????60	????70
Active energy ray-curable (second)	????5	????5	????4	????5	????4	????15	????14	Viscosity (Pas)	????35	????30	????45	????25	????100	????30	????300
Pencil hardness	????HB	????HB	????H	????2B	????2H	????HB	????HB	Viscosity (Pas)	????35	????30	????45	????25	????100	????30	????300
Pencil hardness	????HB	????HB	????H	????2B	????2H	????HB	????HB	Anti-bending	????○	????○	????○	????○	????×	????○	????○
Hot water resistance	????○	????○	????○	????×	????○	????○	????○	Anti-bending	????○	????○	????○	????○	????×	????○	????○

Embodiment 7～10, comparative example 9

The raw material (except the Epo-Tohto YDF-170) that in the flask of being furnished with stirrer, gas introduction tube, Dean-Rodney Stark type water-and-oil separator and thermometer, adds the amount of Table 3, import the gas of air/nitrogen=1/2 on one side, on one side 90～120 ℃ carry out esterification send out should, generate up to no longer including water.Then, add the Epo-Tohto YDF-170 of the amount of Table 3, in 90 ℃ of reactions after 30 minutes, under 100 ℃, 13.3～40.0kPa, remove and desolvate, obtain polyester acrylate.

In addition, the iodine number of being measured according to standard grease analysis laboratory method 2341-96 is as follows, and EMPOL1062 is 75, and EMPOL 1008 is 6, and TSUNODYME 216 is 120.

Table 3

	Embodiment 7	Embodiment 8	Embodiment 9	Embodiment 10	Comparative example 9
	Embodiment 7	Embodiment 8	Embodiment 9	Embodiment 10	Comparative example 9	EMPOL 1062 (part)	????459	????-	????231	????219	????-
EMPOL 1008 (part)	????-	????459	????-	????-	????-	EMPOL 1062 (part)	????459	????-	????231	????219	????-
EMPOL 1008 (part)	????-	????459	????-	????-	????-	TSUNODYME 216 (part)	????-	????-	????-	????-	????474
Hexanodioic acid (part)	????-	????-	????88	????168	????-	TSUNODYME 216 (part)	????-	????-	????-	????-	????474
Hexanodioic acid (part)	????-	????-	????88	????168	????-	Trimellitic acid 1,2-anhydride (part)	????5.4	????5.4	????6.8	????10	????-
Hydrogenated Bisphenol A (part)	????403	????403	????507	????-	????396	Trimellitic acid 1,2-anhydride (part)	????5.4	????5.4	????6.8	????10	????-
Hydrogenated Bisphenol A (part)	????403	????403	????507	????-	????396	Tristane dimethanol (part)	????-	????-	????-	????475	????-
Vinylformic acid (part)	????133	????133	????167	????128	????130	Tristane dimethanol (part)	????-	????-	????-	????475	????-
Vinylformic acid (part)	????133	????133	????167	????128	????130	Tosic acid monohydrate (part)	????5	????5	????5	????5	????5
Thiodiphenylamine (part)	????0.1	????0.1	????0.1	????0.1	????0.1	Tosic acid monohydrate (part)	????5	????5	????5	????5	????5
Thiodiphenylamine (part)	????0.1	????0.1	????0.1	????0.1	????0.1	Toluene (part)	????400	????400	????400	????400	????400
Epo-Tohto YDF-170 (part)	????4.5	????4.5	????4.5	????4.5	????4.5	Toluene (part)	????400	????400	????400	????400	????400

In the table 3, EMPOL 1062 (trade(brand)name) is the dimeracid (acid number 195mg KOH/g) of Cognis JAPAN corporate system, and EMPOL 1008 is materials identical with table 1 with TSUNODYME 216.

Embodiment 11～14, comparative example 10

Use is carried out various evaluation tests by the foregoing description and comparative example synthetic polyester acrylate.The results are shown in table 4.

Peroxide cure evaluation method, active energy ray-curable evaluation method and viscometry are identical with embodiment 4～6.

Embodiment 15

In the flask of being furnished with stirrer, gas introduction tube, Dean-Rodney Stark type water-and-oil separator and thermometer, add 1062,36 parts of hexanodioic acids of 268 parts of EMPOL, 74 parts of trimellitic acid 1,2-anhydrides, 478 parts of Hydrogenated Bisphenol As, 144 parts of vinylformic acid, 5 parts of tosic acid monohydrates, 0.1 part of thiodiphenylamine and 400 parts of toluene, be blown into the gas of air/nitrogen=1/2 on one side, carry out esterification at 90～120 ℃ on one side, till no longer including the water generation.Then, add 4.5 parts of Epo-Tohto YDF-170, after 30 minutes, under 100 ℃, 13.3～40.0kPa, remove and desolvate and vinylformic acid, obtain polyester acrylate in 90 ℃ of reactions.The acid number of the polyester acrylate that obtains is 30mg KOH/g.

Embodiment 16

Use by embodiment 15 synthetic polyester acrylates, carry out the various evaluation experimentals same with embodiment 11～14.The results are shown in table 4.In addition, when carrying out adaptation evaluation experimental as follows, do not see peeling off of film, this film has sufficient adaptation.

The adaptation evaluation method

Polyester acrylate and 30 parts of Viscoat 295s of 70 parts of embodiment 15 are mixed, 5 parts of IRGACURE907 of dissolving in 75 parts of mixtures that obtain as Photoepolymerizationinitiater initiater, add 20 parts of phthalocyanine blues again, after fully kneading, in 25 ℃ air, use spreader being coated with on the PET of Corona discharge Treatment film, thickness is 30 μ m.Then, in its uviolizing machine of packing into (USHIO motor corporate system, commodity are called " PM25C-100 ", use the 250W ultrahigh pressure mercury lamp, predominant wavelength is 365nm), be 43mJ/cm with the per second energy ²30 seconds of uviolizing, make film hardening.In 25 ℃ air, on this cured article, paste scotch tape (Nichiban corporate system, wide 24mm), observe the residual degree of filming when peeling off this scotch tape fast.

The evaluation method of pencil hardness

Utilize 30 seconds the ultraviolet ray of solidified nature evaluation method irradiation of described energy active ray, make film hardening, measure the pencil hardness of cured article on the aluminium sheet according to JIS K 5400.

The evaluation method of anti-bending

Aluminium sheet behind the film hardening that will similarly make with described pencil hardness evaluation method, double flat around pencil, whether viewing film breaks.

Zero: crack-free

*: have and break

The evaluation method of hot water resistance

Use the aluminium sheet behind the film hardening that autoclave will similarly make with described pencil hardness evaluation method, contact 30 minutes with 120 ℃ water vapour, viewing film is at the degradation of test front and back.

Zero: no deterioration

*: deterioration is arranged

The evaluation method of heat-resisting discolouration

In room temperature, composition shown in the table 4 is mixed, 5 parts of IRGACURE 907 of dissolving in 75 parts of these mixtures as Photoepolymerizationinitiater initiater, add 20 parts of phthalocyanine blues again, after fully kneading, in 25 ℃ air, use spreader on the aluminium sheet of fully degreasing, being coated with, forming thickness is the film of 30 μ m.Then, in its uviolizing machine of packing into (USHIO motor corporate system, commodity are called " PM25C-100 ", use the 250W ultrahigh pressure mercury lamp, predominant wavelength is 365nm), irradiation per second energy is 43mJ/cm ²30 seconds of ultraviolet ray, make film hardening.With this aluminium sheet heating 5 minutes,, use the beam split colour-difference meter to measure the aberration (Δ E) of heating front and back film with 200 ℃ baking boxs according to JIS Z 8730.

Table 4

	Embodiment 11	Embodiment 12	Embodiment 13	Embodiment 14	Embodiment 16	Comparative example 10
	Embodiment 11	Embodiment 12	Embodiment 13	Embodiment 14	Embodiment 16	Comparative example 10	The polyester acrylate of embodiment 7 (part)	????70	????-	????-	????-	????-	????-
The polyester acrylate of embodiment 8 (part)	????-	????70	????-	????-	????-	????-	The polyester acrylate of embodiment 7 (part)	????70	????-	????-	????-	????-	????-
The polyester acrylate of embodiment 8 (part)	????-	????70	????-	????-	????-	????-	The polyester acrylate of embodiment 9 (part)	????-	????-	????70	????-	????-	????-
The polyester acrylate of embodiment 10 (part)	????-	????-	????-	????70	????-	????-	The polyester acrylate of embodiment 9 (part)	????-	????-	????70	????-	????-	????-
The polyester acrylate of embodiment 10 (part)	????-	????-	????-	????70	????-	????-	The polyester acrylate of embodiment 15 (part)	????-	????-	????-	????-	????70	????-
The polyester acrylate of comparative example 9 (part)	????-	????-	????-	????-	????-	????70	The polyester acrylate of embodiment 15 (part)	????-	????-	????-	????-	????70	????-
The polyester acrylate of comparative example 9 (part)	????-	????-	????-	????-	????-	????70	Viscoat 295 (part)	????30	????30	????30	????30	????30	????30
Peroxide cure (minute)	????30	????30	????25	????30	????25	????60	Viscoat 295 (part)	????30	????30	????30	????30	????30	????30
Peroxide cure (minute)	????30	????30	????25	????30	????25	????60	Active energy ray-curable (second)	????5	????5	????4	????4	????4	????15
Viscosity (Pas)	????20	????20	????25	????10	????50	????20	Active energy ray-curable (second)	????5	????5	????4	????4	????4	????15
Viscosity (Pas)	????20	????20	????25	????10	????50	????20	Pencil hardness	????HB	????HB	????H	????HB	????H	????HB
Anti-bending	????○	????○	????○	????○	????○	????○	Pencil hardness	????HB	????HB	????H	????HB	????H	????HB
Anti-bending	????○	????○	????○	????○	????○	????○	Hot water resistance	????○	????○	????○	????○	????○	????○
Heat-resisting discolouration (Δ E)	????0.9	????0.3	????0.85	????0.9	????0.85	????2.3	Hot water resistance	????○	????○	????○	????○	????○	????○

According to table 2, embodiment 4～6 and comparative example 5～8 are made comparisons, use the viscosity in the comparative example 8 of epoxy acrylate to be 300Pas, to compare with 30～45Pas among the embodiment, this viscosity is higher, and is therefore relatively poor.In addition, the viscosity in the comparative example 6 is 100Pas, thinks that this is the influence that ester concentration produces.

In the comparative example 5,, cause pencil hardness and hot water resistance variation owing to do not have to use polyvalent alcohol (A-2) with alicyclic ring skeleton, in the comparative example 6, owing to do not use carbonatoms, cause the toughness variation, and proof has and breaks in anti-bending evaluation more than or equal to 12 aliphatic carboxylic acid (A-1).In the comparative example 7, because of do not use carbonatoms smaller or equal to 11 and functionality more than or equal to 3 polycarboxylic acid (A-3), in the comparative example 8 because of being epoxy acrylate, so peroxide cure and energy active ray-curable are all than embodiment difference.Used among the embodiment 4～6 of polyester of the present invention (methyl) acrylate, obtained all excellent material of whole these characteristics.According to table 4, embodiment 11～13 and comparative example 10 are made comparisons, since comparative example 10 do not use carbonatoms smaller or equal to 11 and functionality more than or equal to 3 polycarboxylic acid (A-3), and the iodine number as the TSUNODYME 216 of aliphatics polycarboxylic acid (A-1) has surpassed 100, so peroxide cure, energy active ray-curable and heat-resisting discolouration are all poor than the embodiment 11～13 that has used polyester of the present invention (methyl) acrylate.

Claims

1. polyester (methyl) acrylate, it is characterized by, its be by with carbonatoms more than or equal to 12 aliphatics polycarboxylic acid (A-1), polyvalent alcohol (A-2), carbonatoms with alicyclic ring skeleton smaller or equal to 11 and functionality serve as must composition to react to obtain more than or equal to 3 polycarboxylic acid (A-3) and (methyl) vinylformic acid (A-4).

2. polyester as claimed in claim 1 (methyl) acrylate, it is characterized by, the mass ratio of composition that forms described polyester (methyl) acrylate is as follows: carbonatoms is more than or equal to 12 aliphatics polycarboxylic acid (A-1): the polyvalent alcohol (A-2) with alicyclic ring skeleton: carbonatoms smaller or equal to 11 and functionality more than or equal to 3 polycarboxylic acid (A-3): (methyl) vinylformic acid (A-4) is 1: 0.1～5: 0.001～0.3: 0.01～2.

3. polyester (methyl) acrylate, it is characterized by, it is by serving as must composition to react to obtain with carbonatoms more than or equal to 12 aliphatics polycarboxylic acid (A-1), the polyvalent alcohol (A-2) with alicyclic ring skeleton and (methyl) vinylformic acid (A-4), wherein said carbonatoms more than or equal to the iodine number of 12 aliphatics polycarboxylic acid (A-1) smaller or equal to 100.