JP2006052258A - Active energy ray-curing resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an active energy ray-curing resin composition excellent in curing sensitivity for active energy rays, tight adhesiveness to polyesters and nonpolar polyolefins and flexibility. <P>SOLUTION: The active energy ray-curing resin composition comprises a polyester urethane (meth)acrylate (A) prepared by reacting components (1)-(3) given below and having 1,000-15,000 number average molecular weight and 1.0-1.8 number of constitutional units of the component (1), a urethane (meth)acrylate compound (B) prepared by reacting the component (2) with the component (3) and a photopolymerization initiator (C) and the mass ratio (A)/(B) satisfies the equation: (A)/(B)=100/0-12/88. The component (1) is a copolymerized polyester polyol containing ≥40 mol% aromatic dicarboxylic acid in the acid component and having 1,000-10,000 number average molecular weight. The component (2) is a polyisocyanate compound. The component (3) is a (meth)acrylate compound containing ≥1 hydroxy groups. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an active energy ray-curable resin composition that is excellent in curability for active energy rays and is excellent in adhesion to metals and plastics, boiling water resistance, and weather resistance.

  Conventionally, active energy ray-curable resin compositions have been cured by irradiating energy for a very short time, and the curing process is energy-saving, so they can be used for various coating materials such as adhesives, inks, and paint binders. Development is underway. In particular, urethane (meth) acrylate resins have been studied in various fields because they have excellent properties such as curability to active energy rays and toughness of the coating after curing. For example, Patent Document 1 discloses a urethane (meth) acrylate resin comprising a copolyester polyol, a diisocyanate compound, and a hydroxy group-containing (meth) acrylate compound.

Japanese Patent Laid-Open No. 7-286019

  However, this method is characterized in that when a urethane (meth) acrylate resin is obtained, the constituent component thereof contains a copolymerized polyester polyol having two or more constituent units, and therefore the urethane (meth) acrylate resin Only high molecular weight, high viscosity, and low curing sensitivity to active energy rays were obtained. Therefore, in order to reduce the viscosity of the resin composition and increase the curing sensitivity, a large amount of reactive diluent is used, but the toughness of the film after curing is poor, and plastics, particularly polyethylene terephthalate and nonpolar The adhesion to polyolefins was insufficient.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that (1) a copolymerized polyester polyol having an aromatic dicarboxylic acid in a specific range as an essential component, (2) a polyisocyanate compound, and (3) one Polyester urethane (meth) acrylate (A) having a molecular weight in a specific range obtained by reacting the above hydroxy group-containing (meth) acrylate compound with urethane (meta) obtained by reacting (2) and (3) above. ) When a resin composition obtained by blending an acrylate compound (B) and a photopolymerizable initiator (C) is used, it has excellent curing sensitivity, adhesion and flexibility with respect to active energy rays at low energy. The inventors have found that an active energy ray-curable resin composition that overcomes the above-mentioned drawbacks can be obtained, and reached the present invention.
That is, the gist of the present invention is as follows.

Polyester urethane (meth) acrylate (A) in which the number average molecular weight obtained by reacting the following (1) to (3) components is 1000 to 15000 and the number of structural units of component (1) is 1.0 to 1.8. ), A urethane (meth) acrylate compound (B) obtained by reacting the following (2) and (3), and a photopolymerizable initiator (C), and a mass ratio (A) / (B) = 100 An active energy ray-curable resin composition, which is / 0 to 12/88.
(1) A copolymer polyester polyol having an acid component and containing 40 mol% or more of an aromatic dicarboxylic acid and having a number average molecular weight of 1,000 to 10,000.
(2) Polyisocyanate compound.
(3) One or more hydroxy group-containing (meth) acrylate compounds.

  When the resin composition of the present invention is used, a cured film excellent in curing sensitivity, adhesion and flexibility with respect to active energy rays at low energy can be obtained, and applied to various coating materials such as adhesives, inks, paint binders, etc. can do.

  Hereinafter, the present invention will be described in detail.

[(1) Copolyester polyol]
The (1) copolymer polyester polyol used in the active energy ray-curable resin composition of the present invention is composed of a carboxylic acid component and a glycol component, and the acid component contains 40 mol% or more of an aromatic dicarboxylic acid. And the number average molecular weight is 1000 to 10,000.

  Aromatic dicarboxylic acid is a dicarboxylic acid having an aromatic group in its molecule, for example, phthalic anhydride, terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, etc. As mentioned. Of these, terephthalic acid and isophthalic acid are preferably used. The aromatic dicarboxylic acid needs to be contained in an acid component in an amount of 40 mol% or more, and preferably 50 mol% or more. When the amount is less than 40 mol%, the active energy ray-cured coating film is not preferable because of poor toughness and insufficient adhesion to polyethylene terephthalate or polyolefin. Further, if necessary, tri- and tetracarboxylic acids such as trimellitic acid, trimesic acid and pyromellitic acid may be contained in the acid component in an amount of about 0.2 to 20 mol%.

  Examples of dicarboxylic acids that can be copolymerized other than aromatic dicarboxylic acids include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, eicosandioic acid and other aliphatic dicarboxylic acids, and 1,2-cyclohexanedicarboxylic acid. 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, perhydronaphthalenedicarboxylic acid, dimer acid and other alicyclic dicarboxylic acids, fumaric acid, maleic acid, itaconic acid and other unsaturated dicarboxylic acids, tetrahydrophthalate Examples thereof include unsaturated alicyclic dicarboxylic acids such as acids and cyclobutene dicarboxylic acids, and oxyacids such as p-hydroxyethyloxybenzoic acid and ε-caprolactone.

  The glycol component is not particularly limited. For example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1 , 12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,15-pentadecanediol, 1,16-hexadecanediol, 1,17-heptadecanediol, 1,18-octadecanediol, 1,19-nonadecanediol, 1,20-eicosanediol, 2 Methyl-1,3-propanediol, neopentyl glycol, 2,2-diethyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, diethylene glycol, triethylene glycol, dipropylene glycol , Tripropylene glycol, 2,2,4-trimethyl-1,3-pentanediol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediol, spiroglycol, 1,4-phenylene glycol, 1,4-phenylene Ethylene oxide adduct of glycol, ethylene oxide adduct and propylene oxide adduct of bisphenol A, ethylene oxide adduct and propylene oxide adduct of hydrogenated bisphenol A, polyethylene glycol, polypropylene group Calls, such as diols and polytetramethylene glycol. Among these, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 2-methyl-1,3-propanediol, neopentyl glycol, diethylene glycol, triethylene glycol, tripropylene glycol, polytetra Methylene glycol is preferably used. Further, if necessary, the glycol component may contain about 0.2 to 20 mol% of triol such as trimethylolethane, trimethylolpropane, glycerin and pentaerythritol, and α-methylglucose, mannitol, sorbitol and the like.

  (1) Copolymerized polyester polyol used in the active energy ray-curable resin composition of the present invention is produced by a known production method using a melt polymerization method such as a direct esterification method or a transesterification method. can do.

  The production method by the direct esterification method will be described in more detail. A polyhydric alcohol, a polyvalent carboxylic acid and a catalyst which are raw materials for the copolymer polyester resin of the present invention are collectively charged into a reactor, and air in the system is evacuated. Drain and replace with nitrogen. Thereafter, the temperature is raised to the esterification temperature (200 to 240 ° C.), and the reaction is carried out for 2 to 8 hours while stirring. After completion of the esterification reaction, the temperature is raised to the polymerization temperature (220 to 290 ° C.), and the system is reduced in pressure to carry out the polymerization reaction under high vacuum. The reaction time varies depending on the type of resin to be produced, but is usually 3 to 10 hours. After completion of the polymerization reaction, nitrogen is enclosed in the system, the decompression is released, and the resin is discharged to obtain a copolyester resin.

  The number average molecular weight of the (1) copolymer polyester polyol used in the active energy ray-curable resin composition of the present invention needs to be 1000 to 10,000. If the number average molecular weight is less than 1000, the active energy ray-cured coating film is not preferable because of poor toughness and insufficient adhesion to polyethylene terephthalate or polyolefin. On the other hand, if the number average molecular weight exceeds 10,000, the viscosity becomes excessively high and handling is poor, which is not preferable.

  Methods for controlling the molecular weight of the copolyester polyol include a method of terminating the polymerization of the polyester melt during polymerization at a predetermined viscosity, a method of once producing a high molecular weight polyester and then adding a depolymerizing agent, and a monofunctional method. Examples thereof include a method in which a monofunctional carboxylic acid such as alcohol, (for example, cetyl alcohol, decyl alcohol, lauryl alcohol, myristyl alcohol, octyl alcohol, stearyl alcohol) or benzoic acid is added in advance. The molecular weight of the copolyester resin of the present invention may be controlled by any of the above methods, but a method of controlling the copolyester resin melt during polymerization with a predetermined viscosity is preferably used. Moreover, when increasing alcoholic hydroxyl group, the method of depolymerizing with the low molecular weight substance which has a polyfunctional alcoholic hydroxyl group, advancing polymerization reaction more than the target molecular weight of copolyester resin is preferable.

  Catalysts that can be used in the production of copolymerized polyester polyols include antimony compounds such as antimony trioxide, organic titanate compounds such as tetrabutyl titanate, alkali metals such as zinc acetate and magnesium acetate, alkaline earths Examples thereof include organic tin compounds such as acetates of similar metals and hydroxybutyltin oxide. Moreover, it is preferable that the catalyst usage-amount exists in the range of 0.01-1.0 mass% with respect to the resin mass to produce | generate. If the amount is less than 0.01% by mass, the polyester may not reach the desired molecular weight. On the other hand, if the amount exceeds 1.0% by mass, the molecular weight of the resin rises to a practically acceptable level. Since elution is a concern, it is not preferable.

  The acid value of the (1) copolymer polyester polyol used in the active energy ray-curable resin composition of the present invention may be synthesized so that the acid value is 3.0 mgKOH / g or less, preferably 1.0 mgKOH / g or less. desirable. When 3.0 mgKOH / g is exceeded, when synthesizing a polyester urethane (meth) acrylate resin described later, the number of inert ends in the reaction with the diisocyanate compound increases, and the desired polyester urethane (meth) acrylate resin cannot be obtained. Curability against active energy rays is reduced.

[(2) Polyisocyanate compound]
The (2) polyisocyanate compound used in the present invention includes aromatic polyisocyanates, araliphatic polyisocyanates, alicyclic polyisocyanates, aliphatic polyisocyanates, and the like. Examples of the aromatic polyisocyanate include m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4 or 2,6- Tolylene diisocyanate, 4,4'-toluidine diisocyanate, diisocyanates such as 4,4'-diphenyl ether diisocyanate, triphenylmethane-4,4 ', 4 "-triisocyanate, 1,3,5-triisocyanate benzene, 2, Polyisocyanates such as 4,6-triisocyanatotoluene, 4,4′-diphenylmethane-2,2 ′, 5,5′-tetraisocyanate, etc. Examples of the araliphatic polyisocyanate include 1,3. -Or 1,4-xylyl Diisocyanates such as diisocyanate, or mixtures thereof, 1,3- or 1,4-bis (1-isocyanate-1-methylethyl) benzene or mixtures thereof, and polyisocyanates such as 1,3,5-triisocyanate methylbenzene Can be mentioned.

  Examples of the alicyclic polyisocyanate include 1,3-cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), 4 , 4'-methylenebis (cyclohexyl isocyanate), methyl-2,4-cyclohexane diisocyanate, methyl 2,6-cyclohexane diisocyanate, 1,3- or 1,4-bis (isocyanatomethyl) cyclohexane diisocyanates, 1,3, 5-triisocyanatecyclohexane, 1,3,5-trimethylisocyanatecyclohexane, 2- (3-isocyanatopropyl) -2,5 di (isocyanatemethyl) -bicyclo (2 2.2.1) Heptane, 2- (3-isocyanatopropyl) -2,6-di (isocyanatomethyl) -bicyclo (2.2.1) heptane, 3- (3-isocyanatopropyl) -2,5-di (Isocyanatomethyl) -bicyclo (2.2.1) heptane, 5- (2-isocyanatoethyl) -2-isocyanatomethyl-3- (3-isocyanatopropyl) -bicyclo (2.2.1) heptane, 6- (2-isocyanatoethyl) -2-isocyanatomethyl-3- (3-isocyanatopropyl) -bicyclo (2.2.1) heptane, 5- (2-isocyanatoethyl) -2-isocyanatomethyl-2- (3- Isocyanatopropyl) -bicyclo (2.2.1) -heptane, 6- (2-isocyanatoethyl) -2-isocyanatomethyl-2- (3- Mention may be made of polyisocyanates such as isocyanatopropyl) -bicyclo (2.2.1) heptane.

  Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3- Diisocyanates such as butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methylcaproate, lysine ester triisocyanate, 1,4,8-triisocyanate octane, 1 , 6,11-triisocyanate undecane, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-triisocyanate hexane, 2,5,7-trimethyl-1,8 -Polyisocyanate, such as diisocyanate-5-isocyanate methyl octane, can be mentioned. Furthermore, derivatives from these polyisocyanates can also be used. Examples of the derivative from polyisocyanate include dimer, trimer, burette, allophanate, carbodiimide, polymethylene polyphenyl polyisocyanate (also referred to as crude MDI or polymeric MDI), crude TDI, and addition of isocyanate compound and low molecular weight polyol. The body etc. can be mentioned. Of these polyisocyanates, diisocyanates (for example, aromatic diisocyanates such as 2,4- or 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,3- or 1,4-xylylene diisocyanate, etc. Aroaliphatic diisocyanates, isophorone diisocyanates, alicyclic diisocyanates such as 1,3- or 1,4-bis (isocyanatomethyl) cyclohexane, aliphatic diisocyanates such as hexamethylene diisocyanate, or mixtures thereof are preferably used. . Furthermore, when importance is attached to weather resistance, alicyclics such as araliphatic diisocyanates such as 1,3- or 1,4-xylylene diisocyanate, isophorone diisocyanate, 1,3- or 1,4-bis (isocyanatomethyl) cyclohexane Aliphatic diisocyanates such as diisocyanate and hexamethylene diisocyanate are particularly preferably used, and isophorone diisocyanate is most preferably used.

[(3) One or more hydroxy group-containing (meth) acrylate compounds]
Examples of (3) one or more hydroxy group-containing (meth) acrylate compounds used in the present invention include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) ) Acrylate, 4-hydroxybutyl (meth) acrylate, pentanediol mono (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, 2-hydroxyalkyl (meth) acryloyl phosphate, 4-hydroxycyclohexyl ( (Meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, trimethylolpropane di (meth) acrylate, 2-hydroxy-1- (meth) acryloylio Ci-3- (meth) acryloyloxypropane, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and the like, and glycidyl groups such as alkyl glycidyl ether, allyl glycidyl ether, glycidyl (meth) acrylate and the like. The compound obtained by addition reaction of a containing compound and (meth) acrylic acid is also mentioned. These hydroxyl group-containing (meth) acrylates can be used alone or in combination of two or more. Among these, 2-hydroxyethyl (meth) acrylate, 2-hydroxy-1,3-diacryloxypropane, 2-hydroxy-1,3-dimethacryloxypropane, 2-hydroxy-1-acryloxy-3-methacryloxy Propane, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate and the like are preferably used.

[(A) Polyester urethane (meth) acrylate]
The polyester urethane (meth) acrylate (A) constituting the active energy ray-curable resin composition of the present invention comprises (1) the copolyester polyol and (2) the polyisocyanate compound and (3) one or more hydroxy groups. Although it can synthesize | combine by containing a (meth) acrylate compound, a number average molecular weight is 1000-15000 and the number of structural units of a component (1) is 1.0-1.8, Preferably it is 1.0-1. .6, more preferably 1.0 to 1.2. If the number average molecular weight is less than 1000, the active energy ray-cured coating film is not preferable because of poor toughness and insufficient adhesion to polyethylene terephthalate or polyolefin. On the other hand, if the number average molecular weight exceeds 15,000, the viscosity becomes too high and handling is poor, which is not preferable. Moreover, when the number of structural units of component (1) exceeds 1.8, (2) polyisocyanate increases the molecular weight of (1) polyester polyol, and the viscosity of polyester urethane (meth) acrylate (A) increases. , Handling is bad and not preferred. The reaction method of the above components is not particularly limited, but (1) a urethane prepolymer having almost no side reaction by reacting an excess of (2) polyisocyanate with the OH group of the copolymerized polyester polyol. Then, (3) reaction with one or more hydroxy group-containing (meth) acrylates is optimal for obtaining a polyester urethane (meth) acrylate (A) having a relatively low viscosity. More specifically, first, when (2) is reacted with (1) for urethanization, the ratio of NCO equivalent of (2) / OH equivalent of (1) is 1.55 to 25.0. Range, preferably 1.63-18.0, more preferably 1.88-9.0 to give an NCO-terminated polyester urethane prepolymer, followed by (3) the NCO end of the prepolymer. , The ratio of the remaining NCO group equivalent obtained by subtracting the OH group equivalent of (1) from the NCO group equivalent of (2) to the OH group equivalent of (3) is preferably 0.9 to 1.1. Can be synthesized by reacting at 0.95 to 1.05. At this time, the polyester urethane (meth) acrylate (A) has undergone two reaction steps, but can be produced at one time in one reaction kettle, thus simplifying the production process.

  In the urethanization reaction, a usual urethanization catalyst, that is, a tertiary amine catalyst, a tin-based catalyst, a lead-based catalyst, or the like may be used. For example, the tertiary amine catalyst includes a compound having one or more tertiary nitrogen atoms in one molecule. Examples of the tertiary amine compound having one nitrogen atom include triethylamine, N, N-dimethylcyclohexylamine, N-methylmorpholine, N-ethylmorpholine, N- (2-hydroxyethyl) -morpholine, N, N -Dimethyl-p-toluidine, β- (dimethylamino) propionitrile, N-methylpyrrolidone, N, N-dicyclohexylmethylamine and the like can be mentioned. Examples of the tertiary amine compound having two nitrogen atoms include N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethylpropane-1,3-diamine, N, N, N ′, N′-tetramethylhexane-1,6-diamine, bis (N, N-dimethylaminoethyl) ether, bis (2-dimethylaminoethyl) ether, ethylene glycol bis (3-dimethyl) -Aminopropyl ether, N'-cyclohexyl-N, N-dimethylformamidine, N, N'-dimethylpiperazine, trimethylpiperazine, 1,2-piperidinoethane, bis (aminopropyl) piperazine, N-methyl-N '-( 2-hydroxyethyl) piperazine, N- (N ′, N′-dimethylaminoethyl) morpholine, bis (morpholinoethyl) ether, Su- (2,6-dimethylmorpholinoethyl) ether, 1,2-dimethylimidazole, N-methylimidazole, 1,4-diazine, diazabicyclo [2.2.2] -octane (DABCO), 1,4-diazabicyclo [3.3.0] Oct-4-ene, 1,5-diazabicyclo [4.3.0] non-5-ene (DBN), 1,8-diazabicyclo- [5.4.0] -undec- 7-ene (DBU) and its phenol salt, octylate, etc. can be mentioned. Examples of tertiary amine compounds having 3 nitrogen atoms include N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, N, N, N ′, N ″, N ″ -pentamethyldipropylene. Triamine, tetramethylguanidine, N-cyclohexyl-N ′, N ′, N ″, N ″ -tetramethylguanidine, N-methyl-N ′-(2-dimethylamino) ethylpiperazine, 1,5,7-triaza Bicyclo [4.4.0] dec-5-ene and the like can be mentioned. Tertiary amine compounds having 4 nitrogen atoms include 1,1,4,7,10,10-hexamethyltriethylenetetramine, 1,3,5-tris (N, N-dimethylpropyl) hexahydro-1 2,3,5-triazine and the like. Examples of tin-based catalysts include stannous octoate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin mercaptide, dibutyltin thiocarboxylate, dibutyltin dimaleate, dioctyltin mercaptide, dioctyltin thiocarboxylate, and the like. it can. Examples of the lead-based catalyst include lead 2-ethylhexanoate. Examples of other urethanization catalysts include, for example, phenyl mercury propionate as a mercury-based catalyst. The amount of these urethanization catalysts used is 0.001 to 1.0% by mass, preferably 0.005 to 0.5% by mass, more preferably 0.01 to the polyester urethane (meth) acrylate (A). It is -0.2 mass%.

[(B) Urethane (meth) acrylate compound]
The active energy ray-curable resin composition of the present invention may contain a urethane (meth) acrylate compound (B) obtained by reacting the above (2) and (3). This urethane (meth) acrylate compound (B) corresponds to a reactive diluent, and the content of (B) can be adjusted by adjusting the NCO / OH ratio. (B) is a very useful compound, as its content increases, the resin composition has a reduced viscosity and can have a higher elastic modulus without impairing the elongation of the cured film. The mass ratio of the polyester urethane (meth) acrylate (A) and the urethane (meth) acrylate compound (B) needs to be (A) / (B) = 100/0 to 12/88, preferably 100 / It is 0-24 / 76, More preferably, it is 100 / 0-50 / 50. When the ratio of (A) is smaller than 12/88, the active energy ray-cured coating film has poor toughness, and the adhesion to polyethylene terephthalate or polyolefin is insufficient, which is not preferable.

[(C) Photopolymerizable initiator]
Examples of the photopolymerization initiator (C) added to the active energy ray-curable resin composition of the present invention include photopolymerization initiators such as acetophenone, benzoin, benphenone, thioxanthone, and acylphosphine oxide. It is done. Examples of the acetophenone series include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one (for example, Darocur 1173 manufactured by Ciba Specialty Chemicals), benzyldimethyl ketal (for example, Ciba Specialty Chemicals, Irgacure 651, BASF, Lucilin BDK, etc., 1-hydroxycyclohexyl phenyl ketone (for example, Ciba Specialty Chemicals, Irgacure 184), 2-methyl-2-morpholino (4 -Thiomethylphenyl) propan-1-one (for example, Irgacure 907, manufactured by Ciba Specialty Chemicals), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone (for example, Ciba Pesharuti Chemicals Inc., Irgacure 369), 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone oligomer (e.g., Ranberuchi Co. include Esakyua KIP) and the like. Examples of benzoin ethers include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether. Examples of the benzophenone series include benzophenone, methyl O-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 2,4,6-trimethylbenzophenone, (4-benzoylbenzyl) trimethylammonium chloride. Etc. Examples of the thioxanthone series include 2- or 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and the like. In addition to these, methylphenylglyoxyester (manufactured by AKZO, BYCURE 55), 3,6-bis (2-morpholinoisobutyl) -9-butylcarbazole (manufactured by Asahi Denka Co., Ltd., A-Cure3), titanocene compounds, etc. Can be mentioned. Examples of the acylphosphine oxide photopolymerization initiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide (for example, Lucillin TPO manufactured by BASF), bis (2,6-dimethoxybenzoyl) -2,4,4. -Trimethylpentylphosphine oxide (BAPO), bis (2,4,6-trimethylbenzoyl) methylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (for example, IRGA, manufactured by Ciba Specialty Chemicals) Cure 819), bis (2,4,6-trimethylbenzoyl) ethylphosphine oxide, bis (2,4,6-trimethylbenzoyl) n-butylphosphine oxide and the like. Further, these photopolymerization initiators can be used in combination. Specific examples thereof include Irgacure 1700 [Bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide / 2 as a commercial product. -Hydroxy-2-methylphenylpropan-1-one = 25/75% by mass], Irgacure 1800 [bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide / 1-hydroxycyclohexyl- Phenylketone = 25/75% by mass], Irgacure 1850 [Bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide / 1-hydroxycyclohexyl-phenylketone = 50/50% by mass] ( All are manufactured by Ciba Specialty Chemicals) It can gel. The amount of the photopolymerization initiator (C) used in the present invention is the polyester urethane (meth) acrylate (A) and the urethane (meth) acrylate compound (B) and an ethylenically unsaturated compound described later, which is added as necessary. In many cases, it is selected from the range of about 0.1 to 10 parts by mass, preferably about 0.5 to 5 parts by mass with respect to 100 parts by mass of the total amount of the above.

  In the active energy ray-curable resin composition of the present invention, various photopolymerization accelerators such as dialkylaminobenzoic acid or derivatives thereof (for example, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzoic acid ester, etc.), phosphine photopolymerization accelerators (arylphosphine such as triphenylphosphine, phosphine compounds such as trialkylphosphine) and the like may be added. The addition amount of these polymerization accelerators is, for example, polyester urethane (meth) acrylate (A) and urethane (meth) acrylate compound (B) and, if necessary, the total amount of ethylenically unsaturated compounds described later 100 A range of about 0.01 to 10 parts by mass can be selected with respect to parts by mass.

  The active energy ray-curable resin composition of the present invention can contain an ethylenically unsaturated compound as necessary. The ethylenically unsaturated compound used in the present invention functions as a reactive diluent, and a liquid or solid polymerizable compound can be used at room temperature (about 15 to 30 ° C.). This ethylenically unsaturated compound includes monofunctional compounds, bifunctional compounds and polyfunctional compounds. Monofunctional compounds (monofunctional polymerizable diluents) include, for example, heterocyclic ethylenically unsaturated compounds [for example, N-vinyl heterocyclic compounds such as N-vinyl pyrrolidone, N-vinyl pyridine, N-vinyl caprolactam, etc. , Morpholine (meth) acrylate, heterocyclic (meth) acrylate such as tetrahydrofurfuryl (meth) acrylate, etc.], N-vinylacetamide, N-vinylformamide, diacetone acrylamide, dialkylaminoethyl (meth) acrylate [for example , Dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, etc.], N, N'-dimethylacrylamide, alkoxy (poly) alkylene glycol (meth) acrylate [for example, methoxyethylene glycol (meth) acrylate , Methoxypolyethylene glycol (meth) acrylate, butoxypolyethylene glycol (meth) acrylate, etc.], alkylphenoxyethyl (meth) acrylate [eg, nonylphenoxyethyl (meth) acrylate, etc.], phenoxy (poly) alkylene glycol (meth) acrylate [For example, phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, etc.], cumylphenol (poly) alkylene (meth) acrylate, alkyl (meth) acrylate [for example, butyl (meth) acrylate, 2-ethylhexyl ( Meth) acrylate, etc.], cycloalkyl (meth) acrylate [eg cyclohexyl (meth) acrylate, etc.], aralkyl (meth) acrylate [For example, benzyl (meth) acrylate, etc.], di (meth) acrylate having a crosslinked alicyclic hydrocarbon group [for example, isobornyl (meth) acrylate, dicyclopentanediene (meth) acrylate, dicyclopentenyl (meth) acrylate , Tricyclodecanyl (meth) acrylate, dicyclopentenyloxyalkyl (meth) acrylate, tricyclodecanyloxyethyl (meth) acrylate, isobornyloxyethyl (meth) acrylate, etc.], hydroxyl group-containing (meth) acrylate [For example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, pentanediol mono (me ) Acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meta ) Acryloyloxyethyl-2-hydroxyethylphthalic acid, 3-acryloyloxyglycerin (meth) acrylate, 2-hydroxy-1- (meth) acryloyloxy-3- (meth) acryloyloxypropane, 2-hydroxyalkyl (meth) Acryloyl phosphate, 4-hydroxycyclohexyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, trimethylolproparate Di (meth) acrylate, polypropylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, etc.], poly ε-caprolactone mono (meth) acrylate, glycidyl (meth) acrylate, mono [2- (meth) acryloyloxyethyl ] Acid phosphate, halogen-containing (meth) acrylate [for example, trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 2,2,3,4,4,4 -Hexafluorobutyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, and the like]. Examples of the bifunctional compound (bifunctional polymerizable diluent) include di (meth) acrylate of 2,2-dimethyl-3-hydroxypropyl-2,2-dimethyl-3-hydroxypropionate (for example, Japan). “MANDA” manufactured by Kayaku Co., Ltd.), (polyoxy) alkylene glycol di (meth) acrylate [for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol Di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexane glycol di (meth) acrylate, neopentyl glycol di (Meta) Acrylate, pentanediol di (meth) acrylate, etc.], glycerin di (meth) acrylate, trimethylpropane di (meth) acrylate, pentaerythritol di (meth) acrylate, alkylene oxide of bisphenol A (eg, ethylene oxide, propylene oxide, butylene oxide) Di (meth) acrylate [for example, di (meth) acrylate of 2,2-bis (2-hydroxyethoxyphenyl) propane], di (meth) acrylate having a crosslinked alicyclic hydrocarbon group [For example, tricyclodecane dimethanol di (meth) acrylate, dicyclopentadiene di (meth) acrylate, etc.) (meth) acrylic acid adduct of bifunctional epoxy resin [for example, 2,2-bis (glycidyloxyphenyl) (Meth) acrylic acid adduct of propane], and the like. Examples of the polyfunctional compound (polyfunctional polymerizable diluent) include trimethylolpropane tri (meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol tetra (meth). ) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tris (acryloxy) isocyanurate, tris (hydroxyethyl) isocyanurate tri (meth) acrylate, tris (hydroxypropyl) isocyanurate Examples include tri (meth) acrylate, triallyl trimellitic acid, triallyl isocyanurate and the like. The amount of the ethylenically unsaturated compound used in the active energy ray-curable resin composition of the present invention is the kind of the polyester urethane (meth) acrylate (A) or urethane (meth) acrylate compound (B), which is desired by the resin composition. Depending on the required properties of the viscosity and the cured product, for example, 100 to 100 parts by mass, preferably 20 to 80 parts by mass, and more preferably 30 to 100 parts by mass of polyester urethane (meth) acrylate (A). It can be selected from a range of about 70 parts by mass.

  If necessary, a small amount of a stabilizer may be added to the active energy ray-curable resin composition of the present invention. As the stabilizer, a hindered phenol-based antioxidant, a hindered amine-based antioxidant, a sulfur-based antioxidant, or the like can be used. Examples of the hindered phenol stabilizer include compounds having a hydroxyphenyl group substituted with a t-butyl group, such as 2,6-di-t-butylhydroxytoluene, 2,2'-methylenebis (4-methyl-6- t-butylphenol), 4,4'-butylidenebis (3-methyl-6-t-butylphenol), triethylene glycol-bis [(3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1, 6-hexanediol bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], pentaerythritol-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) Propionate], 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) 1,3,5-triazine, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t -Butyl-4-hydroxyphenyl) propionate, 2,2'-thiobis (4-methyl-6-tert-butyl) phenol, 4,4'-thiobis (3-methyl-6-tert-butyl) phenol, N, N'-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 3,5-di-t-butyl-4-hydroxy-benzylphosphonate-diethyl ester, etc. Can be mentioned. Examples of the hindered amine antioxidant include bis (2,2,6,6-tetramethylpiperidinyl-4-sebacate), dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2, succinate, Examples include 2,6,6-tetramethylpiperidyl polycondensate. Examples of the sulfur-based antioxidant include dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate, pentaerythritol tetrakis -(Β-lauryl-thiopropionate), ditridecyl-3,3′-thiopropionate, 2-mercaptobenzimidazole and the like. The addition amount of these antioxidants is 100 parts by mass of the total amount of an ethylenically unsaturated compound described later, which is added as necessary, and polyester urethane (meth) acrylate (A) and urethane (meth) acrylate compound (B). On the other hand, it is 2.0 mass% or less, and 0.1-1.0 mass% is preferable from the balance of hydrogen gas generation amount and curing rate. In addition to the above components, the resin composition of the present invention includes, for example, other stabilizers such as antioxidants and ultraviolet absorbers, plasticizers, organic solvents, silane coupling agents, and water-repellent silanes. Various additives such as a compound, a modified silicone oil, a leveling agent, a surfactant, a coloring pigment, organic or inorganic fine particles may be added.

  An organic solvent can be added to the active energy ray-curable resin composition of the present invention. Organic solvents are limited to volatile ones, and most or all of them must be volatilized by heat drying or the like before curing with active energy rays. Solvents that can be used include acetone, methyl ethyl ketone, methyl isobutyl ketone, ketones such as cyclohexanone, esters such as methyl acetate and ethyl acetate, ethers such as tetrahydrofuran, dioxane, ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and benzene. , Aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as hexane and heptane, alcohols such as methanol, ethanol and isopropyl alcohol, or mixtures thereof.

  Hereinafter, the present invention will be described in more detail with reference examples, examples and comparative examples. However, the present invention is not limited to the following examples, and various modifications can be made without departing from the spirit of the present invention. Variations and applications are possible.

[Reference Example 1] (Synthesis of copolymer polyester polyol)
In a reaction vessel equipped with a thermometer, stirrer, distillation column, condenser, and decompression device, 83.1 kg of terephthalic acid, 49.8 kg of isophthalic acid, 29.2 kg of adipic acid, 48.4 kg of ethylene glycol, 67.7 kg of neopentyl glycol The reactor was charged with 15.0 kg of triethylene glycol and 42 g of hydroxybutyltin oxide as a catalyst, and the system was replaced with nitrogen. While stirring the charged raw materials at 30 rpm, the reactor was pressurized to 0.4 MPa and heated at 240 ° C. to melt the contents. The esterification reaction was allowed to proceed for 4 hours after the reactor temperature reached 240 ° C. After completion of the esterification reaction, the inside of the system was raised to 245 ° C. and the pressure was reduced, and a polymerization reaction was carried out for 7 hours after the inside of the system reached a high vacuum. After completion of the polymerization reaction, nitrogen is sealed in the system to return to normal pressure, and the produced resin is discharged out of the system, and the number average molecular weight is 1400, the acid value is 0.2 mgKOH / g, and the hydroxyl value is 74.6 mgKOH / g. Polymerized polyester polyol (P) was obtained.

  Hereinafter, the copolyester polyols Q to V were also produced in the same manner as in (Reference Example 1). Table 1 shows the results of analyzing the characteristic values of the obtained copolymer polyester polyol by the following method.

(A) Method for Analyzing Characteristic Values of Copolyester Polyol (1) Composition Analysis The composition analysis of the resin was performed using JEOL proton NMR, apparatus name JOEL LAMDBA300WB (300 MHz).
(2) Number average molecular weight of copolymerized polyester polyol The number average molecular weight is determined using polystyrene using a GPC analyzer (LC-10ADvp type and UV-VIS detector manufactured by Shimadzu Corporation, detection wavelength: 254 nm) using tetrahydrofuran as the mobile phase. Calculated by conversion.
(3) Acid value of copolyesterpolyol 0.5 g of copolyesterpolyol was dissolved in 25 ml of dioxane, titrated with 0.1 N KOH using cresol red as an indicator, and determined in units of mgKOH / g.
(4) Hydroxyl value of copolyesterpolyol After dissolving 2.0 g of copolyesterpolyol in 50 ml of pyridine, add 0.6 ml of acetic anhydride, acetylate by heating under reflux for 1 hour, and then add 5 ml of distilled water. The mixture was heated and refluxed for 10 minutes, and further 50 ml of dioxane was added, followed by heating and stirring for 1 hour. On the other hand, the same blank test was carried out without adding copolymer polyester polyol. After cooling, titration with 0.5N-KOH was performed for both solutions using cresol red and thymol blue as indicators, and the amount of OH groups was determined in mgKOH / g units from the difference between the two solutions.

[Example 1]
In a reaction vessel equipped with a thermometer, a stirrer, and a nitrogen introduction tube, the copolymerized polyester polyol (P) (number average molecular weight 1400, acid value 0.2 mgKOH) obtained in the above (Reference Example 1) and sufficiently dried under vacuum. / G, hydroxyl value 74.6 mgKOH / g) To 1000 parts by mass, 593 parts by mass of isophorone diisocyanate and 0.2 parts by mass of dibutyltin dilaurate are added and reacted at 80 ° C. for 3 hours in a nitrogen atmosphere. Hydroquinone 0.5 parts by mass, 2-hydroxy-1-acryloyloxy-3-methacryloyloxypropane 856 parts by mass and further reacted at 80 ° C. for 4 hours, isocyanate group (NCO) in infrared absorption spectrum (IR-spectrum) It was confirmed that there was no absorption due to. When this resin solution was analyzed by the GPC analyzer, 65% by mass of a polyester urethane (meth) acrylate (A-1) having a number average molecular weight of 2300 and a urethane (meth) acrylate compound (B-1) having a number average molecular weight of 650 were obtained. The mixture was 35% by mass. 100 parts by mass of the obtained polyester urethane (meth) acrylate (A-1), 54 parts by mass of the urethane (meth) acrylate compound (B-1), tetrahydrofurfuryl acrylate as a reactive diluent monomer (Osaka Organic Chemical Co., Ltd.) Resin composition 1 was prepared by blending 40 parts by mass of Biscoat # 150) and 10 parts by mass of Irgacure 651 (manufactured by Ciba Specialty Chemicals).

  Hereinafter, Example 2 to Example 7 and Comparative Example 1 to Comparative Example 5 were carried out in the same manner as in Example 1 to obtain resin compositions. Table 2 shows polyester urethane (meth) acrylate (A) and / or urethane (1) by reacting (1) polyester polyol, (2) polyisocyanate compound and (3) one or more hydroxy group-containing (meth) acrylate compounds. Respective formulations for obtaining the (meth) acrylate compound (B) and the obtained (A) and (B) are shown. Table 3 shows the results of evaluation according to the following method by further blending (C) a photopolymerizable initiator and a reactive dilution monomer with (A) and (B).

[Evaluation methods]
(Cross-cut adhesion test) Polyethylene terephthalate film (No. 542-AB type, manufactured by Yasuda Seiki Co., Ltd.) was used for the resin compositions obtained in Examples 1-7 and Comparative Examples 1-5. 38 μm, made by Unitika) and polypropylene plate (made by Nippon Test Panel, thickness 2 mm, size: 70 mm × 100 mm), copper plate (made by Japan Test Panel, thickness 0.3 mm, size: 70 mm × 100 mm) to a thickness of 10 μm After coating, after curing by irradiating with an ultraviolet irradiation device (eye graphics ECS-401GX, metahalide lamp 160W manufactured by Eye Graphics Co., Ltd.) at an irradiation amount of 200 mJ / cm ² (wavelength 350 nm), in accordance with JISK5400. A cross-cut adhesion test was performed. The measurement results are shown as a fraction of the number of non-peeled cross-cuts / total cross-cuts. The larger the number of molecules, the better the adhesion.

While Examples 1 to 7 all showed good adhesion, Comparative Example 1 was inferior in adhesion as a whole because (1) the molecular weight of the polyester polyol was smaller than the claims of the present invention. It became a thing. In Comparative Example 2, (1) the molecular weight of the polyester polyol was larger than that claimed in the present invention, and a large amount of dilution monomer was required when applying the resin composition, so that the overall adhesion was inferior. Moreover, since the structural component of the comparative example 3 (1) polyester polyol remove | deviated from the claim of this invention, it became inferior to the adhesive force with respect to a polyethylene terephthalate and a polypropylene. Moreover, since the ratio of (A) is smaller than the claim of this invention in the compounding ratio of the polyester urethane (meth) acrylate (A) and the urethane (meth) acrylate compound (B), the comparative example 4 is relative to polyethylene terephthalate and polypropylene. The adhesion was inferior. In Comparative Example 5, the number of repeating units was larger than that claimed in the present invention, and a large amount of dilution monomer was required when applying the resin composition, so that the overall adhesion was inferior.

Claims (1)

Polyester urethane (meth) acrylate (A) in which the number average molecular weight obtained by reacting the following (1) to (3) components is 1000 to 15000 and the number of structural units of component (1) is 1.0 to 1.8. ), A urethane (meth) acrylate compound (B) obtained by reacting the following (2) and (3), and a photopolymerizable initiator (C), and a mass ratio (A) / (B) = 100 An active energy ray-curable resin composition, which is / 0 to 12/88.
(1) A copolymer polyester polyol having an acid component and containing 40 mol% or more of an aromatic dicarboxylic acid and having a number average molecular weight of 1,000 to 10,000.
(2) Polyisocyanate compound.
(3) One or more hydroxy group-containing (meth) acrylate compounds.