JP2008074891A - Thermosetting or active energy ray curing composition and film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin film having high abrasion strength, flexibility and glossiness and to provide the film thereof. <P>SOLUTION: A thermosetting or an active energy ray curing composition comprises one or more selected from the group consisting of a monomer (a1) exhibiting 10-100 times-foldings after curing into a film state by a folding endurance evaluation and an oligomer (a2) exhibiting 10-100 times-foldings after curing into the film state by the folding endurance evaluation and 0-30 wt.% of a filler. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a thermosetting or active energy ray-curable composition that cures when irradiated with active energy rays such as heat, ultraviolet rays, or electron beams, and a film coated with the composition. Furthermore, the present invention also relates to an article protection repair method for protecting or repairing an object such as a flooring.

  In various facilities such as convenience stores and hospitals where many people come and go and are required to maintain a clean state, various floor materials such as vinyl chloride sheets and polyolefin tiles are placed on the concrete floor. is doing. Examples of a method of maintaining the floor material at a predetermined gloss, friction, and wear strength include a method of protecting the floor material by applying various liquid waxes after washing and drying the floor material.

  However, in the floor material of a passage with a lot of people and carts and a large amount of traffic, the applied wax wears in a relatively short period of time, so that the applied wax is frequently removed and new wax is applied. It was necessary to perform maintenance work. Since this maintenance work requires a relatively long working time, the work cost is increased and the facility user is inconvenient.

  Further, the floor surface protection by wax has a limit in the wear strength, and the damage to the floor material itself is likely to proceed. Furthermore, the use of a polisher (floor polisher) in maintenance work also damages the flooring material, so the frequency of re-covering the flooring material has increased.

  Therefore, recently, a floor protection sheet has been proposed that can maintain a floor material in a predetermined state by a simple operation (for example, Japanese Patent Application Laid-Open No. 2005-68687). In these conventional protective sheets for floors, wear resistance was obtained by using a curable resin composition having high hardness after curing.

  However, the floor protective film using such a high-hardness resin composition has a drawback that surface cracking / breaking or the like is likely to proceed under conditions of high frequency of walking such as a person or a carriage. Moreover, although it is excellent in pencil hardness and resistant to scratches, it is inferior in resistance to fine scratches repeatedly given as evaluated by Taber abrasion strength. For this reason, there is a problem that the surface is roughened and the transparency is deteriorated due to scratches under the condition that the passage frequency is high. In addition, since the cured coating is hard and brittle, cracking of the surface may occur when the protective sheet for flooring is produced and stored on a roll or when it is spread on a flooring material, and the handling is inferior. There was a point.

JP 2005-68687 A

  Under the circumstances described above, there is a need for a thermosetting or active energy ray-curable composition that has high wear strength and can be used for a protective sheet for adherends, particularly a protective sheet for floors. In addition, for example, a thermosetting or active energy ray-curable composition having excellent gloss that cannot be expressed in a protective layer obtained by applying a liquid wax is desired. In addition, for example, there is a need for a thermosetting or active energy ray-curable composition that has high abrasion strength but does not cause surface cracks when stored on a roll or spread on a flooring. Yes. In addition, for example, an adherend protective sheet, particularly a floor protective sheet, that can be maintained in a simple and short-time operation and has the above-described properties is demanded.

The present inventors do not add a filler or add a certain amount or more, and the flexibility after curing includes 10 to 100 times of monomer and the like in a bending strength evaluation. The composition and the film obtained using the composition were found to have excellent wear resistance (due to scratching) evaluated by Taber abrasion strength and excellent flexibility. Based on this, the present invention has been completed.
Furthermore, by adding a monomer or the like having a flexibility after curing of 100 times or more in the bending strength evaluation to the composition, it is possible to express higher wear resistance and further improve the flexibility. Based on this finding, the present invention has been completed.
The present invention provides the following thermosetting or active energy ray curable compositions, cured films containing these compositions, and article protection repair methods using them.

[1] A thermosetting or active energy ray-curable composition,
Flexibility after being cured into a film shape is 10 to 100 times of the monomer (a1) according to the bending strength evaluation, and flexibility after being cured into a film shape is from 10 to 100 times of the oligomer (a2) according to the bending strength evaluation. The composition containing 1 or more chosen from the group which consists of, and 0-30 weight% of fillers.

[2] The composition described in [1] above, wherein the monomer constituting the monomer (a1) or the oligomer (a2) is urethane (meth) acrylate.

[3] The monomer constituting the monomer (a1) or oligomer (a2) is a polyfunctional urethane (meth) acrylate having two or more (meth) acryloyl groups in one molecule, as described in [1] above. Composition.

[4] The monomer constituting the monomer (a1) or oligomer (a2) is a polyfunctional urethane (meth) acrylate having 6 or more (meth) acryloyl groups in one molecule. Composition.

[5] Said [2] thru | or [6] whose said urethane (meth) acrylate is 6 functional aliphatic urethane (meth) acrylate which has 6 functional groups in 1 molecule, and has an aliphatic urethane group. 4].

[6] The composition according to any one of [2] to [5], wherein the urethane (meth) acrylate has a weight average molecular weight of 500 to 10,000.

[7] The composition according to any one of [1] to [6], further including a (meth) acrylic copolymer resin (B).

[8] The composition described in [7] above, wherein the (meth) acrylic copolymer resin (B) has a (meth) acryloyl group and a carboxyl group in the side chain.

[9] The above (7), wherein the (meth) acrylic copolymer resin (B) has an acid value of 20 to 200 (KOH mg / g), a weight average molecular weight of 5000 to 20000, and a double bond equivalent of 350 to 450. ] Or the composition as described in [8].

[10] The composition according to any one of [1] to [9], which does not contain a filler.

[11] Further, the monomer (c1) having a flexibility after being cured into a film is 100 times or more by a folding strength evaluation, and an oligomer (100) or more being a flexibility after being cured in a film is evaluated by a bending strength evaluation. The composition according to any one of [1] to [10] above, which comprises one or more selected from the group consisting of c2).

[12] The composition described in [11] above, wherein the monomer constituting the monomer (c1) or the oligomer (c2) is one or more selected from the group consisting of (meth) acrylates, carboxylates, and polyfunctional monomers.

[13] The composition described in [12] above, wherein the monomer constituting the monomer (c1) or the oligomer (c2) has an epoxy group.

[14] The composition described in [12] above, wherein the monomer constituting the monomer (c1) or the oligomer (c2) has an alicyclic epoxy group.

[15] The composition described in [11] above, wherein the monomer constituting the monomer (c1) or the oligomer (c2) is 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate.

[16] The composition described in [11] above, wherein the monomer constituting the monomer (c1) or the oligomer (c2) is phenoxyethyl acrylate.

[17] The weight ratio of one or more components selected from the group consisting of monomer (a1) and oligomer (a2) to one or more components selected from the group consisting of monomer (c1) and oligomer (c2) is 100 to The composition according to any one of [11] to [16] above, which is 65: 0 to 35.

[18] The activity according to any one of [1] to [17] above, further comprising one or more selected from the group consisting of a polyol (D), an active energy ray polymerization catalyst (E), and a leveling agent (F). Energy ray curable composition.

[19] The composition according to any one of [1] to [18], wherein the wear property after curing of the composition is 2000 to 3000 rotations in terms of Taber abrasion strength evaluation.

[20] A film comprising a thermoplastic resin substrate layer and a layer obtained by curing the composition described in any one of [1] to [19].

[21] An object is protected or repaired by applying the composition described in any one of [1] to [19] and then curing, or by attaching the film described in [20]. Article protection repair method.

[22] The article protection repair method according to [21], wherein the object is a flooring.

  In this specification, in order to show both an acrylate and a methacrylate, it may describe as "(meth) acrylate".

The thermosetting or active energy ray-curable composition according to a preferred embodiment of the present invention has, for example, high wear strength. In addition, the thermosetting or active energy ray-curable composition according to a preferred embodiment of the present invention has high flexibility that does not cause surface cracks even when stored on a roll or spread on a flooring. Have Furthermore, the thermosetting or active energy ray-curable composition according to a preferred embodiment of the present invention has excellent gloss, for example.
In addition, by using the floor protection sheet containing the thermosetting or active energy ray-curable composition according to a preferred embodiment of the present invention, the flooring can be maintained in a simple and short work.

1 Thermosetting or active energy ray-curable composition of the present invention The first aspect of the present invention relates to a thermosetting composition or an active energy ray-curable composition. This thermosetting or active energy ray-curable composition contains a monomer and / or oligomer (A), and preferably contains a (meth) acrylic copolymer (B). Furthermore, it is preferable that this composition contains a 2nd monomer and / or oligomer (C). Moreover, 1 or more types chosen from the group which consists of a polyol (D), an active energy ray polymerization catalyst (E), and a leveling agent (F), Furthermore, the filler may be included depending on the case.

1.1 Monomer or oligomer (A)
One or more selected from the group consisting of the monomer (a1) and the oligomer (a2) contained in the thermal curing or active energy ray curing composition of the present invention is itself (including a photopolymerization initiator for curing). Has a property that the flexibility of the resin obtained by curing the resin into a film shape becomes 10 to 100 times according to the bending strength evaluation. In addition, a softness | flexibility is measured by bending strength evaluation. Fracture strength evaluation is measured and evaluated by the method prescribed in JIS P8115, and specific measurement and evaluation methods will be described in detail in Examples (“Production of coating film” and “Flexibility: Resistance to resistance” in Examples). (Refer to "Folding strength (MIT) evaluation").

  The monomer (a1) and the oligomer (a2) have a property of curing when irradiated with active energy rays such as heat or ultraviolet rays or electron beams. The flexibility after curing is 10 to 100 times, preferably 20 to 90 times, and more preferably 30 to 80 times, according to the bending strength evaluation.

  The monomer (a1) and the oligomer (a2) are not particularly limited in chemical structure as long as they have the flexibility described above, but the monomer constituting the monomer (a1) or oligomer (a2) is urethane (meth). An acrylate is preferred. This urethane (meth) acrylate is preferably a polyfunctional urethane (meth) acrylate having a plurality of, for example, 2 or more, 6 or more (meth) acryloyl groups in one molecule, and is contained in one molecule. The number of (meth) acryloyl groups is more preferably 2 to 16, further preferably 3 to 10, and particularly preferably 6.

  Urethane (meth) acrylates preferably used in the present invention, particularly polyfunctional urethane (meth) acrylates having a plurality of (meth) acryloyl groups in one molecule, are (meth) acrylic compounds having a polyisocyanate compound and active hydrogen. Obtained by reaction with monomers. In addition, aliphatic urethane (meth) acrylate may be sufficient as the urethane (meth) acrylate used suitably by this invention, and aromatic urethane (meth) acrylate may be sufficient as it.

  Examples of the polyisocyanate compound used include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylene diisocyanate, 1,4-xylene diisocyanate, xylylene diisocyanate, 1,5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-dibenzyl diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, 2,2,4-trimethylhexamethylene Diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate or these diisocyanate compounds Among them, diisocyanate compounds obtained by hydrogenating aromatic isocyanates (for example, diisocyanate compounds such as hydrogenated xylylene diisocyanate and hydrogenated diphenylmethane diisocyanate), triphenylmethane triisocyanate, dimethylene triphenyl triisocyanate and the like 2 And an isocyanate group-containing compound such as a divalent or trivalent diisocyanate compound or polyisocyanate compound, or a multivalent polyisocyanate compound obtained by multiplying them.

  Furthermore, before reacting the polyisocyanate and the (meth) acrylic monomer having active hydrogen for the purpose of adjusting the molecular weight and molecular flexibility of urethane (meth) acrylate, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, di- Propylene glycol, polypropylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, ethylene oxide / propylene oxide adduct of bisphenyl A, polyester polyol and A chain-extended urethane prepolymer having a terminal isocyanate group is produced by reacting a known general-purpose polyol such as an oxyethylene / oxypropylene copolymer with a polyisocyanate, May be utilized having an active hydrogen on the chain extended urethane prepolymer (meth) product obtained by reacting an acrylic monomer. In order to produce a trifunctional or higher functional urethane (meth) acrylate, a trifunctional or higher functional polyol such as trimethylolpropane, ditrimethylolpropane, pentaerythritol and dipentaerythritol is used.

  In particular, a trifunctional polyisocyanate compound is preferably used to synthesize a 9-functional or 15-functional urethane (meth) acrylate. Specifically, a nurate compound derived from 2,6-hexamethylene diisocyanate and a nurate compound derived from isophorone diisocyanate can be used.

  When a polyisocyanate compound other than nurate is used, a polyester polyol having 3 or more hydroxyl groups in one molecule, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylene diisocyanate, 1 , 4-xylene diisocyanate, xylylene diisocyanate, 1,5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-dibenzyl diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 2,6-hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, 2,2,4-trimethylhexene Diisocyanate, it is possible to use 2,4,4 polyisocyanate compound obtained by the reaction of trimethyl hexamethylene diisocyanate.

  A polyester polyol having two or more hydroxyl groups in one molecule can be obtained by an esterification reaction of a polycarboxylic acid and a polyhydric alcohol. The polyvalent carboxylic acid is not particularly limited, but adipic acid, sebacic acid, succinic acid, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, fumaric acid, maleic acid, Examples include maleic anhydride, itaconic acid, trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, and the like. Further, the polyhydric alcohol is not particularly limited, but ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, 3-methyl 1,5- Examples thereof include pentanediol, bisphenol A ethylene oxide or propylene oxide adduct, glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, dimethylolpropionic acid, dimethylolbutanoic acid, and the like.

  The said polyisocyanate compound may use only 1 type, and may use 2 or more types of polyisocyanate compounds together.

  Examples of the (meth) acrylic monomer having active hydrogen include 2-hydroxyethyl acrylate or methacrylate, 2-hydroxypropyl acrylate or methacrylate, ethylene glycol mono (meth) acrylate, propylene glycol mono (meth) acrylate, 2-hydroxy Examples include -3-methoxypropyl acrylate or methacrylate, pentaerythritol triacrylate or methacrylate, N-methylol acrylamide or methacrylamide, N-hydroxyacrylamide or methacrylamide. These lactone adducts (for example, PCL-FA or PCL-FM series manufactured by Daicel Chemical Industries, Ltd.) can also be used. Further, dipentaerythritol poly (meth) acrylate (for example, “DPHA” manufactured by CYTEC, etc.) can also be used.

  In order to produce a polyfunctional urethane (meth) acrylate having 2 or more, for example, 3 or 6 (meth) acryloyl groups in the present invention, first, 1 mol of poly (di) isocyanate compound and active hydrogen A monoisocyanate compound having an isocyanate group at one end and a (meth) acryloyl group at the other end is synthesized by reacting about 1 mol of a (meth) acrylic monomer having R 3 mol or 6 mol of the same monoisocyanate compound is reacted with 1 mol of a polyol having 3 hydroxyl groups or a polyol having 6 hydroxyl groups such as dipentaerythritol.

  As another method for producing a polyfunctional urethane (meth) acrylate having 2 or more, for example, 3 or 6 (meth) acryloyl groups in the present invention, three hydroxyl groups such as trimethylolpropane are used. A urethane prepolymer having 3 or 6 isocyanate groups by reacting 3 mol or 6 mol of a poly (di) isocyanate compound with 1 mol of a polyol having 6 hydroxyl groups, such as a polyol having a hydroxyl group or dipentaerythritol Then, 1 mol of the urethane prepolymer is reacted with a (meth) acrylic monomer having 3 mol or 6 mol of active hydrogen. In addition, when using the polyisocyanate compound which has three isocyanate groups, it changes by changing suitably the molar ratio of each component in each reaction.

  The former reaction sequence is preferred because a polyfunctional urethane (meth) acrylate having two or more (meth) acryloyl groups in one molecule can be produced without causing much by-product.

  Polyfunctional urethane acrylates having 9 or 15 (meth) acryloyl groups can also be produced in the same manner as described above. For example, when producing a polyfunctional urethane acrylate having 9 (meth) acryloyl groups, 3 such as a polyisocyanate compound or a nurate compound (including a urethane prepolymer) having 3 isocyanate groups and pentaerythritol triacrylate The (meth) acrylic monomer having an active hydrogen having an acryloyl group is reacted.

  During the synthesis of the urethane prepolymer, it is preferable to add an excess of poly (di) isocyanate compound in order to suppress a sudden increase in viscosity during the reaction. In this case, the produced urethane prepolymer contains an unreacted poly (di) isocyanate compound. When a highly pure urethane prepolymer is required, the overall reaction time becomes long, but when one isocyanate group such as (meth) acrylic monomer and isophorone diisocyanate reacts first, There is also a method of reacting a poly (di) isocyanate compound whose reactivity is extremely lowered.

  In order to produce a polyfunctional urethane (meth) acrylate in the present invention, a poly (di) or (tri) isocyanate compound is added to a (meth) acrylic monomer having active hydrogen, and the NCO concentration is adjusted to the OH concentration. It is preferable to make it react so that it may become less than an equivalent. This is because gelation occurs when the NCO concentration of the polyisocyanate compound is equal to the OH concentration, and when the NCO concentration exceeds the OH concentration, unreacted NCO groups remain, resulting in poor curing and gelation. It is a cause. For this reason, it is preferable to make the NCO concentration smaller than the OH concentration.

  The above reaction is preferably performed in the presence of a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, or phenothiazine. The amount of these polymerization inhibitors is preferably 1 to 10000 ppm (weight basis), more preferably 100 to 1000 ppm, and still more preferably 400 to 500 ppm with respect to the polyfunctional urethane (meth) acrylate to be produced. If the amount of the polymerization inhibitor is less than 1 ppm relative to the polyfunctional urethane (meth) acrylate, a sufficient polymerization inhibition effect may not be obtained. If it exceeds 10,000 ppm, the physical properties of the product may be adversely affected. .

  For the same reason, the above reaction is preferably performed in an atmosphere of molecular oxygen-containing gas. The oxygen concentration is appropriately selected in consideration of safety.

  The above reaction may be performed using a catalyst in order to obtain a sufficient reaction rate. As the catalyst, dibutyltin dilaurate, tin octylate, tin chloride or the like can be used, but dibutyltin dilaurate is preferred from the viewpoint of reaction rate. The amount of these catalysts is usually 1 to 3000 ppm (weight basis), preferably 50 to 1000 ppm, based on the polyfunctional urethane (meth) acrylate. When the amount of the catalyst is less than 1 ppm, a sufficient reaction rate may not be obtained, and when it is added in an amount of more than 3000 ppm, the physical properties of the product such as a decrease in light resistance may be adversely affected.

  The above reaction is preferably performed at a temperature of 130 ° C. or lower, and more preferably performed at a temperature of 50 ° C. to 130 ° C. When the temperature is lower than 50 ° C., a practically sufficient reaction rate may not be obtained. When the temperature is higher than 130 ° C., the double bond portion may be cross-linked by radical polymerization due to heat, and a gelled product may be generated. The reaction is usually carried out while analyzing by gas chromatography, titration method or the like until the residual isocyanate group is 0.1% or less.

  The above reaction may be performed in an organic solvent. Usable organic solvents include hydrocarbon solvents such as toluene and xylene, ester solvents such as n-butyl acetate, methyl cellosolve acetate and propylene glycol monomethyl ether acetate, ketone solvents such as methyl isobutyl ketone and diisobutyl ketone, ethylene There are ether solvents such as glycol monomethyl ether and ethylene glycol monoethyl ether. From the viewpoint of PRTR (Pollutant Release and Transfer Register, chemical substance discharge and transfer notification system) method and toxicity, propylene glycol monomethyl ether acetate, ethylene Glycol monoethyl ether. You may comprise the composition which concerns on this invention using the urethane (meth) acrylate containing a solvent. If necessary, an organic solvent such as methyl ethyl ketone, ethyl acetate, butyl acetate, and isopropanol can be used. When an organic solvent is used for the purpose of reducing the viscosity of the resin, the amount used is 1 to 50 parts by weight, preferably 10 to 20 parts by weight, based on 100 parts by weight of the component (A). If the amount of the organic solvent used is less than 1 part by weight, it is meaningless to use, and if it exceeds 50 parts by weight, tackiness may remain in the cured coating film, which is not preferable.

  As for the weight average molecular weight of urethane (meth) acrylate, 500-10000 are preferable, More preferably, it is 500-5000, More preferably, it is 500-3000, Most preferably, it is 1000-2000. If the molecular weight is less than 500, there is a risk of impairing the wear resistance and low shrinkage required for the cured film after light irradiation. Conversely, if the molecular weight exceeds 10,000, a curing failure will occur, and the appearance of tack and a decrease in solvent resistance will occur. May be accompanied. Furthermore, since the hardness is lowered, there is a possibility that the film cannot serve as a top coat.

  As a commercial product of a polyfunctional urethane (meth) acrylate having two or more (meth) acryloyl groups in one molecule in the present invention, a specific product name is bifunctional urethane (meth) acrylate (Nippon Kayaku) “UX-2201” or “UX-8101” manufactured by Kyoeisha Co., Ltd. “UF-8001”, “UF-8003”, “UX-6101”, “UX-8101” manufactured by Kyoeisha Chemical Co., Ltd., manufactured by Daicel Cytec Co., Ltd. "Ebecryl 244", "Ebecryl 284", "Ebecryl 2002", "Ebecryl 4835", "Ebecryl 4883", "Ebecryl 8807", "Ebecryl 8700" acrylate (Metal Urethane Co., Ltd.) "Ebecryl 254", "E becryl 264 "," Ebecryl 265 "), tetrafunctional urethane (meth) acrylate (" Ebecryl 8210 "manufactured by Daicel-Cytech Co., Ltd.), hexafunctional urethane (meth) acrylate (" Ebecryl 1290k "manufactured by Daicel-Cytec Co., Ltd.) , “Ebecryl 5129”, “Ebecryl 220”).

  The composition of this invention may contain the other crosslinking | crosslinked monomer or oligomer with a component (A).

  The crosslinkable monomer or oligomer is not particularly limited, and a monomer or oligomer containing a known (meth) acryloyl group can be used. Examples of the monomer containing (meth) acryloyl group include phenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, polycaprolactone-modified hydroxyethyl acrylate, dicyclopentenyloxy. Ethyl acrylate, acryloyl morpholine, 1,6-hexanediol (meth) acrylate, tripropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) Acrylate, 3 mol of trimethylolpropane, 3 mol of propylene oxide adduct, 6 mol of tri (meth) acrylate, trimethylolpropane Tri (meth) acrylate b pyrene oxide adduct, glycerin propoxy tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, polyfunctional monomers such as hexa (meth) acrylate caprolactone modified products of dipentaerythritol. Furthermore, monofunctional or polyfunctional monomers such as (meth) acrylate having an epoxy group such as glycidyl (meth) acrylate, glycidoxybutyl (meth) acrylate, and 3,4-epoxycyclohexylmethyl (meth) acrylate may be mentioned. A mixture of two or more of these may be used.

  Moreover, as an oligomer containing a typical (meth) acryloyl group, urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate, etc. are mentioned, These 2 types A mixture of the above may also be used. In addition, when mix | blending and hardening the (meth) acrylate etc. which have an epoxy group, it is preferable to use a cationic initiator together.

  The compounding amount of the various (meth) acryloyl group-containing monomers or oligomers blended as necessary is 1 to 2000 parts by weight, preferably 1 to 700 parts by weight, based on 100 parts by weight of the component (A) in the present invention. Parts, more preferably 1 to 600 parts by weight. If the amount is less than 1 part by weight, there is no meaning to add. If the amount is more than 2000 parts by weight, the characteristics of the component (A), and further, the characteristics due to the combination with the component (B) and the component (C) to be described later do not appear.

  The production method of urethane (meth) acrylate in the present invention is also described in, for example, JP-A-7-157531, JP-A-2000-95837, JP-A-2002-145936, and the like.

  The content of the component (A) in the composition of the present invention is preferably 100 to 65% by weight, more preferably 97 to 80% by weight, and still more preferably 95 to 90% by weight. Moreover, 100-80: 0-20 are preferable, as for the weight ratio of a component (A): component (B), 95-90: 5-10 are more preferable, and 95-92: 5-8 are more preferable. Moreover, 100-65: 0-35 are preferable, as for the weight ratio of a component (A): component (C), 97-80: 3-20 are more preferable, and 95-90: 5-10 are more preferable.

1.2 (Meth) acrylic copolymer (B)
The chemical structure of the (meth) acrylic copolymer (B) in the present invention is not particularly limited, but preferably has a (meth) acryloyl group and a carboxyl group in the side chain. As a method for synthesizing the (meth) acrylic copolymer resin (B), first, for example, a (meth) acrylic monomer having a carboxyl group such as acrylic acid or methacrylic acid is used, and another radical polymerizable monomer is used. A radical copolymer is used as a polymerization component to synthesize a (meth) acrylic copolymer having a carboxyl group in the side chain. Next, for example, an epoxy (meth) acrylate such as 3,4-epoxycyclohexylmethyl (meth) acrylate is added to a part or all of the carboxyl groups of the (meth) acrylic copolymer having a carboxyl group in the side chain. The (meth) acrylic copolymer resin (B) can be obtained by reacting to form a (meth) acryloyl group in the side chain.

  In addition, monofunctional acrylate monomers such as acryloylmorpholine, β-carboxyethyl acrylate, isobornyl acrylate, octyl / decyl acrylate, ethoxylated phenyl acrylate, and the like can be used as a dilution monomer for viscosity adjustment.

  The radical copolymerization is carried out under normal conditions, for example, at a temperature of 60 to 120 ° C., preferably 70 to 100 ° C., preferably in an inert gas atmosphere.

  Examples of the (meth) acrylic monomer having a carboxyl group include acrylic acid and methacrylic acid, as well as a modified unsaturated monocarboxylic acid chain-extended between an unsaturated group and a carboxylic acid, such as β-carboxyethyl (meth) acrylate. 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, 2-acryloyloxyethyl hexahydrophthalic acid, unsaturated monocarboxylic acid having an ester bond such as lactone modification, modified unsaturated monocarboxylic acid having an ether bond And the like.

  Other radical polymerizable monomers include (meth) acrylic such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, and hexyl (meth) acrylate. (Meth) acrylic acid esters having a hydroxyl group such as acid alkyl esters, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, caprocactone modified 2-hydroxyethyl (meth) acrylate , Methoxydiethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, isooctyloxydiethylene glycol (meth) acrylate, phenoxytriethylene glycol Lumpur (meth) acrylate, methoxy triethylene glycol (meth) acrylate, (meth) acrylates such as methoxy polyethylene glycol (meth) acrylate.

  The copolymerization ratio of the (meth) acrylic monomer having a carboxyl group and other radical polymerizable monomers can be arbitrarily changed, but the former / the latter (molar ratio) = 5/95 to 99/1 is preferable. More preferably, it is the range of 5 / 95-50 / 50.

  A part or all of the carboxyl groups of the (meth) acrylic copolymer having a carboxyl group in the side chain thus produced are alicyclic such as 3,4-epoxycyclohexylmethyl (meth) acrylate. A (meth) acrylic copolymer resin (B) is obtained by reacting an epoxy (meth) acrylate such as epoxy (meth) acrylate or glycidyl (meth) acrylate to form a (meth) acryloyl group in the side chain. be able to.

  The epoxy (meth) acrylate is appropriately adjusted in consideration of the copolymerization ratio of the (meth) acrylic monomer having a carboxyl group and another radical polymerizable monomer. Moreover, it is preferable to adjust suitably so that the acid value of (meth) acrylic-type copolymer resin (B) may be 20-200 (KOHmg / g) and a double bond equivalent may be 350-450.

  The acid value of the (meth) acrylic copolymer resin (B) is preferably 20 to 200 (KOHmg / g), more preferably 20 to 80 (KOHmg / g). If the acid value is less than 20 (KOHmg / g), the adhesiveness of the cured film to the (meth) acrylic copolymer resin may be reduced. Conversely, if the acid value exceeds 200 (KOHmg / g), the component ( The compatibility with A) is lowered, making it difficult to prepare a blend.

  The double bond equivalent of the (meth) acrylic copolymer resin is preferably 350 to 450, more preferably 380 to 450. If the double bond equivalent is less than 350, it may cause curing failure. Conversely, if the double bond equivalent exceeds 450, curing proceeds excessively, causing shrinkage of the film and giving the film brittleness. This is not preferable because it may be

  In order to perform the radical copolymerization reaction under stable conditions, the reaction may be performed in an organic solvent. Usable organic solvents include hydrocarbon solvents such as toluene and xylene, ester solvents such as n-butyl acetate, methyl cellosolve acetate and propylene glycol monomethyl ether acetate, ketone solvents such as methyl isobutyl ketone and diisobutyl ketone, ethylene There are ether solvents such as glycol monomethyl ether and ethylene glycol monoethyl ether, and propylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether are preferable from the viewpoint of PRTR method and toxicity. Among them, it is preferable to use a high-boiling solvent such as propylene glycol monomethyl ether or the same acetate, and epoxy (meth) acrylate can be reacted while containing the solvent, or the solvent is left as it is in the composition according to the present invention. It may be left. If necessary, an organic solvent such as methyl ethyl ketone, ethyl acetate, butyl acetate, isopropyl alcohol, and isobutyl alcohol can also be used.

  The usage-amount of an organic solvent is 40-900 weight part with respect to 100 weight part of total amounts of the (meth) acrylic-type monomer which has a carboxyl group, and another radical polymerizable monomer, Preferably it is 100-300 weight part. If the amount of the organic solvent used is less than 40 parts by weight, it is meaningless to use, and if it exceeds 900 parts by weight, the molecular weight of the (meth) acrylic copolymer resin (B) does not increase and the residual amount of monomer also increases. Therefore, neither is preferable.

  The (meth) acrylic copolymer resin (B) has a weight average molecular weight of 5,000 to 20,000, preferably 7,000 to 20,000. If the weight average molecular weight of the (meth) acrylic copolymer resin (B) is less than 5000, the heat resistance and the coating strength may be reduced. Conversely, if the molecular weight exceeds 20000, the solubility in a solvent or the like is reduced. However, workability may be reduced.

  The production method of the (meth) acrylic copolymer resin (B) is also described in, for example, JP-A-1-289820, JP-A-8-21607 and JP-A-8-262221.

  As a commercial product of (meth) acrylic copolymer resin (B), Cyclomer P (ACA200) manufactured by Daicel Chemical Industries, whose basic skeleton is composed of an acrylic copolymer [weight average molecular weight 15000 to 18000, Acid value 105-125 mgKOH / g], cyclomer P (ACA230AA) [weight average molecular weight 10,000-16000, acid value 33-47 mgKOH / g], cyclomer P (ACA200M) [weight average molecular weight 10,000-13000, acid value 105- 125 mg KOH / g], cyclomer P (ACAZ250) [weight average molecular weight 9000 to 12000, acid value 70 to 80 mg KOH / g], cyclomer P (ACA 320) [weight average molecular weight 20000 to 27000, acid value 120 to 140 mg KOH / g] Can be used That.

  0-20 weight% is preferable, as for content of a component (B) in the composition of this invention, 5-10 weight% is more preferable, and 5-8 weight% is further more preferable. Moreover, 0-30: 100-70 are preferable, as for the weight ratio of a component (B): component (C), 5-20: 95-80 are more preferable, and 10-15: 90-85 are more preferable.

1.3 Monomer or oligomer (C)
One or more selected from the group consisting of the monomer (c1) and the oligomer (c2) contained in the thermal curing or active energy ray curing composition of the present invention is itself (including a photopolymerization initiator for curing). Has a property that the flexibility of the resin obtained by curing the resin into a film shape is 100 times or more according to the bending strength evaluation. In addition, a softness | flexibility is measured by bending strength evaluation. Fracture strength evaluation is measured and evaluated by the method prescribed in JIS P8115, and specific measurement and evaluation methods will be described in detail in Examples (“Production of coating film” and “Flexibility: Resistance to resistance” in Examples). (Refer to "Folding strength (MIT) evaluation").

  The monomer (c1) and the oligomer (c2) have a property of curing when irradiated with active energy rays such as heat or ultraviolet rays or electron beams. The flexibility after curing is 100 times or more, preferably 200 times or more, more preferably 300 times or more according to the bending strength evaluation. The upper limit of flexibility is not particularly defined, but when component (C) having extremely high flexibility is used and component (A) and component (C) are compatible with each other, the above-described component (A The performance can be maintained / expressed by selecting a relatively low flexibility or adjusting the flexibility of the entire composition by increasing the content of the component (A).

  The monomer (c1) and the oligomer (c2) are not particularly limited in chemical structure as long as they have the above flexibility, but the monomer constituting the monomer (c1) or oligomer (c2) has an epoxy group. It is more preferable to have an alicyclic epoxy group.

  As the monomer having an alicyclic epoxy group constituting the monomer (c1) or oligomer (c2) of the present invention, for example, a polyglycidyl ether, cyclohexene or cyclopentene ring-containing compound having at least one alicyclic ring is oxidized. Examples include cyclohexane oxide obtained by epoxidation with an agent, and a compound containing cyclopentene oxide. In addition, examples of the monomer include hydrogenated bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methylcyclohexyl-3,4. -Epoxy-1-methylcyclohexanecarboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4- Epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro- 3 4-epoxy) cyclohexane-methanedioxane, bis (3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene dioxide, 4-vinylepoxycyclohexane, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3, 4-epoxy-6-methylcyclohexylcarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol di (3,4-epoxycyclohexylmethyl) ether, ethylenebis (3,4-epoxycyclohexane) Carboxylate), dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, and the like.

  Furthermore, as a monomer which comprises the monomer (c1) or oligomer (c2) of this invention which has an alicyclic epoxy group, the alicyclic epoxy compound which has a structure shown to following General formula (1) is also mentioned, for example. .

（一般式（１）中、Ｒ¹〜Ｒ¹⁰は、水素又はＣ₁〜Ｃ₂₀の飽和又は不飽和炭化水素基であり、該炭化水素基内にはエーテル結合、エステル結合またはアルコール性水酸基を含んでいてもよい。さらにＲ¹〜Ｒ¹⁰は、一般式（１）に示す構造からＲ¹〜Ｒ¹⁰のいずれか１つが除かれた残基又はＲ¹〜Ｒ¹⁰のいずれか１つから水素が除かれた残基であってもよい。なお、基内とは、基の内部、基の末端、又は基の結合を含むことを意味する。）

(In the general formula (1), R ^{1 to} R ¹⁰ are hydrogen or a C _{1 to} C ₂₀ saturated or unsaturated hydrocarbon group, and an ether bond, an ester bond or an alcoholic hydroxyl group is contained in the hydrocarbon group. Further, R ^{1 to} R ¹⁰ may be a residue obtained by removing any one of R ^{1 to} R ¹⁰ from the structure represented by the general formula (1) or any one of R ^{1 to} R ^10. (It may be a residue from which hydrogen is removed. In addition, the term “inside group” means that the inside of the group, the end of the group, or the bonding of the group is included.)

  Furthermore, as a monomer which comprises the monomer (c1) or oligomer (c2) of this invention which has an alicyclic epoxy group, the alicyclic epoxy compound which has a structure shown in following General formula (2) is mentioned, for example. .

（一般式（２）中、Ｒ²¹は、水素又はｋ価のＣ₁〜Ｃ₂₀の炭化水素基であり、該炭化水素基内にはエーテル結合、エステル結合またはアルコール性水酸基を含んでいてもよく、Ｒ²²は水素、ヒドロキシ基、又はＣ₁〜Ｃ₂₀の炭化水素基であり、該炭化水素基内にはエーテル結合、エステル結合またはアルコール性水酸基を含んでいてもよく、Ｒ²³およびＲ²⁴は水素またはＣ₁〜Ｃ₂₀の炭化水素基であり、好ましくは水素またはメチル基であり、Ｒ²¹またはＲ²²のいずれか少なくとも１つに上記一般式（１）に示す構造からＲ¹〜Ｒ¹⁰のいずれか１つが除かれた残基を含む。ｎは３〜１０の整数であり、ｍは２〜１０の整数であり、ｋは１〜１０の整数であり、複数個のＲ³及びＲ⁴は互いに同一または異なっていてもよく、ｋが２以上のときはｋ個の基構造は互いに同一又は異なっていてもよい。なお、基内とは、基の内部、基の末端、又は基の結合を含むことを意味する。）

(In the general formula (2), R ²¹ is hydrogen or a C ₁ -C ₂₀ hydrocarbon group of k valence, and the hydrocarbon group may contain an ether bond, an ester bond or an alcoholic hydroxyl group. R ²² is hydrogen, a hydroxy group, or a C _{1 to} C ₂₀ hydrocarbon group, and the hydrocarbon group may contain an ether bond, an ester bond or an alcoholic hydroxyl group, and R ²³ and R ²⁴ is hydrogen or a C _{1 to} C ₂₀ hydrocarbon group, preferably hydrogen or a methyl group, and at least one of R ^{21 and} R ²² is represented by the structure represented by the above general formula (1) from R ¹ to Including a residue from which any one of R ¹⁰ is removed, n is an integer of 3 to 10, m is an integer of 2 to 10, k is an integer of 1 to 10, and a plurality of R ³ And R ⁴ may be the same or different from each other, and when k is 2 or more, The k group structures may be the same as or different from each other, and the term “inside of the group” means that the inside of the group, the terminal of the group, or the bonding of the group is included.)

  Specific examples of the monomer constituting the monomer (c1) or oligomer (c2) of the present invention having an alicyclic epoxy group represented by the general formula (1) include 1-vinyl-3,4, for example. -An alicyclic monoepoxide having an epoxycyclohexane vinyl group (trade name “CEL-2000” manufactured by Daicel Chemical Industries, Ltd.), 1,2,8,9-diepoxy limonene alicyclic epoxy diluent (Daicel Chemical) Kogyo Co., Ltd., trade name “CEL-3000”).

  Moreover, as a compound applicable to the said General formula (2), an alicyclic epoxy resin (the Daicel Chemical Industries Ltd. make, brand name "CEL-2081"), a tetrafunctional alicyclic epoxy resin (Daicel Chemical Industries, Ltd.) ), Trade name “Epolide GT-401”; made by Daicel Chemical Industries, trade name “Epolide GT-403”), trifunctional alicyclic epoxy resin (produced by Daicel Chemical Industries, trade name “Epolide”) GT-301 "; manufactured by Daicel Chemical Industries, Ltd., trade name" Epolide GT-302 "), adipic acid diglycidyl ester (manufactured by Nagase Kasei Kogyo Co., Ltd., trade name" Denacol 701 ") and the like. In addition, as a compound corresponding to the above general formula (2), resorcin diglycidyl ether (manufactured by Nagase Kasei Kogyo Co., Ltd., trade names “Denacol EX-421”, “Denacol EX-201”), neopentyl glycol diglycidyl ether (Nagase Kasei Kogyo Co., Ltd., trade names “Denacol EX-211”, “Denacol EX-911”), adipic acid diglycidyl ester (manufactured by Nagase Kasei Kogyo Co., Ltd., trade name “Denacol EX-701”), etc. Is mentioned.

  The monomer constituting the monomer (c1) or oligomer (c2) of the present invention having an alicyclic epoxy group is particularly 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate. preferable.

  The weight average molecular weight of the monomer constituting the monomer (c1) and the oligomer (c2) of the present invention having an epoxy group is usually about 200 to 20000, preferably about 300 to 10,000.

  The content of the component (C) in the composition of the present invention is preferably 0 to 35% by weight, more preferably 3 to 20% by weight, and still more preferably 5 to 10% by weight.

As the monomer (c1) or oligomer (c2) of the present invention, the monomer or oligomer described below can also be used. The monomer or oligomer described below is relatively less flexible after curing than the monomer or oligomer described above, but constitutes the composition according to the present invention by, for example, suppressing the content in the composition. be able to.
That is, the content of the monomer and oligomer having a relatively low flexibility after curing with respect to the entire composition is determined in consideration of the flexibility after curing of the composition. %, Preferably 1 to 10% by weight, more preferably 3 to 7% by weight.

  Monomers and oligomers (constituent monomers) having relatively low flexibility after curing are acrylates such as epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, and polyether (meth) acrylate, A polyfunctional monomer or a combination thereof. In particular, phenoxyethyl acrylate is preferable.

<Epoxy (meth) acrylate>
Epoxy (meth) acrylate can be obtained, for example, by reacting an epoxy compound with a carboxyl group-containing acrylic compound. In this case, when the epoxy compound is reacted in an amount of 25 to 75 parts by weight and the carboxyl group-containing acrylic compound is reacted in an amount of 75 to 25 parts by weight, the flexibility of the resulting epoxy (meth) acrylate after curing becomes a preferable range.

  The epoxy compound used for producing the (meth) acrylate having an epoxy group is not particularly limited as long as it has an epoxy group. For example, a glycidyl ether type epoxy resin such as a bisphenol type epoxy resin (bisphenol A) Type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, etc.), glycidyl ester type epoxy resin, novolac type epoxy resin (phenol novolak type epoxy resin, cresol novolak type epoxy resin, etc.) and the like. The epoxy resin also includes an epoxy resin having a large molecular weight (phenoxy resin). Etc.

  Similarly, the carboxyl group-containing acrylic compound used for producing the (meth) acrylate having an epoxy group is not particularly limited as long as it has such a group. For example, acrylic acid, methacrylic acid, These lower alkyl esters (methyl esters, ethyl esters, etc.), acrylate monomers, and the like. Examples of the acrylate monomer include diacrylate (1,6-hexanediol diacrylate, 1,4-butanediol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, tetraethylene glycol diacrylate, tripropylene glycol diacrylate, Neopentyl glycol diacrylate, 1,4-butanediol dimethacrylate, poly (butanediol) diacrylate, tetraethylene glycol dimethacrylate, 1,3-butylene glycol diacrylate, triethylene glycol diacrylate, triisopropylene glycol diacrylate , Polyethylene glycol diacrylate and bisphenol A dimethacrylate, etc.); triacrylate ( Limethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol monohydroxytriacrylate, and trimethylolpropane triethoxytriacrylate); tetraacrylate (such as pentaerythritol tetraacrylate and di-trimethylolpropane tetraacrylate) and pentaacrylate ( And dipentaerythritol (monohydroxy) pentaacrylate).

  When the (meth) acrylate having an epoxy group is produced, the amount of the acrylic compound used relative to the epoxy compound is not particularly limited. It is preferably 3 to 2.0 chemical equivalents, and more preferably 0.5 to 1.5 chemical equivalents. This is because the flexibility after curing of the obtained (meth) acrylate having an epoxy group is within a preferable range.

  The reaction is usually performed at a temperature in the range of 50 ° C. to 150 ° C. for about 1 to 8 hours under normal pressure. In the reaction, a catalyst is preferably used. Specific examples of the catalyst include amines such as triethylamine, dimethylbutylamine and tri-n-butylamine, quaternary ammonium salts such as tetramethylammonium salt, tetraethylammonium salt, tetrabutylammonium salt and benzyltriethylammonium salt, Alternatively, quaternary phosphonium salts, phosphines such as triphenylphosphine, and imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole can be used.

  In the reaction, alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, ethyl cellosolve, esters such as methyl isobutyl ketone (MIBK), methyl cellosolve acetate, ethyl celloacetate, methyl ethyl ketone, etc. A ketone solvent, aromatic compounds such as benzene, toluene, chlorobenzene, and dichlorobenzene can be used as the reaction solvent. During the reaction, hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, 4-methylquinoline, phenothiazine, or the like may be allowed to coexist in the reaction system as a polymerization inhibitor.

  In the reaction, in order to suppress the polymerization reaction, in some cases, the reaction can be performed under an air stream such as air. At that time, an antioxidant such as 2,6-di-t-butyl-4-methylphenol may be used in combination in order to prevent an oxidation reaction by air.

  Furthermore, as the epoxy (meth) acrylate, specifically, a polyolefin-based epoxy resin synthesized by a peroxidation method; a fat such as a polyglycidyl ester obtained from cyclopentadiene oxide, cyclohexene oxide or hexahydrophthalic acid and epichlorohydrin Cyclic epoxy resin; polyhydric phenols such as bisphenol A, catechol, and resorcinol or polyvalents such as (poly) ethylene glycol, (poly) propylene glycol, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol, diglycerol, sorbitol Polyglycidyl ethers obtained from alcohol and epichlorohydrin; epoxides obtained from epoxidized vegetable oil or novolac-type phenolic resin and epichlorohydrin Rack; epoxy resin obtained from phenolphthalein and epichlorohydrin; copolymer of glycidyl methacrylate and methyl methacrylate acrylic monomer or styrene; ring opening of glycidyl group of the above epoxy compound and monocarboxylic acid-containing (meth) acrylic acid Examples include epoxy acrylate obtained by the reaction. These synthetic reactions can be carried out according to known methods, for example, the method described in JP-A No. 2000-327950.

  In addition to these, as an epoxy (meth) acrylate, an acrylate having an alicyclic epoxy group (manufactured by Daicel Chemical Industries, Ltd., trade name “Cyclomer A200”), a methacrylate having an alicyclic epoxy group (Daicel) Chemical Industry Co., Ltd., trade name “Cyclomer M100”) and the like.

  Thus, the weight average molecular weight of the epoxy (meth) acrylate oligomer obtained is about 200-20000 normally, Preferably it is about 300-10000.

<Urethane (meth) acrylate>
Urethane (meth) acrylate can be obtained, for example, by reacting a polyol compound, (poly) isocyanate, and a hydroxyl group-containing (meth) acrylate. In this case, when 12.5 to 37.5 parts by weight of the polyol compound, 12.5 to 37.5 parts by weight of (poly) isocyanate, and 25 to 75 parts by weight of the hydroxyl group-containing (meth) acryl compound are polymerized. The flexibility after curing of the resulting urethane acrylate is within a preferred range.

  The reaction is usually performed at a temperature in the range of 50 ° C. to 150 ° C. for about 1 to 8 hours under normal pressure.

  Examples of the polyol compound used for producing urethane (meth) acrylate include diol (polyester diol, polyether diol, polycarbonate diol, polyoxytetramethylene glycol, ethylene glycol, propylene glycol, trimethylene glycol, tetramethylene glycol) 1,2-butanediol, 2,2-dimethyl-1,3-propanediol, 1,6-hexanediol, C2-10 alkylene glycol such as cyclohexanedimethanol, polyethylene glycol, polypropylene glycol, polyoxytetramethylene Polyoxy C2-4 alkylene glycol such as glycol); polyol (glycerin, diglycerin, polyglycerin, trimethylolethane, Trimethylol propane, pentaerythritol, alkylene oxide adduct) of bisphenol A and the like.

(Poly) isocyanate compounds can be used to produce urethane (meth) acrylates. For example, as the isocyanates, compounds having at least one isocyanate group in the molecule are preferable.
Examples of the (poly) isocyanate compound used for producing urethane (meth) acrylate include aromatic diisocyanate (tolylene diisocyanate, phenylene diisocyanate, xylylene diisocyanate, tetramethylxylene diisocyanate, diphenylmethane diisocyanate, tolidine diisocyanate [bis ( 4-isocyanate-3-methylphenyl) methane], triphenylmethane triisocyanate, aromatic diisocyanates such as 1,5-naphthalene diisocyanate); aliphatic diisocyanates (1,4-tetramethylene diisocyanate, 1,6-hexamethylene) Diisocyanate, trimethylhexamethylene diisocyanate, 1,10-decamethylene diisocyanate, lysine diisocyanate Alicyclic diisocyanates (isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, etc.); modified polyisocyanates (polyvalent) Examples thereof include adducts obtained by adding polyisocyanate to alcohol, dimers, trimers having an isocyanurate ring, allophanate-modified products, urea-modified polyisocyanates, and burette-modified polyisocyanates). The polyhydric alcohol in the adduct includes low molecular weight polyols having three or more hydroxyl groups, triols such as glycerin, trimethylolpropane and trimethylolethane, tetraols such as pentaerythritol, and the like. Divalent isocyanate compounds such as hexamethylene diisocyanate and isophorone diisocyanate are preferred.

A hydroxyl group-containing acrylic compound can be used to produce urethane (meth) acrylate.
Examples of hydroxyl group-containing acrylic compounds include hydroxyalkyl (meth) acrylates (2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) ) Acrylate, hydroxy C2-10 alkyl (meth) acrylate such as pentanediol mono (meth) acrylate); halogen-containing hydroxy C2-6 alkyl (meth) acrylate (3-chloro-2-hydroxypropyl (meth) acrylate etc.) Polyalkylene glycol mono (meth) acrylate (polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, etc.); 2-hydroxy-3-phenyloxy Propyl (meth) acrylate; 2-hydroxyalkyl (meth) acryloyl phosphate; trimethylolpropane di (meth) acrylate; pentaerythritol tri (meth) acrylate.

In order to produce urethane (meth) acrylate, together with a polyol compound, (poly) isocyanate, and hydroxyl group-containing (meth) acrylate, a hydroxyl group-containing polyester or a hydroxyl group-containing polyether can be used.
As the hydroxyl group-containing polyester, a hydroxyl group-containing polyester obtained by reaction of one or more polyhydric alcohols with one or more polybasic acids or one or two or more lactones is preferable. Examples of the polyhydric alcohol used in this reaction include 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, neopentyl glycol, polyethylene glycol, polypropylene glycol, Examples thereof include polybutylene glycol, trimethylolpropane, glycerin, pentaerythritol, dipentaerythritol, and the like. These polyhydric alcohols may be used alone or in combination of two or more.

  Examples of the polybasic acid used in the reaction include adipic acid, terephthalic acid, phthalic anhydride, trimellitic acid, and the like. Examples of lactones include β-propiolactone, γ-butyrolactone, and ε-caprolactone.

  As the hydroxyl group-containing polyether, a hydroxyl group-containing polyether obtained by adding one or more alkylene oxides to a polyhydric alcohol is preferable. The polyhydric alcohol used in this reaction is the same as the compound described above, and examples thereof include alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide.

<Polyester (meth) acrylate>
The polyester (meth) acrylate can be obtained, for example, by reacting a hydroxyl group-containing polyester with (meth) acrylic acid. The reaction is usually performed at a temperature in the range of 50 ° C. to 150 ° C. for about 1 to 8 hours under normal pressure.

  Preferred as the hydroxyl group-containing polyester used in this reaction is a hydroxyl group-containing polyester obtained by an esterification reaction of one or more polyhydric alcohols with one or more monobasic acids or polybasic acids. It is. Examples of the polyhydric alcohol include the same compounds as those described above. Examples of the monobasic acid used in the reaction include formic acid, acetic acid, butyric acid, and benzoic acid, and examples of the polybasic acid include adipic acid, terephthalic acid, phthalic anhydride, trimellitic acid, and the like. It is done.

<Polyether (meth) acrylate>
The polyether (meth) acrylate can be obtained, for example, by reacting a hydroxyl group-containing polyether with meth (acrylic) acid. The reaction is usually performed at a temperature in the range of 50 ° C. to 150 ° C. for about 1 to 8 hours under normal pressure.

  A preferred hydroxyl group-containing polyether that can be used in this reaction is a hydroxyl group-containing polyether obtained by adding one or more alkylene oxides to a polyhydric alcohol. Examples of the polyhydric alcohol used in the reaction include the same compounds as those described above. Examples of the alkylene oxide used in the reaction include ethylene oxide, propylene oxide, and butylene oxide.

  What is preferably used as the polyether (meth) acrylate is obtained by reacting an aromatic or aliphatic alcohol having at least one hydroxyl group in the molecule and an alkylene oxide adduct thereof with (meth) acrylic acid. (Meth) acrylates such as 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, isoamyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) Acrylate, isooctyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butane All di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate , Polypropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, Dipentaerythritol hexa (meth) acrylate, ε-caprolactone modified dipentaerythritol hexa (meth) acrylate Is mentioned.

<Multifunctional monomer>
Polyfunctional monomers are, for example, polyfunctional (meth) acrylates, such as bifunctional (meth) acrylates (ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol Di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) Acrylate, 1,4-butylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentanedio Di (meth) acrylate of (polyoxy) C2-20 alkylene glycol such as rudi (meth) acrylate; bisoxyethylenated bisphenol A di (meth) acrylate, bisoxypropylenated bisphenol A di (meth) acrylate, glycerin di (meth) ) Acrylate, etc.), trifunctional (meth) acrylate (trimethylolpropane tri (meth) acrylate, tetramethylol methane tri (meth) acrylate, pentaerythritol tri (meth) acrylate (PETIA), etc.), tetrafunctional (meth) acrylate (Tetramethylol methane tetra (meth) acrylate etc.), hexafunctional (meth) acrylate (dipentaerythritol hexa (meth) acrylate (DPHA) etc.), etc. are mentioned. In addition, as a polyfunctional monomer, you may use the above-mentioned hydroxyl group or carboxyl group containing (meth) acrylate. Moreover, you may use these polyfunctional monomers individually or in combination of 2 or more types.

1.4 Polyol (D)
The thermosetting or active energy ray-curable composition of the present invention preferably further contains a polyol (D). The polyol (D) is not particularly limited as long as it has such a group. Examples of the polyol (B) include ethylene glycol, propylene glycol, 1,4-butylene glycol, 1,6-hexanediol, Low molecular weight diols such as neopentyl glycol, diethylene glycol, triethylene glycol, dipropylene glycol, bisphenol A, hydrogenated bisphenol A, xylene glycol, etc., for example, low molecular weights such as glycerin, 1,1,1-tris (hydroxymethyl) propane Low molecular weight polyols having 4 or more hydroxyl groups such as triols such as D-sorbitol, xylitol, D-mannitol and D-mannitol, such as polyether polyols, polyester polyols, polycarbonate poly Lumpur, acrylic polyol, epoxy polyol, natural oil polyol, silicone polyol, fluorine polyol, polyolefin polyols, and the like.

  The polyol (D) used in the present invention is a (meth) acrylic copolymer comprising at least one ethylenically unsaturated monomer having a hydroxyl group, wherein a lactone monomer is added to the hydroxyl group. Or a trifunctional polyester polyol is preferred.

  The polyol (D) is preferably contained in an amount of 30 to 60% by weight, more preferably 35 to 50% by weight, based on the total weight of the composition of the present invention.

1.5 Active energy ray polymerization catalyst (E)
The composition of the present invention preferably further contains an active energy ray polymerization catalyst (E).
As the active energy ray polymerization catalyst (E), any of the commonly used ultraviolet cationic polymerization catalysts can be used. For example, allyldiazonium salts, diallyliodonium salts and VIa group allylonium salts (PF ₆ , AsF ₆ , SbF ₆ ). Allylsulfonium salts having such anions), iron-allene complexes, sulfonate esters, silyl ether-aluminum complexes, and the like. Among these, an allylsulfonium salt is particularly preferable, and a triarylsulfonium hexafluorophosphate salt is particularly preferable. These may be used alone or in combination of two or more.

  The active energy ray polymerization catalyst (E) is a photopolymerization initiator (aromatic ketones, morpholine polymerization initiator, phosphine polymerization initiator, sulfide polymerization initiator, etc.), radical polymerization initiator (for example, And peroxides such as benzoyl peroxide and di-t-butyl peroxide, and azo compounds such as azobisisobutyronitrile).

  Examples of aromatic ketones include acetophenone or propiophenone polymerization initiators, and specific examples include acetophenone diethyl ketal, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1- ON, benzyl methyl ketal (for example, Ciba Geigy: Irgacure 651), 1-hydroxy-cyclohexyl-phenyl ketone (for example, Ciba Geigy, trade name “Irgacure 184”), 1- [4- (2-hydroxyethoxy) -[Phenyl] -2-hydroxydi-2-methyl-1-propan-1-one. Aromatic ketones include benzophenone polymerization initiators (benzophenone, 4-phenylbenzophenone, etc.), benzoin polymerization initiators (benzoin, benzoin ethyl ether, benzoin isobutyl ether, etc.), thioxanthone polymerization initiators (isopropylthioxanthone). , Diethylthioxanthone, etc.), 2,2-dimethoxy-1,2-diphenylethane-1-one, benzyl and the like. These polymerization initiators can be used alone or in combination of two or more.

  Examples of the morpholine-based polymerization initiator include 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one (for example, Ciba Geigy Inc .: Irgacure 907) and 2-benzyl-2-dimethylamino- 1- (4-morpholinophenyl) -butane (for example, trade name “Irgacure 369” manufactured by Ciba Geigy Co., Ltd.) and the like can be mentioned.

  Examples of the phosphine-based polymerization initiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide (for example, manufactured by Ciba Geigy Corporation): Irgacure 1700; bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide / 2-hydroxy-2-methylphenylpropan-1-one = 25/75 (% by weight)) It is done.

  Examples of the sulfide-based polymerization initiator include tetramethylthiuram monosulfide and diphenyl disulfide.

  In particular, when an epoxy compound having an alicyclic epoxy group is used for the polymerizable monomer and / or oligomer, it is preferable to use a cationic polymerization initiator that generates a cationic species by light or heat. As the cationic polymerization initiator, compounds such as sulfonium salt, iodonium salt, diazonium salt, and allene-ion complex can be used. For example, sulfonium salt-based VACURE1590, UVACURE1591 (above, manufactured by Daicel UCB), DAICAT11 (made by Daicel Chemical), CD-1011 (made by Sartomer), SI-60L, SI-80L, SI-100L (above, Sanshin) Chemicals), etc .; iodonium salt-based DAICAT12 (manufactured by Daicel Chemical), CD-1012 (manufactured by Sartomer); Furthermore, silanol-based cation catalysts such as triphenylsilanol can also be used.

  Moreover, an acid anhydride can also be used as an active energy ray polymerization catalyst (E). Examples of acid anhydrides include tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, methylhymic anhydride, pyromellitic dianhydride, benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 2, 2-bis (3,4-dicarboxyphenyl) propane dianhydride, etc., preferably having one or two aliphatic or aromatic rings in the molecule and one or two acid anhydride groups An acid anhydride having 4 to 25 carbon atoms, preferably about 8 to 20 carbon atoms, is preferable.

  In this case, as the acid anhydride, the content of the compound having a carboxyl group (COOH group) is 0.5% by weight or less (that is, 0 to 0.5% by weight) based on the acid anhydride curing agent. Preferably, 0.4% by weight or less (that is, 0 to 0.4% by weight) is used. Furthermore, the content of the compound having a carboxyl group (COOH group) as the acid anhydride is preferably 0.3% by weight or less (that is, 0 to 0.3% by weight) with respect to the acid anhydride curing agent, It is preferably 0.25% by weight or less (that is, 0 to 0.25% by weight). It is because there exists a possibility that it may crystallize that carboxyl group content is more than fixed amount (for example, 0.5 weight%).

  In addition, the compounding quantity of the acid anhydride as an active energy ray polymerization catalyst (E) is 0.3-0 of the ratio of the acid anhydride group in a hardening | curing agent with respect to 1 mol of epoxy groups of the epoxy compound which has an epoxy group. It is desirable to be in the range of 7 moles. If the amount is less than 0.3 mol, the curability is insufficient. If the amount exceeds 0.7 mol, unreacted acid anhydride remains, and the glass transition temperature may be lowered. More desirably, it is in the range of 0.4 to 0.6 mol. In addition, phenolic curing agents and the like can also be used.

  When the active energy ray polymerization catalyst (E) contains a photopolymerization initiator with respect to the total weight of the composition of the present invention, the addition amount (total amount) of the photopolymerization initiator is 100 monomers or oligomers (A or C). It is preferable that it is about 1 to 20 parts by weight, preferably about 2 to 15 parts by weight, and more preferably about 3 to 10 parts by weight with respect to parts by weight. If the addition amount of the photopolymerization initiator is less than 1 part by weight, the curability of the coating is insufficient and sufficient wear resistance, adhesion and weather resistance are difficult to obtain. On the other hand, when the total addition amount of the photopolymerization initiator exceeds 20 parts by weight, the effect of increasing the amount is not recognized, which is uneconomical, and there is a risk of coloring of the film and precipitation of the unreacted initiator, and also the weather resistance is lowered. This is not preferable because it tends to reduce the physical properties of the cured product.

1.6 Leveling agent (F)
When applying the composition of the present invention onto a substrate or the like, if the wettability on the substrate is poor or the surface property of the formed composition layer is poor, It is possible to add various leveling agents (F) in the composition. As the type of the leveling agent (F), various compounds such as silicon-based, fluorine-based, polyether-based, acrylic acid copolymer-based and titanate-based compounds can be used. Among these, it is particularly preferable to use an acrylic copolymer or an acrylic copolymer solution.

The leveling agent (F) comprises the wettability of the liquid crystalline compound on the alignment film when the liquid crystalline compound layer is formed on the alignment film of the present invention obtained by curing the composition with ultraviolet rays, It is preferable to add to the extent that it does not affect the alignment of the liquid crystal compound layer.
Therefore, the leveling agent (F) is preferably contained in an amount of 3 to 9% by weight, more preferably 4 to 6% by weight, based on the total weight of the composition of the present invention.

1.7 Filler The thermosetting or active energy ray-curable composition of the present invention is characterized in that it contains no filler or does not contain more than 30% by weight. If the filler is contained in a certain amount or more, the coating hardness becomes high but becomes brittle, and it is easily affected by collision / impact on the coating surface, and the Taber abrasion strength is lowered. As a result, the composition containing a certain amount or more of the filler is not suitable for applications in which fine scratches are repeated by shoes, trolley wheels, sand, dust, etc., like a floor protection material. It is.

  The filler contained in the thermosetting or active energy ray-curable composition of the present invention may be an inorganic filler or an organic filler.

  Examples of inorganic fillers include calcium sulfate, calcium silicate, clay, diatomaceous earth, graphite, evening lime, graphite, silica sand, glass, iron oxide, alumina and other metals, and the shape is granular, flat, scale-like Any of a needle shape, a spherical shape, a hollow shape, and a fibrous shape may be used. Specifically, granular fillers such as silicon carbide, silicon nitride, silicic force, boron nitride, aluminum nitride, carbon black, flat or scaly fillers such as mica, sericite, pyrophyllite, graphite, shirasu Examples thereof include hollow fillers such as balloons, metal balloons, glass balloons, and pumice, mineral fibers such as glass fibers, carbon fibers, graphite fibers, whiskers, metal fibers, silicon carbide fibers, asbestos, and wstonite. The surface of these inorganic fillers was subjected to surface treatment using stearic acid, oleic acid, valmitic acid or a metal salt thereof, paraffin wax, polyethylene wax or a modified product thereof, organic silane, organic borane, organic titanate, etc. It is preferable to use an inorganic filler that has been subjected to surface treatment since the filler is well mixed in the resin composition.

The shape of these inorganic fillers is not particularly limited, but is preferably substantially spherical or elliptical. The particle size of the inorganic filler measured by the light scattering method is preferably 0.01 to 300 μm, more preferably 0.05 to 100 μm, and particularly preferably 0.1 to 10 μm.
The inorganic filler does not contain more than 30% by weight, preferably does not contain 20% by weight or more, more preferably does not contain 10% by weight or more, and most preferably does not contain at all.

  Examples of the organic filler include acrylic monomers (acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters, etc.), styrene monomers (styrene, alkyl-substituted styrene, etc.), and crosslinkable monomers. Copolymers (divinylbenzene, divinylsulfone, ethylene glycol dimethacrylate, trimethylolpropane trimethyl acrylate, pentaerythritol tetramethyl acrylate, etc.); melamine resins; benzoguanamine resins; phenol resins; silicone resins, etc. It is done. These may be obtained by an addition polymerization method, or may be obtained by polycondensation or polyaddition reaction. The organic polymer constituting the filler may be a non-crosslinked type or a crosslinked type, but the crosslinked type is preferred from the viewpoint of heat resistance. The method for making the organic polymer into fine particles is not limited, but a method of directly making fine particles at the time of polymerization using a method such as emulsion polymerization or suspension polymerization is preferable. When these polymerization methods are employed, means for copolymerizing a small amount of a polar monomer having a special structure capable of imparting self-emulsifying properties may be employed.

The shape of these organic fillers is not particularly limited, but is preferably substantially spherical or elliptical. The particle size of the organic filler measured by the light scattering method is preferably 0.01 to 300 μm, more preferably 0.05 to 100 μm, and particularly preferably 0.1 to 10 μm.
The organic filler does not contain more than 30% by weight of the composition, preferably does not contain 20% by weight or more, more preferably does not contain 10% by weight or more, and most preferably does not contain at all.

1.8 Solvent The solvent that may be included in the composition of the present invention is not particularly limited, and examples thereof include methyl ethyl ketone (MEK), toluene, methyl isobutyl ketone (MIBK), methyl cellosolve acetate, and ethyl cellob. Examples thereof include esters such as acetate, ketone solvents such as methyl ethyl ketone, aromatic compounds such as benzene, toluene, chlorobenzene, and dichlorobenzene, isopropyl alcohol (IPA), methanol, and ethanol. These solvents may be used alone or in combination of two or more.

1.9 Other Additives The thermosetting or active energy ray-curable composition of the present invention may contain various additives (polymerization inhibitors, antifoaming agents, coatability improving agents, thickeners, lubricants, if necessary). Stabilizers (antioxidants, active energy ray absorbers, active energy ray stabilizers, heat stabilizers, etc.), antistatic agents, pigments, fillers, antiblocking agents, etc.) may be included.

<Polymerization inhibitor>
The polymerization inhibitor that may be contained in the thermosetting or active energy ray-curable composition of the present invention is not particularly limited, and a known polymerization inhibitor can be used. Specifically, hydroquinone, hydroquinone monomethyl ether, mono-tert-butylhydroquinone, catechol, p-tert-butylcatechol, p-methoxyphenol, p-tert-butylcatechol, 2,6-di-tert-butyl-m -Phenols such as cresol, pyrogallol, β-naphthol, quinones such as benzoquinone, 2,5-diphenyl-p-benzoquinone, p-toluquinone, p-xyloquinone; nitrobenzene, m-dinitrobenzene, 2-methyl-2- Nitro compounds or nitroso compounds such as nitrosopropane, α-phenyl-tert-butylnitrone, 5,5-dimethyl-1-pyrroline-1-oxide; chloranil-amine, diphenylamine, diphenylpicrylhydrazine, phenol-α-naphthylami , Pyridine, amines such as phenothiazine; dithio benzoylsulfamoyl sulfide, sulfides such as dibenzyl tetrasulfide and the like.
These polymerization inhibitors may be used alone or in combination of two or more. Moreover, the addition amount of a polymerization inhibitor is although it does not specifically limit, The range of 0.1-10 weight part is preferable with respect to 100 weight part of compositions of this invention.

<Antifoaming agent>
The antifoaming agent that may be contained in the thermosetting or active energy ray-curable composition of the present invention is not particularly limited, and a known antifoaming agent can be used. Specifically, any of a silicone type compound and a non-silicone type compound may be sufficient, and as a silicone type compound, a polysiloxane copolymer etc. are mentioned, for example. Non-silicone compound compounds include fatty acid ester compounds, urea resin compounds, paraffinic compounds having an HLB of 1 or more and less than 4, polyoxyalkylene glycol compounds, acrylic ester copolymers, ester polymers, Ether polymer, mineral oil emulsification type, polysiloxane adduct, fluorine compound, vinyl polymer, acetylene alcohol, acrylic polymer, special vinyl polymer, ethylene glycol, higher alcohol (octyl alcohol, cyclohexanol, etc.), etc. Is mentioned.
These antifoaming agents may be used alone or in combination of two or more. Moreover, the addition amount of an antifoamer is although it does not specifically limit, The range of 0.1-5 weight part is preferable with respect to 100 weight part of resin compositions of this invention.

<Applicability improver>
The coatability improving agent that may be contained in the thermosetting or active energy ray-curable composition of the present invention is not particularly limited, and a known coatability improving agent can be used. Specifically, an alicyclic epoxy diluent (Celoxide 3000 (manufactured by Daicel Chemical Industries, Ltd.)) and the like can be mentioned.
These coating property improving agents may be used alone or in combination of two or more. Moreover, the addition amount of a coating property improving agent is not specifically limited, However, The range of 0.1-10 weight part is preferable with respect to 100 weight part of compositions of this invention.

<Thickener>
The thickener that may be contained in the thermosetting or active energy ray-curable composition of the present invention is not particularly limited, and a known thickener can be used. Specific examples include magnesium oxide, magnesium hydroxide, calcium oxide, potassium oxide, potassium hydroxide, and zinc oxide. An isocyanate thickener can also be used in some cases.
These thickeners may be used alone or in combination of two or more. Moreover, the addition amount of a thickener is although it does not specifically limit, The range of 0.1-5 weight part is preferable with respect to 100 weight part of compositions of this invention.

<Lubricant>
The lubricant that may be contained in the thermosetting or active energy ray-curable composition of the present invention is not particularly limited, and a known lubricant can be used. Specific examples include silane compounds, polyolefin waxes, fatty acid amides (such as lauric acid amide, stearic acid amide, oleic acid amide, behenic acid amide, and erucic acid amide).
These lubricants may be used alone or in combination of two or more. The amount of lubricant added is not particularly limited, but is preferably in the range of 0.1 to 3 parts by weight with respect to 100 parts by weight of the composition of the present invention.

<Antioxidant>
The antioxidant which may be contained in the thermosetting or active energy ray-curable composition of the present invention is not particularly limited, and a known antioxidant can be used. Specifically, 6-ethoxy-1-phenyl-2,2,4-trimethyl-1,2-dihydroquinoline, 6-ethoxy-1-octyl-2,2,4-trimethyl-1,2-dihydroquinoline 6-ethoxy-1-phenyl-2,2,4-trimethyl-1,2,3,4-tetrahydroquinoline, 6-ethoxy-1-octyl-2,2,4-trimethyl-1,2,3 4-tetrahydroquinoline, nickel cyclohexaneate, 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) -2-ethylhexane, 2-methyl-4-methoxy-diphenylamine, 1 -Methyl-2-phenylindole and the like.
These antioxidants may be used alone or in combination of two or more. Moreover, although the addition amount of antioxidant is not specifically limited, The range of 0.1-3 weight part is preferable with respect to 100 weight part of compositions of this invention.

<Active energy ray absorbent and active energy ray stabilizer>
As the stabilizer that may be contained in the thermosetting or active energy ray-curable composition of the present invention, an active energy ray absorber or an active energy ray stabilizer can be used.

  The active energy ray absorbent that may be contained in the thermosetting or active energy ray-curable composition of the present invention is not particularly limited, and it is uniformly dissolved in the composition and provides the necessary weather resistance. You can use it if you can. In particular, active energy ray absorbers having a maximum absorption wavelength in the range of 240 to 380 nm with compounds derived from benzophenone series, benzotriazole series, phenyl salicylate series, and phenyl benzoate series are preferred. A triazole-based active energy ray absorbent is preferable, and the combination of the above two types is most preferable. Examples of the active energy ray absorbent include 2-hydroxybenzophenone, 5-chloro-2-hydroxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octatesiloxybenzophenone, 2,2'-dihydroquin-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone phenyl salicylate, p -Tert-butylphenyl salicylate, p- (1,1,3,3, -tetramethylptyl) phenyl salicylate, 3-hydroxyphenylbenzoate, phenylene-1,3-dibenzoate, 2- (2- Loxy-5'-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydrogishi-3,5-tert-butylphenyl) benzotriazole, 2- (2-Hydroxy-5-tert-ptylphenyl) benzotriazole, 2- (2-Hydroxy-4-octylphenyl) benzotriazole, 2- (2'hydroxy-5'-methacryloxyethylphenyl) -2H- Benzotriazole, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -2H-benzotriazole, 2- (2,4-dihydroxyphenyl) -4,6-bis ( 2,4-Dimethylphenyl) -1,3,5-triazine and glycidyl alkyl (C1 -C13) Reaction products with ether, etc., among which benzophenone-based 2-hydroxy-4-octoxybenzophenone, 2,4-dihydroxybenzophenone, benzotriazole-based 2- (2-hydroxy) -Tert-Putylphenyl) benzotriazole is particularly preferred, and these are more preferably used in combination of two or more.

  The addition amount (total amount) of the active energy ray absorbent is preferably 2 to 30 parts by weight, more preferably 5 to 15 parts by weight with respect to 100 parts by weight of the composition of the present invention. When the addition amount of the active energy ray absorbent is less than 2 parts by weight, the curable film becomes insufficient and sufficient wear resistance, adhesion and weather resistance are difficult to obtain. On the other hand, if the total amount of the active energy ray absorbent exceeds 30 parts by weight, the coating is likely to be colored, and the weather resistance is likely to deteriorate.

  The active energy ray stabilizer that may be contained in the thermosetting or active energy ray-curable composition of the present invention is not particularly limited, and examples thereof include bis (2,2,6,6-tetramethyl-4- Piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-biberidyl) sebacate, bis (1-methoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1 -Ethoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1-propoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1-butoxy-2) , 2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1-pentyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1- Xyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1-heptyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1-octoxy-2, 2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1-nonyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1-decanyloxy-2,2,6, 6-tetramethyl-4-piperidyl) sebacate, bis (1-dodecyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, and the like. Among these, bis (1-octoxy-2, 2,6,6-tetramethyl-4-piperidyl) sebacate is preferred.

The addition amount (total amount) of the active energy ray stabilizer is preferably 0.1 to 5 parts by weight, more preferably 0.5 to 2 parts by weight with respect to 100 parts by weight of the composition of the present invention.
If the amount of the active energy ray stabilizer added is less than 0.1 parts by weight, the weather resistance and durability of the cured film tends to be insufficient, and if it exceeds 5 parts by weight, the film itself will be insufficiently cured. The toughness, heat resistance, and wear resistance of the steel are likely to decrease.

<Heat stabilizer>
The heat stabilizer which may be contained in the thermosetting or active energy ray-curable composition of the present invention is not particularly limited, and a known heat stabilizer can be used. Specific examples include hindered phenols, hydroquinones, thioethers, phosphites, and substituted products thereof.
These heat stabilizers may be used alone or in combination of two or more. Moreover, the addition amount of a heat stabilizer is not specifically limited, However, The range of 0.1-3 weight part is preferable with respect to 100 weight part of compositions of this invention.

<Antistatic agent>
The antistatic agent that may be contained in the thermosetting or active energy ray-curable composition of the present invention is not particularly limited, and a known antistatic agent can be used. Specific examples include metal oxides such as tin oxide, tin oxide / antimony oxide composite oxide, and tin oxide / indium oxide composite oxide, and quaternary ammonium salts.
These antistatic agents may be used alone or in admixture of two or more. The amount of the antistatic agent added is not particularly limited, but is preferably in the range of 10 to 30 parts by weight with respect to 100 parts by weight of the composition of the present invention.

<Pigment>
The pigment that may be contained in the thermosetting or active energy ray-curable composition of the present invention is not particularly limited, and a known pigment can be used. Specifically, titanium white, zinc white, carbon black, iron black, petal, chrome vermillion, ultramarine, cobalt blue, yellow lead, titanium yellow, and other inorganic pigments, phthalocyanine blue, indanthrene blue , Isoindolinone yellow, benzidine yellow, quinacridone red, polyazo red, perylene red, aniline black and other organic pigments (including dyes), or metallic pigments made of scaly foils such as aluminum, brass, titanium dioxide coated mica And pearlescent pigments (pearl pigments) composed of scaly foil pieces such as basic lead carbonate.
These pigments may be used alone or in combination of two or more. Moreover, the addition amount of a pigment is not specifically limited, However, The range of 0.1-25 weight part is preferable with respect to 100 weight part of compositions of this invention.

<Anti-blocking agent>
The antiblocking agent that may be contained in the thermosetting or active energy ray-curable composition of the present invention is not particularly limited, and a known antiblocking agent can be used. Specifically, organic anti-blocking agents (polymethyl methacrylate, polymethylsilyltosesquioxane (silicone), polyamide, polytetrafluoroethylene, epoxy resin, polyester resin, benzoguanamine / formaldehyde resin, phenol resin, etc.); Examples include inorganic antiblocking agents (calcium carbonate, calcium nitrate, barium sulfate, calcium phosphate, silica, clay, talc, mica, etc.). The fine shape of the anti-blocking agent may be any shape, and can be any shape such as spherical, square, columnar, needle-like, plate-like, or indefinite shape. You may use, and may mix and use 2 or more types. Moreover, although the addition amount of an antiblocking agent is not specifically limited, The range of 0.1-3 weight part is preferable with respect to 100 weight part of compositions of this invention.

<Surfactant>
By using a known filler, antifoaming agent, etc., it is possible to adjust the filling property of the composition into the minute recesses, the surface smoothness of the cured coating film, the defoaming property and surface tension of the composition. As another method, the present invention uses as an additive a fluorosurfactant obtained by substituting a part or all of the hydrophobic groups of a silicon surfactant or hydrocarbon surfactant having a dimethylsiloxane skeleton with a fluorine atom. May be included in the thermosetting or active energy ray-curable composition.
As a silicon-based surfactant having a dimethylsiloxane skeleton, for example, BYK333 (manufactured by BYK Chemie), as a fluorine-based surfactant in which a hydrophobic group of a hydrocarbon-based surfactant is partially or entirely substituted with fluorine atoms, For example, FC-430 (made by Sumitomo 3M) is mentioned.
These surfactants may be used alone or in combination of two or more. The addition amount of the surfactant is not particularly limited, but is 100 which is the total amount of the monomer (A, C), (meth) acrylic copolymer resin (B) and polyol (D) of the present invention. The range of 0.05 to 5 parts by weight, more preferably 0.1 to 2 parts by weight is preferred with respect to parts by weight. When the blending amount of the surfactant is less than 0.05 parts by weight, it tends to cause problems in the filling property to the fine recesses, the surface smoothness, and the defoaming property of the composition, while the blending amount is 5%. If the amount is more than the part, craters, floating, orange peel, and fish eyes at the time of coating the composition are likely to occur due to a decrease in surface tension, and problems such as defoaming properties of the composition are likely to occur, resulting in an effect of increasing the amount. The above-mentioned range is preferable because it is not recognized and is uneconomical and causes a decrease in physical properties of the cured product.

1.10 Characteristics of the composition of the present invention A resin composition (resin film) obtained by curing the above-described composition of the present invention has excellent flexibility and wear resistance.
Regarding flexibility, the results obtained by the bending strength evaluation described in detail below are preferably 200 times or more, more preferably 250 times or more, and even more preferably 300 times or more. If the evaluation value is less than 200 times, the coating film may be worn out in a short time or the coating film may be cracked.
Moreover, about abrasion resistance, it is preferable that the result obtained by the Taber abrasion strength evaluation demonstrated in detail below is 2000-3000 rotation, More preferably, it is 2100-3000 rotation, More preferably, it is 2200-2900 rotation . If the evaluation value is less than 2,000 revolutions, the film containing the base material and the hard coat film may be perforated in a shorter period than desired, and the material to be protected from the base material may be damaged. If it is too large, the flexibility of the hard coat film itself will be extremely lowered, and there is a risk that the film will crack when it is turned into a film and wound on a roll, or it may break due to bending or bending during practical use. is there.

In addition, a softness | flexibility is measured by bending strength evaluation. The bending strength evaluation is measured and evaluated by a method defined in JIS P8115, and a specific measurement and evaluation method will be described in detail in Examples.
Abrasion is measured by Taber abrasion strength evaluation. The Taber abrasion strength evaluation is measured and evaluated by a method defined in JIS K5600, and a specific measurement / evaluation method will be described in detail in Examples.

1.11 Applications The resin of the present invention can be used as a flooring repair (protection) resin composition used for flooring repair or flooring protection by being applied to the flooring and cured.
In addition, the resin of the present invention can be used as a resin composition for an automobile exterior part or an automobile part interior part by being applied and cured on a film or the like that is a base material of the automobile exterior part.
The resin of the present invention may be directly applied to a base material, a flooring material or the like and cured, or may be used in the form of a film as described later.

2 Film of the Present Invention The second aspect of the present invention is obtained by curing the thermoplastic resin substrate layer and the thermosetting or active energy ray-curable composition according to the first aspect of the present invention. It is a film containing the layer of a resin composition.

2.1 Substrate The substrate of the thermoplastic resin is not particularly limited as long as it is such a resin. For example, a vinyl chloride film, an acrylic film, a polyester film, a polypropylene film, a polyethylene film, a poval film, A cellulose acetate film, a polycarbonate film, a PI film, a PEN film, or the like is used. Among these, a polyethylene terephthalate (PET) film, a polycarbonate (PC) film, and a thermoplastic polyester film are preferably used as a substrate because they have high transparency, excellent mechanical strength, and selectivity in thickness.

  Moreover, the thickness of a base material is not specifically limited. However, if the film is too thin, wrinkles are generated when the film is attached to the flooring material, and the film is easily deformed, so that the construction becomes difficult. On the other hand, if the film is too thick, a step is generated in the flooring material. Accordingly, the substrate used in the present invention is preferably 50 to 300 μm, more preferably 75 to 125 μm.

  The thickness of the active energy ray-curable resin film obtained by applying the active energy ray-curable composition of the present invention to the surface of the substrate and then irradiating the active energy ray is not particularly limited. However, if it is too thin, a cured film having sufficient strength cannot be obtained. On the other hand, if it is too thick, processability and transparency are lowered, and the film is warped. Therefore, in general, the thickness of the active energy ray-curable resin film is preferably 2 to 30 μm, and more preferably 3 to 25 μm.

2.2 Adhesive layer can be formed on the back surface of the adhesive layer base material by applying a tacky adhesive in advance for adhering to the flooring material. The component of the adhesive layer is not particularly limited as long as it has a predetermined adhesive force. For example, a solvent-diluted acrylic copolymer is the main component, and the diluent is ethyl acetate, toluene, methyl ethyl ketone, water. Etc. are selected. A hot-melt type adhesive that exhibits tackiness when heated, such as a urethane hot-melt adhesive, can also be used.

  The adhesive strength of the adhesive layer in the film of the present invention is not particularly limited, but if the adhesive strength is too low, it will be immediately peeled off by a vacuum cleaner or the like, and if the strength is too high, peeling from the flooring will occur. It becomes difficult. Therefore, generally, the initial adhesive strength of the adhesive layer is preferably 4.0 to 14.0 N / 25 mm, and more preferably 10.0 to 14.0 N / 25 mm. In addition, since it is peeled off after being applied for a long time, it is desirable that its adhesive strength does not change greatly over time from the initial stage (it does not become lower or higher than the initial stage).

  Moreover, it is preferable that an adhesive bond layer is colorless and transparent so that the color and gloss by a base material and active energy ray curable resin may not be inhibited.

  The thickness of the adhesive layer formed on the back surface of the substrate is not particularly limited. However, if the thickness of the adhesive layer is too thick, the adhesive force is increased more than necessary, and the peelability is deteriorated to hinder the repair work. On the other hand, if the adhesive layer is too thin, the adhesive force is reduced. Therefore, generally, the thickness of the adhesive layer is preferably 20 to 60 μm, and more preferably 25 to 50 μm.

  As an adhesive layer, it is also possible to stick a commercially available double-sided tape on the back surface of the protective sheet of the present invention. The double-sided tape uses a polyester film as a base material and has an acrylic pressure-sensitive adhesive on both sides, and since it is excellent in transparency, the joining portion does not stand out, and the adhesive is also in the adhesive strength and removability. A material comparable to the layer is preferably selected and used.

  Moreover, you may apply | coat an antifouling agent to the surface of an adhesive bond layer from a viewpoint of the preservation | save of the film of this invention. Since the adhesive component forming the adhesive layer inevitably easily takes in dust and the like, it is desirable to coat the surface with a fluorine-based solvent (for example, perfluorocarbon, hydrofluorocarbon, hydrofluoroether) or the like.

2.3 Production Method of Film of the Present Invention The film of the present invention is obtained by applying the thermosetting or active energy ray curable composition of the first aspect to either the front or back surface of a thermoplastic resin substrate. The coating film is formed by heating, and then the coating film is cured by heating or irradiating active energy rays such as ultraviolet rays and electron beams, and an active energy ray-curable resin film is formed on the surface. Is done. For example, when cured using ultraviolet rays, a high-pressure mercury lamp, a metal halide lamp, or the like can be used as the UV lamp that irradiates ultraviolet rays. The emission line generated from the lamp is not particularly limited as long as it has a wavelength shorter than 400 nm, but can be cured more effectively by using a UV lamp having a strong emission line in the absorption wavelength region of the photoinitiator. The atmosphere during curing may be air or an inert atmosphere such as nitrogen or argon, and curing can be performed at various oxygen concentrations.

  Also, optionally, a slightly sticky adhesive layer can be formed on the back surface of the substrate, or a double-sided tape with release paper can be attached by a known method.

3. Article protection and repair method of the present invention The third aspect of the present invention relates to a method of protecting or repairing an article (protection repair method). Specifically, a coating film is formed by applying the thermosetting or active energy ray-curable composition of the first aspect to a part (for example, the surface) of an article to be protected or repaired, and then Protecting or repairing the article by heating or irradiating active energy rays such as ultraviolet rays or electron rays to cure the coating film and forming an active energy ray curable resin film on the surface Can do.
Although the article to be protected or repaired is not particularly limited, for example, a base material such as a building material such as a flooring can be the target article.

3.1 Floor material protective repair method The floor material protective repair method is performed by applying the thermosetting or active energy ray-curable composition of the first aspect to the floor material. Moreover, the floor material protection repair method of this invention is performed also by making the film of this invention stick to a flooring. When sticking a film, it is preferable to spray or apply an aqueous surfactant solution to the flooring material because the film can be easily positioned and corrected. Moreover, when sticking a film, a uniform adhesion surface can be obtained by removing air and moisture remaining between the flooring and the film with a squeegee or the like.
In addition, in order to prevent dirt, dust, moisture, oil, etc. from adhering to the part where the films of the present invention are connected to each other and impairing the aesthetics, an antifouling agent is further applied to the seams between the films. It is preferable to keep it. It is also possible to overlap the seam part in order to avoid (reduce) dust, dust, moisture, oil or the like from adhering to and accumulating on the seam part.

  In addition, when a film such as a resin is already attached to the floor material to be protected and repaired, after removing these by peeling or grinding, the active energy ray-curable composition of the present invention is applied, or It is preferable to attach the film of the present invention.

4. Manufacturing method of automobile parts The manufacturing method of the automobile parts using the resin composition of the present invention is performed, for example, as follows.
First, prepare a film (acrylic film or the like) previously applied with a coating such as a plating substitute such as a silver layer, and apply the thermosetting or active energy ray curable composition of the first aspect to this film, The composition is cured. After the composition is cured, the film is formed into a container shape by vacuum forming. Thereafter, insert molding is performed by inserting the film in a container shape into a mold and making it thick by injection molding. In this way, automobile parts using the composition of the present invention are produced.

  Moreover, the thermosetting or active energy ray-curable composition according to the first aspect is obtained by using a film not provided with a coating film in place of a film previously provided with a coating film such as a silver layer. After the composition is applied and the composition is cured, a silver layer or the like can be laminated on the back with a laminate. The process after bonding is the same as the above method.

The automobile parts manufactured by the manufacturing method include automobile exterior parts (door mirror, emblem, side molding, light box, door molding, grill, garnish, etc.) and automobile interior parts (meter panel, center console, glove box, etc.).
Since the thermosetting or active energy ray-curable composition of the first aspect is rich in flexibility even after curing, even if the resin is attached to the substrate and then punched out by vacuum forming, the resin is cracked or wrinkled. Therefore, it is possible to provide extremely high quality automobile parts.

  EXAMPLES Hereinafter, although an Example etc. demonstrate this invention further, this invention is not limited by these.

1. Preparation of active energy ray-curable compositions 1 to 3 and monomers 1 to 6 Active energy ray-curable compositions 1 to 3 and active energy ray-curable monomers 1 to 6 were prepared according to the following formulation. .

[Active energy ray-curable composition 1]
The following component (a) “polyfunctional aliphatic urethane (meth) acrylate”, component (b) “(meth) acrylic copolymer resin” and component (e) “photopolymerization initiator” are blended, and active energy rays The curable composition 1 was prepared.
Component (a): 90 parts by weight Ebecryl 254 (Trifunctional aliphatic urethane acrylate, manufactured by Daicel-Cytec Co., Ltd.)
Component (b): 10 parts by weight Cyclomer P ACA230AA (Propylene glycol monomethyl ether (MMPG) solution of acrylic copolymer resin having a weight average molecular weight of 14,000 and an acid value of 40 mg KOH / g in a solid content of 45% by weight, Daicel Chemical Industries, Ltd. Made)
Component (e): 5 parts by weight DAROCUR 1173 (2-hydroxy-2-methyl-1-phenyl-propan-1-one, manufactured by Ciba Specialty Chemicals Co., Ltd.)

[Active energy ray-curable composition 2]
The following component (a) “polyfunctional aliphatic urethane (meth) acrylate”, component (b) “(meth) acrylic copolymer resin” and component (e) “photopolymerization initiator” are blended, and active energy rays The curable composition 2 was prepared.
Ingredient (a): 90 parts by weight Ebecryl 1290K (hexafunctional aliphatic urethane acrylate, manufactured by Daicel Cytec Co., Ltd.)
-Component (b): 10 parts by weight Cyclomer P ACA230AA (Propylene glycol monomethyl ether (MMPG) solution of acrylic copolymer resin having a weight average molecular weight of 14,000 and an acid value of 40 mgKOH / g and a solid content of 45% by weight, Daicel Chemical Industries, Ltd. Made)
Component (e): 5 parts by weight DAROCUR 1173 (2-hydroxy-2-methyl-1-phenyl-propan-1-one, manufactured by Ciba Specialty Chemicals Co., Ltd.)

[Active energy ray-curable composition 3]
The following component (c) “alicyclic epoxy group-containing carboxylate”, component (d) “polyol”, component (e) “photopolymerization initiator” and component (f) “leveling agent”, methyl ethyl ketone 46.6 as a solvent The active energy ray-curable composition 3 was prepared by stirring and mixing parts by weight at a temperature of 60 ° C. for 1 hour.
-Component (c): 28.4 parts by weight Celoxide 2021P (3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, manufactured by Daicel Chemical Industries, Ltd.)
-Component (d): 66.8 parts by weight PLACCEL EPA5860 ((meth) acrylic copolymer containing at least one ethylenically unsaturated monomer having a hydroxyl group, with a lactone monomer added to the hydroxyl group) Combined, manufactured by Daicel Chemical Industries, Ltd.)
Component (e): 4.4 parts by weight UV-sensitive catalyst, Uvacure 1590 (triarylsulfonium hexafluorophosphate salt, manufactured by Daicel Cytec Co., Ltd.)
Component (f): 0.4 parts by weight BYK-361N (polyacrylate copolymer, manufactured by BYK CHEMIE)

[Active energy ray-curable monomer 1]
100 parts by weight of Ebecryl 114 (phenoxyethyl acrylate, manufactured by Daicel Cytec Co., Ltd.) and a photopolymerization initiator DAROCUR 1173 (2-hydroxy-2-methyl-1-phenyl-propan-1-one, Ciba Specialty Chemicals Co., Ltd.) 5 parts by weight were stirred and mixed at a temperature of 60 ° C. for 1 hour to prepare an active energy ray-curable monomer 1.

[Active energy ray-curable monomer 2]
DPHA-B (dipentaerythritol hexaacrylate, manufactured by Daicel Cytec Co., Ltd.) 100 parts by weight and photopolymerization initiator DAROCUR 1173 (2-hydroxy-2-methyl-1-phenyl-propan-1-one, Ciba Specialty 5 parts by weight of Chemicals Co., Ltd.) was stirred and mixed at a temperature of 60 ° C. for 1 hour to prepare an active energy ray-curable monomer 2.

[Active energy ray-curable monomer 3]
100 parts by weight of PETIA (pentaerythritol triacrylate, manufactured by Daicel Cytec Co., Ltd.) and photopolymerization initiator DAROCUR 1173 (2-hydroxy-2-methyl-1-phenyl-propan-1-one, Ciba Specialty Chemicals Co., Ltd.) 5 parts by weight was stirred and mixed at a temperature of 60 ° C. for 1 hour to prepare an active energy ray-curable monomer 3.

[Active energy ray-curable monomer 4]
Ebecryl 254 (aliphatic urethane acrylate, manufactured by Daicel Cytec Co., Ltd.) and a photopolymerization initiator DAROCUR 1173 (2-hydroxy-2-methyl-1-phenyl-propan-1-one, Ciba Specialty Chemicals Co., Ltd.) The active energy ray-curable monomer 4 was prepared by stirring and mixing 5 parts by weight of a product manufactured by a company at a temperature of 60 ° C. for 1 hour.

[Active energy ray-curable monomer 5]
100 parts by weight of Ebecry 1290K (hexafunctional aliphatic urethane acrylate, manufactured by Daicel Cytec Co., Ltd.) and a photopolymerization initiator DAROCUR 1173 (2-hydroxy-2-methyl-1-phenyl-propan-1-one, Ciba Specialty 5 parts by weight of Chemicals Co., Ltd.) was stirred and mixed at a temperature of 60 ° C. for 1 hour to prepare an active energy ray-curable monomer 5.

[Active energy ray-curable monomer 6]
Celoxide 2021P (3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, manufactured by Daicel Chemical Industries, Ltd.) and an ultraviolet-sensitive catalyst, Uvacure 1590 (triarylsulfonium hexafluorophosphate salt, 4.4 parts by weight of Daicel Cytec Co., Ltd.) and 0.4 parts by weight of BYK-361N (polyacrylate copolymer, manufactured by BYK CHEMIE) are stirred and mixed at a temperature of 60 ° C. for 1 hour, and active energy ray curability Monomer 6 was prepared.

2. Preparation of coating materials according to Examples 1 to 10 and Comparative Examples 1 to 10 By using the active energy ray curable compositions 1 to 3 and the active energy ray curable monomers 1 to 6 described above, according to the following formulation The active energy ray-curable coating materials (coating materials) according to Examples 1 to 10 and Comparative Examples 1 to 10 were prepared.

<Example 1>
The coating material was prepared by diluting composition 1 with methyl ethyl ketone so that the solid content of composition 1 was 40% by weight.

<Example 2>
The coating material was prepared by diluting the composition 2 with methyl ethyl ketone so that the solid content of the composition 2 was 40% by weight.

<Example 3>
Coating composition is prepared by diluting composition 1 and composition 3 with methyl ethyl ketone so that the weight ratio of the solids of composition 1 and composition 3 is 90:10 and the total solids is 40% by weight. Adjusted.

<Example 4>
The composition 1 and the monomer 1 were diluted with methyl ethyl ketone so that the weight ratio of the solid content of the composition 1 and the monomer 1 was 90:10 and the total solid content was 40% by weight. The coating material was adjusted.

<Example 5>
The composition 2 and the composition 3 are diluted with methyl ethyl ketone so that the weight ratio of the solids of the composition 2 and the composition 3 is 90:10 and the total solids is 40% by weight. Adjusted.

<Example 6>
The composition 2 and the monomer 1 were diluted with methyl ethyl ketone so that the weight ratio of the solid content of the composition 2 and the monomer 1 was 90:10, and the total solid content was 40% by weight. The coating material was adjusted.

<Example 7>
Coating composition is prepared by diluting composition 1 and composition 3 with methyl ethyl ketone so that the weight ratio of the solids of composition 1 and composition 3 is 80:20 and the total solids is 40% by weight. Adjusted.

<Example 8>
The composition 1 and the composition 3 are diluted with methyl ethyl ketone so that the weight ratio of the solid content of the composition 1 to the composition 3 is 70:30 and the total solid content is 40% by weight. Adjusted.

<Example 9>
Coating composition is prepared by diluting composition 2 and composition 3 with methyl ethyl ketone so that the weight ratio of the solids of composition 2 and composition 3 is 80:20 and the total solids is 40% by weight. Adjusted.

<Example 10>
The composition 2 and the composition 3 are diluted with methyl ethyl ketone so that the weight ratio of the solid content of the composition 2 to the composition 3 is 70:30 and the total solid content is 40% by weight. Adjusted.

<Comparative Example 1>
Coating composition is prepared by diluting composition 1 and composition 3 with methyl ethyl ketone so that the weight ratio of the solids of composition 1 and composition 3 is 60:40 and the total solids is 40% by weight. Adjusted.

<Comparative example 2>
The composition 2 and the composition 3 are diluted with methyl ethyl ketone so that the weight ratio of the solid content of the composition 2 to the composition 3 is 60:40 and the total solid content is 40% by weight. Adjusted.

<Comparative Example 3>
The monomer 2 was diluted with methyl ethyl ketone so that the solid content of the monomer 2 was 40% by weight, thereby preparing a coating material.

<Comparative Example 4>
The monomer 3 was diluted with methyl ethyl ketone so that the solid content of the monomer 3 was 40% by weight, thereby preparing a coating material.

<Comparative Example 5>
The monomer 2 and the composition 3 were diluted with methyl ethyl ketone so that the weight ratio of the solid content of the monomer 2 to the composition 3 was 90:10 and the total solid content was 40% by weight. The coating material was adjusted.

<Comparative Example 6>
The monomer 3 and the monomer 1 were diluted with methyl ethyl ketone so that the weight ratio of the solids of the monomer 3 and the monomer 1 was 90:10 and the total solid content was 40% by weight. The coating material was adjusted.

<Comparative Example 7>
The monomer 1 was diluted with methyl ethyl ketone so that the solid content of the monomer 1 was 40% by weight, thereby preparing a coating material.

<Comparative Example 8>
The coating material was prepared by diluting the monomer 4 with methyl ethyl ketone so that the solid content of the monomer 4 was 40% by weight.

<Comparative Example 9>
The monomer 5 was diluted with methyl ethyl ketone so that the solid content of the monomer 5 was 40% by weight, thereby preparing a coating material.

<Comparative Example 10>
The monomer 6 was diluted with methyl ethyl ketone so that the solid content of the monomer 6 was 40% by weight, thereby preparing a coating material.

3. Production of Coating Films According to Examples 1 to 10 and Comparative Examples 1 to 10 Using the coating materials according to Examples 1 to 10 and Comparative Examples 1 to 10 described above, Examples 1 to 10 and Comparative Films 1-10 were produced.

Each of the above coating coating solutions was coated on a single-sided easy-adhesive coated PET film (trade name “HS74 (PET # 100)”, thickness of 100 μm, manufactured by Teijin DuPont Films Ltd.) using a Mayer bar under the following conditions.
Count: # 48 (WET 48g / m ² equivalent)
Coating material concentration: Solid content ≈ 40% by weight
Coating amount: about 20 g / m ²
After coating, it was dried at 100 ° C. for 1 minute using a hot air dryer, and then irradiated with ultraviolet rays under the following conditions to form a resin film on the PET film. The thickness of the resin film was 20 μm.
Device: Desktop UV irradiation device manufactured by Fusion Japan Co., Ltd. Lamp type: High-pressure mercury lamp UV intensity: 120 W / cm ²
Irradiation speed: 15 m ² / min Irradiation frequency: 3 times

4). Evaluation of physical properties of coating films according to Examples 1 to 10 and Comparative Examples 1 to 10 About the coating films according to Examples 1 to 10 and Comparative Examples 1 to 10 thus obtained, wearability (Taber abrasion strength evaluation) ), Flexibility (evaluation of bending strength), pencil hardness, steel wool resistance, total light transmittance, and physical properties of haze (HAZE). Below, the evaluation method of each physical property is demonstrated.

Abrasion: Taber Abrasion Strength Evaluation Abrasion was evaluated by a Taber abrasion strength evaluation, and the Taber abrasion strength was measured according to JIS K5600. Specifically, the wear wheel is rotated while applying a predetermined load on each coating film, and the resin film on the PET film and the PET film itself are peeled off by the wear, and the point at which the wear begins to reach the lower substrate. The wear end point was determined. The total number of revolutions that the wear wheel has rotated up to this end point is defined as the Taber wear strength. The evaluation conditions are as follows.
Equipment: Yasuda Seiki Seisakusho "Taber ABRASER"
Wear wheel: CS-0 + S-42 (coarse paper) x 2
Load: 500gf
Rotation speed: 60rpm
Vacuum distance: 3mm
Remarks: Replace worn wheels with new ones every 500 revolutions Measurement environment: 23 ° C 50% RH
In addition, the coating film used for a test used what was humidity-controlled for 24 hours with the constant temperature / humidity machine of 23 degreeC x 50% RH.

Flexibility: Folding strength (MIT) evaluation The flexibility of the resin layer on the PET film was evaluated by folding strength (MIT) evaluation, and the bending strength was measured according to JIS P8115. Specifically, a square film piece of 50 mm in the longitudinal direction and 50 mm in the width direction was cut out from each coating film and used as a sample for evaluation. The both ends in the longitudinal direction of the sample for evaluation were set in the following evaluation apparatus, and the bending was performed at the bending angle shown below a plurality of times, and the number of bendings when the resin film was cracked was defined as the bending strength. . The evaluation conditions are as follows.
Apparatus: Yasuda Seiki Seisakusho "MIT Folding Tester"
Distance between chucks: 50mm
Bending angle: ± 135 degrees ± 2 degrees Tensile load: 1 kgf
N number: N = 3
Measurement environment: 23 ° C, 50% RH
In addition, the coating film used for a test used what was humidity-controlled for 24 hours with the constant temperature / humidity machine of 23 degreeC x 50% RH.

Pencil hardness Pencil hardness was evaluated according to JIS K5600. The evaluation was performed by external appearance observation, and the resin film on the PET film was rubbed with a pencil. Even in the same JIS evaluation, there are cases where NG is “scratched” or NG is “peeling of the resin film”, but in this evaluation, NG was evaluated as “scratched”. Specifically, an evaluation is first performed with a pencil having a certain hardness, and when a scratch is found, the evaluation is repeated with a pencil having a higher hardness, and if a scratch is confirmed, the next lower hardness is confirmed. It was re-evaluated. If scratches cannot be confirmed, a pencil with a hardness of one level is used again. If reproducibility is confirmed twice or more, the hardness of the hardest pencil without scratches is defined as the pencil hardness of the resin film. . The evaluation result is represented by the hardness of the pencil lead. The evaluation conditions are as follows.
Equipment: “SURFACE PROPERTY TESTER HEIDON-14D” manufactured by HEIDON
Evaluation pencil: “Pencil hardness test pencil” manufactured by Mitsubishi Pencil Co., Ltd.
Load: 1kgf
Scratch distance: 50 mm or more Scratch angle: 45 degrees Measurement environment: 23 ° C. 50% RH
In addition, the coating film used for a test used what was humidity-controlled for 24 hours with the constant temperature / humidity machine of 23 degreeC x 50% RH.

Steel wool resistance Steel wool resistance was evaluated according to JIS K5600. Specifically, steel wool # 0000 was used and reciprocated 20 times with a load of 1 kgf, and the degree of damage when the surface of the resin film on the PET film was rubbed was subjected to sensory evaluation based on appearance. The measurement environment was 23 ° C. and 50% RH.
Judgment criteria were as follows.
No scratch: No scratches on the surface of the resin film can be confirmed. Scratch: There are fine and small scratches on the surface of the resin film. Scratches: There are small scratches on the surface of the resin film and a few large scratches. Scratch size: A large amount on the surface of the resin film. In addition, the coating film used for a test used what adjusted the humidity for 24 hours with the constant temperature and humidity machine of 23 degreeC x 50% RH.

Total light transmittance / haze (HAZE)
The total light transmittance and haze of the coating film were measured under the following evaluation conditions.
Apparatus: JASCO Corporation "A-300 type"
N number: N = 5
Measurement environment: 23 ° C, 50% RH

  In Tables 1-4, the evaluation result about the coating film which concerns on Examples 1-10 and Comparative Examples 1-10 is shown.

Claims (22)

A thermosetting or active energy ray curable composition comprising:
Flexibility after being cured into a film shape is 10 to 100 times of the monomer (a1) according to the bending strength evaluation, and flexibility after being cured into a film shape is from 10 to 100 times of the oligomer (a2) according to the bending strength evaluation. The composition containing 1 or more chosen from the group which consists of, and 0-30 weight% of fillers.   The composition according to claim 1, wherein the monomer constituting the monomer (a1) or the oligomer (a2) is urethane (meth) acrylate.   The composition according to claim 1, wherein the monomer constituting the monomer (a1) or the oligomer (a2) is a polyfunctional urethane (meth) acrylate having two or more (meth) acryloyl groups in one molecule.   The composition according to claim 1, wherein the monomer constituting the monomer (a1) or the oligomer (a2) is a polyfunctional urethane (meth) acrylate having 6 or more (meth) acryloyl groups in one molecule.   The urethane (meth) acrylate is a hexafunctional aliphatic urethane (meth) acrylate having 6 functional groups in one molecule and having an aliphatic urethane group. The composition described.   The composition according to any one of claims 2 to 5, wherein the urethane (meth) acrylate has a weight average molecular weight of 500 to 10,000.   The composition according to any one of claims 1 to 6, further comprising a (meth) acrylic copolymer resin (B).   The composition according to claim 7, wherein the (meth) acrylic copolymer resin (B) has a (meth) acryloyl group and a carboxyl group in the side chain.   The (meth) acrylic copolymer resin (B) has an acid value of 20 to 200 (KOHmg / g), a weight average molecular weight of 5000 to 20000, and a double bond equivalent of 350 to 450. The composition described.   The composition according to any one of claims 1 to 9, which does not contain a filler.   Furthermore, from the oligomer (c2) whose flexibility after being cured into a film is 100 times or more according to the bending strength evaluation and from which the flexibility after being cured into a film is 100 times or more according to the bending strength evaluation The composition according to any one of claims 1 to 10, comprising one or more selected from the group consisting of:   The composition according to claim 11, wherein the monomer constituting the monomer (c1) or the oligomer (c2) is one or more selected from the group consisting of (meth) acrylates, carboxylates, and polyfunctional monomers.   The composition according to claim 12, wherein the monomer constituting the monomer (c1) or the oligomer (c2) has an epoxy group.   The composition according to claim 12, wherein the monomer constituting the monomer (c1) or the oligomer (c2) has an alicyclic epoxy group.   The composition according to claim 11, wherein the monomer constituting the monomer (c1) or the oligomer (c2) is 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate.   The composition according to claim 11, wherein the monomer constituting the monomer (c1) or the oligomer (c2) is phenoxyethyl acrylate.   The weight ratio of one or more components selected from the group consisting of the monomer (a1) and the oligomer (a2) and one or more components selected from the group consisting of the monomer (c1) and the oligomer (c2) is 100 to 65: 0. The composition according to any one of claims 11 to 16, which is -35.   The active energy ray-curable composition according to any one of claims 1 to 17, further comprising one or more selected from the group consisting of a polyol (D), an active energy ray polymerization catalyst (E), and a leveling agent (F). object.   The composition according to any one of claims 1 to 18, wherein the wear property after curing of the composition is 2000 to 3000 rotations in terms of Taber abrasion strength evaluation.   The film containing a thermoplastic resin base material layer and the layer formed by hardening | curing the composition in any one of Claims 1 thru | or 19.   An article protection repair method for protecting or repairing an object by applying the composition according to any one of claims 1 to 19 and then curing or applying the film according to claim 20.   The article protection repair method according to claim 21, wherein the object is a flooring.