KR20180035125A - Resin composition for decorative molding - Google Patents

Abstract

Provided is a resin composition for decorative molding which has excellent tracking properties with respect to a substrate without hindering scratch resistance. The resin composition for decorative molding of the present invention comprises a compound represented by general formula (I). -(AO)_(k)-R, -(AO)_(l)-H, -H, and -R are each independently bonded to general formula (I), number of -(AO)_(k)-R bonded to general formula (I) is m, number of -(AO)_(l)-H bonded to general formula (I) is n, number of -H bonded to general formula (I) is o, number of -R bonded to general formula (I) is p, R indicates a substituent represented by general formula (II), AO indicates one or more selected from predetermined alkylene oxide units, k and l are more than 0 to not more than 20, an average value of m is more than 0 to not more than 6, average values of n, o and p are each not less than 0 to less than 6, a sum of m, n, o and p is 6, a sum of k×m and l×n is more than 2 to not more than 20, and R^2 in general formula (II) indicates a hydrogen atom or a methyl group.

Description

[0001] RESIN COMPOSITION FOR DECORATIVE MOLDING [0002]

The present invention relates to a resin composition for decorative molding.

In the field of printing, a so-called " foil stamping " method in which a hot-melt adhesive is applied to a metal vapor deposition film, heat is applied to an imprint processed in an arbitrary pattern, . Presently, as a means of adding value to packages, plastic containers, toys, home products, etc., pressurization is used in various products. In this field, in addition to the conventional hot-printing method using the above-mentioned heat, recently, a technique called cold printing in which heating is not performed by using an ultraviolet ray hardening resin, or a technique in which hot printing and cold printing are used in combination ought. In addition to the conventional metal vapor deposition film, in addition to the conventional metallic vapor deposition film, a metallic wind-like base in which flakes of metals such as aluminum and glass and inorganic substances are dispersed is also increased. (Patent Documents 1 to 4).

Japanese Unexamined Patent Application Publication No. 1-180338 Japanese Unexamined Patent Application Publication No. 5-320582 Japanese Laid-Open Patent Publication No. 2003-326845 Japanese Patent Application Laid-Open No. 2005-271405

Conventionally, the resin composition for decorative molding has a problem in that glossiness of the undergarment is impaired when the resin composition is printed on a base having strong luster such as aluminum foil, aluminum flake or glass flake. In addition, when printing is performed on a three-dimensional object to be applied such as concavity and convexity or curved surface, lettering defects or the like of the decorative sheet due to lack of adhesiveness and flexibility are caused, and the yield is lowered. Patent Document 4 measures and compares the gloss of a commercially available ultraviolet curable metallic paint as a comparative example, but no change in gloss due to the structure of the resin has been investigated. Patent Document 1 is also the same.

On the other hand, the curable resin composition having excellent scratch resistance contains a polyfunctional monomer such as pentaerythritol, dipentaerythritol, trimethylolpropane, etc. as a crosslinking component, and has excellent scratch resistance because of its high crosslinking density . However, the flexibility of the cured coating is lacking, and the followability to the substrate is insufficient. Further, since the curing shrinkage is large, the deformation of the film substrate is large, which is not suitable for this purpose. Accordingly, the present invention provides a resin composition for edging molding, which contains, as a crosslinking component, dipentaerythritol having an additionally adjusted number of moles of alkylene oxide so as not to impair scratch resistance and excellent followability to a substrate The purpose is to do.

The present invention provides the following [1] to [4].

[1] A resin composition for edging molding, characterized by containing a compound represented by the following general formula (I).

[Chemical Formula 1]

In formula (I), - (AO) _(k) -R, - (AO) _(l) -H, -H and -R are each independently bonded and - ( _{AO) (k)} is the number of -R _{m, - (AO) (l} ) is the number of n number of -H, -H is the number of o, -R denotes a p, wherein R is formula (II) , AO represents -CH ₂ CH ₂ O-, -CH ₂ CH (CH ₃ ) O-, -CH (CH ₃ ) CH ₂ O-, -CH ₂ CH ₂ CH ₂ CH ₂ O-, Or an alkylene oxide unit represented by -CH ₂ CH (C ₂ H ₅ ) O-, -CH (C ₂ H ₅ ) CH ₂ O-, and k and l are each an integer from 0 to And the average value of m, n, o, and p is 6, and the average value of m, n, o, and p is 6, n is more than 2 and not more than 20, and in the general formula (II), R ² represents a hydrogen atom or a methyl group.

(2)

[2] The resin composition for edging molding according to [1], wherein in the compound represented by the general formula (I), the sum of k × m and l × n is 3 or more and 12 or less.

[3] A laminate characterized by comprising a layer containing a cured product of the resin composition for embossing described in [1] or [2], and a mirror polished layer.

The resin composition for decorative molding of the present invention is excellent in scratch resistance and followability to a substrate. In addition, since the dispersibility of fine particles is excellent, a silica-based deglossing agent or the like can be stably dispersed without a dispersant, and a wide gloss value can be adjusted from high gloss to low gloss without hindering the scratch resistance and followability to the substrate . In addition, since the viscosity is low, it is possible to make it solvent-free.

Next, embodiments of the present invention will be described in detail.

≪ Alkylene oxide-modified dipentaerythritol (meth) acrylate >

The resin composition for decorative molding of the present invention contains a compound represented by the following general formula (I) (hereinafter sometimes referred to as alkylene oxide-modified dipentaerythritol (meth) acrylate).

(3)

[Chemical Formula 4]

In formula (I), - (AO) _(k) -R, - (AO) _(l) -H, -H and -R are each independently bonded and - ( _{AO) (k)} is the number of -R _{m, - (AO) (l} ) is the number of n number of -H, -H is the number of o, -R denotes a p, wherein R is formula (II) AO represents -CH ₂ CH ₂ O-, -CH ₂ CH (CH ₃ ) O-, -CH ₂ CH ₂ CH ₂ CH ₂ O-, or -CH ₂ CH (C ₂ H ₅ ) And k and l are more than 0 and not more than 20, and the average values of n, m, o, and p are each 1 or more and less than 6, and m and p , The total value of m, n, o, and p is 6, and the sum of k x m and l x n is more than 2 and not more than 20, and in the formula (II), R ² represents a hydrogen atom or a methyl group.

The alkylene oxide-modified dipentaerythritol (meth) acrylate is obtained by addition polymerization of an alkylene oxide to dipentaerythritol followed by introduction of a (meth) acrylate ester group. In the general formula (I), the sum of k × m and l × n represents the number of moles of alkylene oxide units addition-polymerized to 1 mole of dipentaerythritol, and is more than 2 but not more than 20 Is 3 or more and 16 or less, more preferably 3 or more and 12 or less, and further preferably 4 or more and 8 or less. When the addition mole number of the alkylene oxide unit is within the above range, it is possible to obtain a coating film excellent in curling property, resistance to weathering and the like and having high linearity. In the general formula (I), the sum of m and p represents the number of the (meth) acrylate groups of the compound represented by the general formula (I), and the sum of m and p is greater than 0 and 6 or less, More preferably 3 or more and 6 or less, and still more preferably 4 or more and 6 or less. When the number of (meth) acrylic acid ester groups is within the above range, a resin composition for edible molding having a high photosensitivity and a high polymerization degree can be obtained.

<Preparation of alkylene oxide-modified dipentaerythritol (meth) acrylate>

The alkylene oxide-modified dipentaerythritol (meth) acrylate can be produced, for example, by the following method, but the production process thereof is not particularly limited, and any production method can be employed.

The alkylene oxide modification method using dipentaerythritol as a raw material can be arbitrarily selected. As a general method, a method using a cyclic carbonate such as ethylene carbonate, propylene carbonate or butylene carbonate, or a method using ethylenechlorohydrin may be employed in addition to a method using an alkylene oxide such as ethylene oxide, propylene oxide or butylene oxide .

In addition, in the production method described below, since the (meth) acrylic acid compound used as a raw material of the compound represented by the above general formula (I) is highly polymerizable, Prohibited agents can be used appropriately. Examples of the polymerization inhibitor include hydroquinones such as p-benzoquinone, hydroquinone, hydroquinone monomethyl ether, and 2,5-diphenylparabenquoquinone; N (N, N'-tetramethylpiperidinyl) -Oxyl radicals and t-butyl catechol, amines such as phenothiazine, diphenylamine and phenyl-β-naphthylamine, coumarone, nitrosobenzene, picric acid, molecular oxygen, sulfur, Copper (II) chloride, and the like. Of these, hydroquinone, phenothiazine and N-oxy radicals are preferable from the viewpoint of versatility and polymerization inhibiting effect.

The amount of the polymerization inhibitor to be added is preferably 10 ppm or more, more preferably 30 ppm or more, and the upper limit is usually 5000 ppm or less, preferably, Is not more than 1000 ppm. If the amount is too small, a sufficient polymerization inhibiting effect is not exhibited, and there is a risk that the polymerization will proceed during the production or storage of the product, and if too much, there is a possibility that the curing and polymerization reaction will be inhibited. Therefore, the compound of the present invention alone or in the case of the polymerizable resin composition may cause deterioration of photosensitivity, poor crosslinking of the cured product, deterioration of physical properties such as mechanical strength, and the like, which is not preferable.

As a general introduction method of the (meth) acrylic acid ester group in the production of the alkylene oxide-modified dipentaerythritol (meth) acrylate, there is a method in which a (meth) acrylate corresponding to a desired structure such as methyl acrylate, methyl methacrylate, Ester exchange using acrylic ester, acid chloride method using (meth) acrylic acid chloride, N, N'-dicyclohexylcarbodiimide, 2-chloro-1,3-dimethylimidazolium chloride, propanephosphonic acid anhydride, (CDI) and WSCD (water-soluble carbodiimide), dehydrating esterification method of azeotropically dehydrating (meth) acrylic acid in the presence of an acid catalyst, and the like. Hereinafter, the possible conditions for the production of the esterification reaction of a representative alkylene oxide-modified dipentaerythritol will be described.

The reaction can be carried out by distilling off the resulting water in the presence of an acid catalyst with (meth) acrylic acid and alkylene oxide-modified dipentaerythritol. The acid to be used is not particularly limited as long as it is an acid used in a conventional esterification reaction. For example, there may be mentioned inorganic acids such as sulfuric acid and hydrochloric acid, organic sulfonic acids such as p-toluenesulfonic acid, methanesulfonic acid and camphorsulfonic acid, acid type ion exchange resins, Lewis acids such as boron fluoride- Lewis acid and the like. These acids may be used singly or in combination of two or more of arbitrary acids.

The lower limit of the amount of acid used is 0.1 mol equivalent or more, preferably 0.5 mol equivalent or more with respect to the alkylene oxide-modified dipentaerythritol as the substrate. On the other hand, the upper limit is not limited, but is usually 20 mol or less, preferably 10 mol or less. When the amount of the acid catalyst is too small, the progress of the reaction is delayed or stopped, which is not preferable. When the amount is too large, problems such as product coloring and remaining of the catalyst may occur, And there is a tendency that a side reaction that does not occur occurs.

The reaction can be carried out in either a solvent system or a solventless system, but a solvent system is preferable in terms of generation of by-products and handling in the process. In the case of using a solvent, there is no particular restriction on the solvent to be used, but examples thereof include aromatic hydrocarbon solvents such as toluene and xylene, aliphatic hydrocarbon solvents such as hexane and heptane, diethyl ether, tetrahydrofuran, monoethylene glycol dimethyl ether, Ether type solvents such as ethylene glycol dimethyl ether and the like, halogen type solvents such as methylene chloride, chloroform and carbon tetrachloride are preferably used. These solvents may be used alone or in combination of any two or more of them.

When a solvent is used, the amount of the alkylene oxide-modified dipentaerythritol as the raw material is usually not less than 1% by mass, preferably not less than 20% by mass, and the upper limit is not particularly limited, Is 80 mass% or less, preferably 70 mass% or less. The reaction is usually carried out at a boiling point or higher of the solvent to be used, and the resulting water is distilled off. However, when the reaction is carried out using the (meth) acrylic acid chloride or the condensing agent, the reaction may be carried out at a temperature lower than the boiling point of the solvent or under ice-cooling. The reaction time is arbitrarily selected, but the end point of the reaction can be recognized by measuring the amount of water produced and the acid value in the system.

The reaction time is usually 30 minutes or longer, preferably 60 minutes or longer, and the upper limit is not particularly limited, but is usually 20 hours or shorter, preferably 10 hours or shorter.

The alkylene oxide-modified dipentaerythritol (meth) acrylate prepared by the above reaction can be purified without any particular limitation by a conventionally used purification method. For example, distillation method, recrystallization method, extraction washing method, adsorption treatment method, and the like. When the distillation is carried out, the distillation can be arbitrarily selected as the form thereof, for example, distillation, fine distillation, thin film distillation, molecular distillation and the like.

Since the alkylene oxide-modified dipentaerythritol (meth) acrylate has polymerizability, it is preferably stored in a cool dark place. In addition, in order to prevent polymerization, the above-mentioned polymerization inhibitor may be stored in the above-mentioned amount.

&Lt; Other polymerizable monomers (oligomers) >

The resin composition for decorative molding of the present invention may contain, in addition to the compound represented by the above general formula (I), a polymerizable monomer having another acryloyl group and / or methacryloyl group or a polymerizable oligomer (hereinafter simply referred to as a polymerizable monomer or polymer It may be referred to as &quot; star oligomer &quot;). When the polymerizable monomer and / or the polymerizable oligomer is contained, the total amount of the compound represented by the general formula (I) and the polymerizable oligomer in the total amount of 100 parts by mass of the compound represented by the general formula (I) and the polymerizable monomer and / May be 25 parts by mass or more and less than 100 parts by mass, preferably 35 parts by mass or more and 80 parts by mass or less.

<Polymerizable Monomer>

Any of the above-mentioned polymerizable monomers can be used as far as they perform polymerization reaction together with the compound represented by the above general formula (I). Specifically, (meth) acrylates having 4 to 30 carbon atoms, (meth) acrylamides having 5 to 35 carbon atoms, aromatic vinyls having 5 to 35 carbon atoms, vinyl ethers having 2 to 20 carbon atoms, and other radically polymerizable Compounds and the like. Examples of the non-crosslinkable (monofunctional) (meth) acrylate include hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, tert-octyl (meth) acrylate, isoamyl (meth) (Meth) acrylate, isodecyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, cyclohexyl (meth) acrylate, 4-n-butylcyclohexyl (Meth) acrylate, butenyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, 2-ethylhexyldiglycol (Meth) acrylate, 3-bromobutyl (meth) acrylate, cyanoethyl (meth) acrylate, benzyl (meth) acrylate, butoxymethyl (meth) acrylate, methoxypropylene monoacrylate, 3 (Meth) acrylate, methoxybutyl (meth) acrylate, alkoxy (Meth) acrylate, 2-ethylhexylcarbitol (meth) acrylate, alkoxyethyl (meth) acrylate, 2- (Meth) acrylate, 2,2,2-tetrafluoroethyl (meth) acrylate, 1H, 1H, 2H, 2H-perfluorodecyl (meth) acrylate, 4-butylphenyl (Meth) acrylate, phenoxymethyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2,4,5-tetramethylphenyl ) Acrylate, glycidyl (meth) acrylate, glycidyloxybutyl (meth) acrylate, glycidyloxyethyl (meth) acrylate, glycidyloxypropyl (meth) acrylate, tetrahydrofurfuryl (Meth) acrylate, hydroxyalkyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3- (Meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (Meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminopropyl (meth) acrylate, trimethoxysilylpropyl (meth) acrylate, trimethoxysilylpropyl (Meth) acrylate, polyethylene oxide monomethyl ether (meth) acrylate, oligoethylene oxide monomethyl ether (meth) acrylate, polyethylene oxide (meth) acrylate, oligoethylene oxide (meth) (Meth) acrylate, polyethylene oxide monoalkyl ether (meth) acrylate, polyethylene oxide monoalkyl ether (Meth) acrylate, propylene oxide monoalkyl ether (meth) acrylate, oligo propylene oxide monoalkyl ether (meth) acrylate, 2-methacryloyloxyethyl succinic acid, 2-methacryloyl (Meth) acrylate, 2-methacryloyloxyethyl-2-hydroxypropyl phthalate, butoxy ethyleneglycol (meth) acrylate, triploloethyl (meth) acrylate, Acrylate, EO-modified cresol (meth) acrylate, EO-modified nonylphenol (meth) acrylate, PO-modified nonyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl Phenol (meth) acrylate, and EO-modified 2-ethylhexyl (meth) acrylate.

Examples of the (meth) acrylamides having 5 to 35 carbon atoms include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N- (Meth) acrylamide, N-methyl (meth) acrylamide, N-butyl (meth) acrylamide, Nt- , N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide and (meth) acryloylmorpholine.

&Lt; Polymerizable oligomer &

Examples of the polymerizable oligomer include epoxy acrylates, urethane acrylates, polyester acrylates, polyether acrylates, copolymer acrylates, polybutadiene acrylates, alicyclic epoxy compounds, glycidyl ether type epoxy compounds, A cetyl compound, and a vinyl ether compound. The epoxy acrylate may be obtained, for example, by an addition reaction of a glycidyl ether compound and an acrylic acid.

Examples of the glycidyl ether compound include 1,6-hexane diglycidyl ether, polyethylene glycol diglycidyl ether, bisphenol A type epoxy resin, phenol novolak type epoxy resin and cresol novolak type epoxy resin.

Examples of the acrylic acid include acrylic acid, methacrylic acid, and lower alkyl esters such as methyl acrylate, ethyl acrylate, propyl acrylate, methacrylate methyl ester, methacrylic acid ethyl ester and methacrylic acid propyl ester. Further, a compound having an ester bond obtained by reacting a hydroxyl group of an epoxy acrylate with a polybasic acid compound may be used.

Examples of the polybasic acid compound include maleic anhydride, succinic anhydride, itaconic anhydride, dodecylsuccinic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid anhydride , Methylcyclohexene dicarboxylic acid anhydride, and the like.

The urethane acrylate may be obtained by an addition reaction between a reactant of a polyol and a polyisocyanate and an acrylate containing a hydroxyl group.

Examples of the polyol include 1,6-hexanediol diglycidyl ether, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polycarbonate diol, and polyester diol.

As the polyisocyanate, known ones can be used, and examples thereof include hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate and the like An isocyanurate type polyisocyanate comprising a diisocyanate compound, an adduct type polyisocyanate of the above diisocyanate compound and trimethylol propane, and a buret type polyisocyanate comprising the above diisocyanate compound.

Examples of the acrylate containing a hydroxyl group include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate and 4-hydroxybutyl acrylate. Further, other monomers copolymerizable with each other may be used, and methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, t-butyl acrylate, styrene,? -Methyl styrene and the like may be used.

The polyester acrylate may be obtained by esterification of a polyester polyol comprising a polyol and a polybasic acid and acrylic acid.

Examples of the polyol used for the synthesis of the polyester acrylate include 1,3-butanediol, 1,4-butanediol, trimethylolethane, trimethylolpropane, ditrimethylolethane, ditrimethylolpropane, pentaerythritol , Dipentaerythritol, tripentaerythritol, diglycerol, glycerin, and numerous polysiloxane polyols, poly (oxyalkylene) polyols, polyester polyols, polyether polyols, polyether polyester polyols, polyolefin polyols, poly Alkyl acrylate) polyol, polycarbonate polyol and the like.

Examples of the polybasic acid used in the synthesis of the polyester acrylate include saturated polybasic acids such as adipic acid, succinic acid and sebacic acid; unsaturated polybasic acids such as maleic acid, fumaric acid, itaconic acid and citraconic acid; , Aromatic polybasic acids such as terephthalic acid and trimellitic acid. The polyether acrylate may be a reaction product of a polyether polyol such as polyethylene glycol or polypropylene glycol with an unsaturated carboxylic acid.

The above-mentioned copolymer acrylate may be an acrylic compound obtained by adding a (meth) acryloyl group to the side chain of the acrylic ester copolymer. Examples of the copolymer acrylate include a compound obtained by copolymerizing glycidyl methacrylate and acrylic acid, a compound obtained by copolymerizing acrylic acid and methacrylic acid to add glycidyl methacrylate, 2- A compound obtained by copolymerizing HEMA (2-hydroxyethyl methacrylate) and 2-HEA (2-hydroxyethyl acrylate) and adding isocyanate-containing acrylate.

The polybutadiene acrylate may be an acrylic compound having a polybutadiene or a hydrogenated polybutadiene skeleton.

The polybutadiene acrylate is obtained by, for example, a method of acrylating a hydroxyl group-containing polybutadiene, and a method of adding a hydroxyl group-containing acrylate to a hydroxyl group-containing polybutadiene via a diisocyanate.

<Polymerization Initiator>

The resin composition for decorative molding of the present invention contains a polymerization initiator.

Examples of the polymerization initiator include an energy ray polymerization initiator of radical polymerization or cation polymerization, and examples thereof include aromatic ketones, aromatic onium salt compounds, organic peroxides, hexaarylbimidazole compounds, keto oxime ester compounds, , An azinium compound, a metallocene compound, and a compound having an active ester compound.

For example, there may be mentioned acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, xanthone, fluorenone, benzaldehyde, , Anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, benzoin propyl ether, Hydroxy-2-methyl-1-phenylpropan-1-one, ethyl (2-hydroxypropyl) Methylthioxanthone, 2-methylthioxanthone, 2-methylthio-1- [4- (methylthio) phenyl] -2-morpholino- (2-hydroxy-2-propyl) ketone &lt; / RTI &gt; , 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2, 4-trimethylpentylphosphine oxide, oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone).

Examples of commercial products of the polymerization initiator by an active energy ray include commercial products of Irgacure 184, 369, 651, 500, 819, 907, 784, 2959, CGI1700, CI 1750, CGI1850, CG24-61, DARACURE 1116, 1173, manufactured by BASF, trade name: Lucirin TPO, manufactured by UCB, trade name: Yubechryl P36, manufactured by Furatetsuri Lambertish, trade name: Ezacure KIP150, KIP65LT, KIP100F, KT37, KT55, KTO46, KIP75 / B, and the like.

The amount of the polymerization initiator to be used by the active energy ray may be selected in accordance with a known polymerization reaction. For example, the radical polymerization initiator is suitably used in an amount of usually 0.0001 to 10 parts by weight, preferably 0.001 to 5 parts by weight, based on the total amount of the active energy linear polymerizable monomer. The lower limit of the temperature at the time of the curing reaction is usually 0 ° C or higher, preferably 10 ° C or higher, and the upper limit is usually 200 ° C or lower, preferably 100 ° C or lower.

<Other combinations>

The resin composition for decorative molding of the present invention may contain, depending on the purpose, organic solvents such as hydrocarbon organic solvents such as toluene and xylene, ester organic solvents such as ethyl acetate and butyl acetate, ketone organic solvents such as methyl ethyl ketone, Various fillers and pigments such as calcium carbonate, talc, mica, clay, silica powder, colloidal silica, barium sulfate, aluminum hydroxide, zinc stearate, zincation, spinach and azo pigment may be added.

The content of the organic solvent is preferably 20 parts by mass or more and 80 parts by mass or less with respect to 100 parts by mass of the total amount of the compound represented by the general formula (I), the polymerizable monomer, and the polymerizable oligomer, More preferably 30 parts by mass or more and 70 parts by mass or less.

<Laminate>

The laminate of the present invention comprises a layer made of a cured product of the resin composition for edging molding and a mirror polished layer. The mirror surface gloss layer may be a metal vapor deposition film, a metal such as aluminum or glass, or a metallic wind in which flakes of an inorganic substance are dispersed.

<Processing method>

The resin composition for decorative molding of the present invention can be coated on various substrates or on the surface of an article by a conventional method for forming a coating film. The coating film can be formed by using, for example, a dipping method, a spraying method, a screen printing method, a rotary coating method, an electrostatic coating method, a roll coater, a brush or the like.

The resin composition for decorative molding of the present invention can be formed into a curing film by applying the resin composition for decorative molding of the present invention on a film and drying the organic solvent. It is preferably applied to a film as a substrate and then heated and dried at 20 ° C to 150 ° C for 1 to 100 minutes. The heating and drying conditions are suitably selected in consideration of coating film forming conditions and the like. Examples of the film include polyethylene terephthalate, polycarbonate, polyethylene, polypropylene, polyethersulfone, and fluorine-based polymers, and a film obtained by treating the surface of these films with a releasing agent is preferably used.

Example

Hereinafter, the present invention will be described in further detail with reference to Examples, but the present invention is not limited by the following Examples within the scope not exceeding the gist of the present invention. Unless otherwise stated, &quot;% &quot; is expressed in mass% and &quot; part &quot;

<Analysis of synthesis example of alkylene oxide-modified dipentaerythritol (meth) acrylate>

The products obtained in the following Synthesis Examples were analyzed by the following methods, respectively.

&Lt; Liquid chromatographic mass spectrometry (hereinafter abbreviated as LC-MS analysis) conditions >

LC-MS analysis for each synthesis example was carried out under the following conditions.

LC section: 1100 series column manufactured by Agilent Technologies: InertsilODS-2 (4.6 mmφ × 250 mm, 5 μm) eluent: water 80.0% - 30 minutes → 0.0%, methanol 20.0% - 30 minutes → 100.0% 40 占 폚, flow rate: 1 ml / min, injection amount: 5 占 ((200 ppm methanol solution), detector: UV, RI

· MS part: JMS T100LP (manufactured by NIPPON ELECTRONICS CO., LTD.) Ring lens voltage: 10 V, ionization method: APCI +

Solvent removal temperature: 350 占 폚, needle voltage: 2500 V, orifice 1 temperature: 80 占 폚 orifice 1 voltage: 60 V, ion guide peak voltage: 1000 V, orifice 2 voltage: 5 V

&Lt; Measurement condition of hydroxyl group (OH)

Acetic acid and pyridine were mixed at a weight ratio of 1: 9 to prepare an acetylation reagent. The sample was weighed into a flask, added with an acetylating reagent, and heated at 80 DEG C for 2 hours. After the reaction, titration with 1 mol / l potassium hydroxide aqueous solution was carried out using phenolphthalein as an indicator.

<NMR analysis>

The results of NMR analysis are shown by the numbers ((1) to (3)) describing the attribution of each peak to the following formula.

[Chemical Formula 5]

< ¹³ C-NMR analysis (400 MHz) of EO adduct acrylate, in CDCl ₃ >

45 ppm: derived from (2), 60 ppm derived from (3), 61 to 63 ppm derived from ethylene oxide, 68 to 73 ppm derived from ethylene oxide added to (3), 77 to 79 ppm : Derived from chloroform in a medium, 128 to 131 ppm: derived from an ester-bonded acrylic acid, 165 to 167 ppm:

< ¹ H-NMR analysis of EO adduct acrylate (400 MHz), in CDCl ₃ >

3.3 to 4.1 ppm (16 H): derived from ethylene oxide derived from (3), 3.6 to 4.4 ppm (8 H): (3) OH, 5.7 to 6.4 ppm (18 H) , 7.3 ppm: derived from deuterated chloroform

<LC-MS analysis of EO adduct acrylate>

8.8 to 11.5 minutes: ethylene oxide polymer diacrylate, 14 to 16 minutes: dipentaerythritol ethylene oxide modified monoacrylate, 16 to 20 minutes: dipentaerythritol ethylene oxide modified hexaacrylate

[Synthesis of alkylene oxide-modified dipentaerythritol (meth) acrylate]

[Synthesis Example 1]

(Synthesis of dipentaerythritol 2EO adduct acrylate)

254 g (1.0 mol) of dipentaerythritol (OH 1324, manufactured by Hiroe Kagaku Kogyo Co., Ltd.), 127 g of toluene and 0.3 g of KOH were charged into an autoclave having a capacity of 1 liter equipped with a stirrer, The temperature was raised and stirred to obtain a slurry-like liquid. Subsequently, the mixture was heated to 130 DEG C, and 132 g (3 mol) of ethylene oxide was slowly introduced into the autoclave and reacted. With the introduction of ethylene oxide, the temperature in the autoclave rose. Cooling was applied at any time, and the reaction temperature was maintained at 140 캜 or lower. After the reaction, the pressure was reduced to 140 mmHg or lower at 10 mmHg to remove excessive ethylene oxide and ethylene glycol as a by-product. Thereafter, the mixture was neutralized with acetic acid to adjust the pH to 6-7. The OH value of the obtained dipentaerythritol 2EO adduct was 982.

343 g (1 mol) of the obtained ethylene glycol-modified dipentaerythritol (OH = 982), 562 g (7.8 mol) of acrylic acid, 45 g of paratoluene sulfonic acid, 900 g of toluene and 0.9 g of hydroquinone were poured into a glass four- , And a heating reaction was carried out while blowing air. The water formed in the reaction was removed at any time from the system by azeotropic distillation with toluene. The reaction temperature was 100 to 110 ° C, and the reaction product removed from the system at the end of the reaction was 112 g. After the reaction, the reaction mixture was washed with water and washed with water to separate the upper toluene layer. The toluene was distilled off under reduced pressure to obtain 594 g (yield: 89%) of dipentaerythritol 2EO adduct acrylate represented by the general formula (I) &Lt; / RTI &gt;

On the other hand, the measurement of the hydroxyl value and the analysis by ¹ H-NMR, ¹³ C-NMR, HPLC, and LC-MS revealed that it was dipentaerythritol 2 EO adduct acrylate. Hereinafter, the results of NMR analysis and LC-MS analysis are shown, and the titles of NMR peaks are indicated by the above numbers.

&Lt; Dipentaerythritol 2EO adduct acrylate &gt; ( ¹³ C-NMR analysis (400 MHz), InCDCl3)

45 ppm: derived from (2), 60 ppm derived from (3), 61 to 63 ppm derived from ethylene oxide, 68 to 73 ppm derived from ethylene oxide added to (3), 77 to 79 ppm : Derived from chloroform in a medium, 128 to 131 ppm: derived from an ester-bonded acrylic acid, 165 to 167 ppm:

&Lt; Dipentaerythritol 2EO adduct acrylate &gt; ( ¹ H-NMR analysis (400 MHz), In CDCl 3)

3.3 to 4.1 ppm (16 H): derived from (1), (3), 3.6 to 4.4 ppm (8H): ethylene oxide derived from ethylene oxide added to OH in (3), 5.7 to 6.4 ppm (18H) Derived from double bond, 7.3 ppm: derived from heavy chloroform

&Lt; Dipentaerythritol 2EO adduct acrylate &gt; (LC-MS analysis)

8.8 to 11.5 minutes: ethylene oxide polymer diacrylate, 14 to 16 minutes: dipentaerythritol ethylene oxide modified monoacrylate, 16 to 20 minutes: dipentaerythritol ethylene oxide modified hexaacrylate

[Synthesis Example 2]

(Synthesis of dipentaerythritol 3EO adduct acrylate)

254 g (1.0 mol) of dipentaerythritol (OH 1324, manufactured by Hiroe Kagaku Kogyo Co., Ltd.), 127 g of toluene and 0.3 g of KOH were charged into an autoclave having a capacity of 1 liter equipped with a stirrer, The temperature was raised and stirred to obtain a slurry-like liquid. Subsequently, the mixture was heated to 130 DEG C, and 176 g (4 mol) of ethylene oxide was slowly introduced into the autoclave and reacted. With the introduction of ethylene oxide, the temperature in the autoclave rose. Cooling was applied at any time, and the reaction temperature was maintained at 140 캜 or lower. After the reaction, the pressure was reduced to 140 mmHg or lower at 10 mmHg to remove excessive ethylene oxide and ethylene glycol as a by-product. Thereafter, the mixture was neutralized with acetic acid to adjust the pH to 6-7. The OH value of the obtained dipentaerythritol 3EO adduct was 897.

375 g (1 mol) of the obtained ethylene glycol-modified dipentaerythritol (OH 897), 562 g (7.8 mol) of acrylic acid, 46 g of paratoluene sulfonic acid, 900 g of toluene and 0.9 g of hydroquinone were charged into a glass four- , And a heating reaction was carried out while blowing air. The water formed in the reaction was removed at any time from the system by azeotropic distillation with toluene. The reaction temperature was 100 to 110 ° C, and the reaction product removed from the system at the end of the reaction was 112 g. After the reaction, the reaction mixture was washed with water and washed with water to separate the upper toluene layer. The toluene was distilled off under reduced pressure to obtain 615 g (yield: 88%) of dipentaerythritol 3EO adduct acrylate represented by the general formula (I) &Lt; / RTI &gt;

On the other hand, the measurement of the hydroxyl value and the analysis by ¹ H-NMR, ¹³ C-NMR, HPLC, and LC-MS revealed that it was dipentaerythritol 3 EO adduct acrylate. Hereinafter, the results of NMR analysis and LC-MS analysis are shown, and the titles of NMR peaks are indicated by the above numbers.

&Lt; Dipentaerythritol 3EO adduct acrylate &gt; ( ¹³ C-NMR analysis (400 MHz), InCDCl3)

45 ppm: derived from (2), 60 ppm derived from (3), 61 to 63 ppm derived from ethylene oxide, 68 to 73 ppm derived from ethylene oxide added to (3), 77 to 79 ppm : Derived from chloroform in a medium, 128 to 131 ppm: derived from an ester-bonded acrylic acid, 165 to 167 ppm:

&Lt; Dipentaerythritol 3EO adduct acrylate &gt; ( ¹ H-NMR analysis (400 MHz), In CDCl 3)

3.3 to 4.1 ppm (16 H): derived from (3), 3.6 to 4.4 ppm (12 H): derived from ethylene oxide added to OH in (3), 5.7 to 6.4 ppm (18 H) , 7.3 ppm: derived from deuterated chloroform

&Lt; Dipentaerythritol 3EO adduct acrylate &gt; (LC-MS analysis)

8.8 to 11.5 minutes: ethylene oxide polymer diacrylate, 14 to 16 minutes: dipentaerythritol ethylene oxide modified monoacrylate, 16 to 20 minutes: dipentaerythritol ethylene oxide modified hexaacrylate

[Synthesis Example 3]

(Synthesis of dipentaerythritol 4EO adduct acrylate)

254 g (1.0 mol) of dipentaerythritol (OH 1324, manufactured by Hiroe Kagaku Kogyo Co., Ltd.), 127 g of toluene and 0.3 g of KOH were poured into an autoclave having a capacity of 1 liter equipped with a stirrer, The temperature was raised and stirred to obtain a slurry-like liquid. Subsequently, the mixture was heated to 130 DEG C, and 220 g (5 mol) of ethylene oxide was slowly introduced into the autoclave and reacted. With the introduction of ethylene oxide, the temperature in the autoclave rose. Cooling was applied at any time, and the reaction temperature was maintained at 140 캜 or lower. After the reaction, the pressure was reduced to 140 mmHg or lower at 10 mmHg to remove excessive ethylene oxide and ethylene glycol as a by-product. Thereafter, the mixture was neutralized with acetic acid to adjust the pH to 6-7. The OH value of the obtained dipentaerythritol 4EO adduct was 765.

440 g (1 mol) of the obtained ethylene glycol-modified dipentaerythritol (OH 765), 562 g (7.8 mol) of acrylic acid, 50 g of paratoluene sulfonic acid, 900 g of toluene and 1 g of hydroquinone were poured into a glass four- , And a heating reaction was carried out while blowing air. The water formed in the reaction was removed at any time from the system by azeotropic distillation with toluene. The reaction temperature was 100 to 110 ° C, and the reaction product removed from the system at the completion of the reaction was 113 g. After the reaction, the reaction mixture was washed with water and water, and the toluene layer in the upper layer was separated. The toluene was distilled off under reduced pressure to obtain 665 g (yield 87%) of dipentaerythritol 4EO adduct acrylate represented by the general formula (I) &Lt; / RTI &gt;

On the other hand, when the hydroxyl value was measured and analyzed by ¹ H-NMR, ¹³ C-NMR, HPLC, and LC-MS, it became clear that dipentaerythritol 4 EO adduct acrylate. Hereinafter, the results of NMR analysis and LC-MS analysis are shown, and the titles of NMR peaks are indicated by the above numbers.

&Lt; Dipentaerythritol 4EO adduct acrylate &gt; ( ¹³ C-NMR analysis (400 MHz), InCDCl3)

45 ppm: derived from (2), 60 ppm derived from (3), 61 to 63 ppm derived from ethylene oxide, 68 to 73 ppm derived from ethylene oxide added to (3), 77 to 79 ppm : Derived from chloroform in a medium, 128 to 131 ppm: derived from an ester-bonded acrylic acid, 165 to 167 ppm:

&Lt; Dipentaerythritol 4EO adduct acrylate &gt; ( ¹ H-NMR analysis (400 MHz), In CDCl 3)

3.3 to 4.1 ppm (16 H): derived from (3), 3.6 to 4.4 ppm (16 H): derived from ethylene oxide added to OH in (3), 5.7 to 6.4 ppm (18 H) , 7.3 ppm: derived from deuterated chloroform

&Lt; Dipentaerythritol 4EO adduct acrylate &gt; (LC-MS analysis)

8.8 to 11.5 minutes: ethylene oxide polymer diacrylate, 14 to 16 minutes: dipentaerythritol ethylene oxide modified monoacrylate, 16 to 20 minutes: dipentaerythritol ethylene oxide modified hexaacrylate

[Synthesis Example 4]

Synthesis of dipentaerythritol 5EO adduct acrylate

254 g (1.0 mol) of dipentaerythritol (OH 1324, manufactured by Hiroe Kagaku Kogyo Co., Ltd.), 127 g of toluene and 0.3 g of KOH were poured into an autoclave having a capacity of 1 liter equipped with a stirrer, The temperature was raised and stirred to obtain a slurry-like liquid. Subsequently, the mixture was heated to 130 DEG C, and 264 g (6 mol) of ethylene oxide was slowly introduced into the autoclave and reacted. With the introduction of ethylene oxide, the temperature in the autoclave rose. Cooling was applied at any time, and the reaction temperature was maintained at 140 캜 or lower. After the reaction, the pressure was reduced to 140 mmHg or lower at 10 mmHg to remove excessive ethylene oxide and ethylene glycol as a by-product. Thereafter, the mixture was neutralized with acetic acid to adjust the pH to 6-7. The OH value of the obtained dipentaerythritol 5EO adduct was 706.

477 g (1 mol) of the obtained ethylene glycol-modified dipentaerythritol (OH: 706), 562 g (7.8 mol) of acrylic acid, 52 g of paratoluene sulfonic acid, 900 g of toluene and 1 g of hydroquinone were poured into a glass four- , And a heating reaction was carried out while blowing air. The water formed in the reaction was removed at any time from the system by azeotropic distillation with toluene. The reaction temperature was 100 to 110 ° C, and the reaction product removed from the system at the completion of the reaction was 113 g. After the reaction, the reaction mixture was washed with water and water, and the toluene layer as an upper layer was separated. The toluene was distilled off under reduced pressure to obtain 697 g (yield 87%) of dipentaerythritol 5EO adduct acrylate represented by the general formula (I) &Lt; / RTI &gt;

On the other hand, the measurement of the hydroxyl value and the analysis by ¹ H-NMR, ¹³ C-NMR, HPLC, and LC-MS revealed that it was dipentaerythritol 5 EO adduct acrylate. Hereinafter, the results of NMR analysis and LC-MS analysis are shown, and the titles of NMR peaks are indicated by the above numbers.

&Lt; Dipentaerythritol 5EO adduct acrylate &gt; ( ¹³ C-NMR analysis (400 MHz), InCDCl3)

45 ppm: derived from (2), 60 ppm derived from (3), 61 to 63 ppm derived from ethylene oxide, 68 to 73 ppm derived from ethylene oxide added to (3), 77 to 79 ppm : Derived from chloroform in a medium, 128 to 131 ppm: derived from an ester-bonded acrylic acid, 165 to 167 ppm:

&Lt; Dipentaerythritol 5EO adduct acrylate &gt; ( ¹ H-NMR analysis (400 MHz), In CDCl 3)

3.3 to 4.1 ppm (16 H): derived from (3), 3.6 to 4.4 ppm (20 H): derived from ethylene oxide added to OH in (3), 5.7 to 6.4 ppm (18 H) , 7.3 ppm: derived from deuterated chloroform

&Lt; Dipentaerythritol 5EO adduct acrylate &gt; (LC-MS analysis)

8.8 to 11.5 minutes: ethylene oxide polymer diacrylate, 14 to 16 minutes: dipentaerythritol ethylene oxide modified monoacrylate, 16 to 20 minutes: dipentaerythritol ethylene oxide modified hexaacrylate

[Synthesis Example 5]

(Synthesis of dipentaerythritol 6EO adduct acrylate)

254 g (1.0 mol) of dipentaerythritol (OH 1324, manufactured by Hiroe Kagaku Kogyo Co., Ltd.), 127 g of toluene and 0.3 g of KOH were poured into an autoclave having a capacity of 1 liter equipped with a stirrer, The temperature was raised and stirred to obtain a slurry-like liquid. Subsequently, the mixture was heated to 130 DEG C, and 352 g (8 mol) of ethylene oxide was slowly introduced into the autoclave and reacted. With the introduction of ethylene oxide, the temperature in the autoclave rose. Cooling was applied at any time, and the reaction temperature was maintained at 140 캜 or lower. After the reaction, the pressure was reduced to 140 mmHg or lower at 10 mmHg to remove excessive ethylene oxide and ethylene glycol as a by-product. Thereafter, the mixture was neutralized with acetic acid to adjust the pH to 6-7. The OH value of the obtained dipentaerythritol 6EO adduct was 646.

521 g (1 mol) of the obtained ethylene glycol-modified dipentaerythritol (OH 646), 562 g (7.8 mol) of acrylic acid, 54 g of paratoluene sulfonic acid, 900 g of toluene and 1.1 g of hydroquinone were charged into a glass four- , And a heating reaction was carried out while blowing air. The water formed in the reaction was removed at any time from the system by azeotropic distillation with toluene. The reaction temperature was 100 to 110 ° C, and the reaction product removed from the system at the completion of the reaction was 113 g. After the reaction, the reaction mixture was washed with water and water, and the toluene layer in the upper layer was separated. The toluene was distilled off under reduced pressure to obtain 727 g (yield: 86%) of dipentaerythritol 6EO adduct acrylate represented by the general formula (I) &Lt; / RTI &gt;

On the other hand, the measurement of hydroxyl value and the analysis by ¹ H-NMR, ¹³ C-NMR, HPLC, and LC-MS revealed that it was dipentaerythritol 6 EO adduct acrylate. Hereinafter, the results of NMR analysis and LC-MS analysis are shown, and the titles of NMR peaks are indicated by the above numbers.

&Lt; Dipentaerythritol 6EO adduct acrylate &gt; ( ¹³ C-NMR analysis (400 MHz), InCDCl3)

45 ppm: derived from (2), 60 ppm derived from (3), 61 to 63 ppm derived from ethylene oxide, 68 to 73 ppm derived from ethylene oxide added to (3), 77 to 79 ppm : Derived from chloroform in a medium, 128 to 131 ppm: derived from an ester-bonded acrylic acid, 165 to 167 ppm:

&Lt; Dipentaerythritol 6EO adduct acrylate &gt; ( ¹ H-NMR analysis (400 MHz), In CDCl 3)

3.3 to 4.1 ppm (16 H): derived from (3), 3.6 to 4.4 ppm (24 H): derived from ethylene oxide added to OH in (3), 5.7 to 6.4 ppm (18 H) , 7.3 ppm: derived from deuterated chloroform

&Lt; Dipentaerythritol 6EO adduct acrylate &gt; (LC-MS analysis)

8.8 to 11.5 minutes: ethylene oxide polymer diacrylate, 14 to 16 minutes: dipentaerythritol ethylene oxide modified monoacrylate, 16 to 20 minutes: dipentaerythritol ethylene oxide modified hexaacrylate

[Synthesis Example 6]

(Synthesis of dipentaerythritol 8EO adduct acrylate)

254 g (1.0 mol) of dipentaerythritol (OH 1324, manufactured by Hiroe Kagaku Kogyo Co., Ltd.), 36 g of distilled water and 0.3 g of KOH were charged into an autoclave having a capacity of 1 liter equipped with a stirrer, The temperature was raised and stirred to obtain a slurry-like liquid. Subsequently, the mixture was heated to 130 DEG C, and 396 g (9 mol) of ethylene oxide was gradually introduced into the autoclave and reacted. With the introduction of ethylene oxide, the temperature in the autoclave rose. Cooling was applied at any time, and the reaction temperature was maintained at 140 캜 or lower. After the reaction, the pressure was reduced to 140 mmHg or lower at 10 mmHg to remove excessive ethylene oxide and ethylene glycol as a by-product. Thereafter, the mixture was neutralized with acetic acid to adjust the pH to 6-7. The OH value of the obtained dipentaerythritol 8EO adduct was 555.

607 g (1 mol) of the obtained ethylene glycol-modified dipentaerythritol (OH 555), 569 g (7.9 mol) of acrylic acid, 59 g of paratoluene sulfonic acid, 850 g of toluene and 1.2 g of hydroquinone were charged into a glass four- , And a heating reaction was carried out while blowing air. The water formed in the reaction was removed at any time from the system by azeotropic distillation with toluene. The reaction temperature was 100 to 110 ° C, and the reaction product removed from the system at the completion of the reaction was 113 g. After the reaction, the reaction mixture was washed with water and water to remove the toluene layer of the upper layer. The toluene was distilled off under reduced pressure to obtain 791 g (yield: 85%) of dipentaerythritol 8EO adduct acrylate represented by the general formula (I) &Lt; / RTI &gt;

On the other hand, the measurement of the hydroxyl value and the analysis by ¹ H-NMR, ¹³ C-NMR, HPLC, and LC-MS revealed that it was dipentaerythritol 8 EO adduct acrylate. Hereinafter, the results of NMR analysis and LC-MS analysis are shown, and the titles of NMR peaks are indicated by the above numbers.

&Lt; Dipentaerythritol 8EO adduct acrylate &gt; ( ¹³ C-NMR analysis (400 MHz), InCDCl3)

45 ppm: derived from (2), 60 ppm derived from (3), 61 to 63 ppm derived from ethylene oxide, 68 to 73 ppm derived from ethylene oxide added to (3), 77 to 79 ppm : Derived from chloroform in a medium, 128 to 131 ppm: derived from an ester-bonded acrylic acid, 165 to 167 ppm:

&Lt; Dipentaerythritol 8EO adduct acrylate &gt; ( ¹ H-NMR analysis (400 MHz), In CDCl 3)

3.3 to 4.1 ppm (16 H): derived from (3), 3.6 to 4.4 ppm (24 H): derived from ethylene oxide added to OH in (3), 5.7 to 6.4 ppm (18 H) , 7.3 ppm: derived from deuterated chloroform

&Lt; Dipentaerythritol 8EO adduct acrylate &gt; (LC-MS analysis)

8.8 to 11.5 minutes: ethylene oxide polymer diacrylate, 14 to 16 minutes: dipentaerythritol ethylene oxide modified monoacrylate, 16 to 20 minutes: dipentaerythritol ethylene oxide modified hexaacrylate

[Synthesis Example 7]

(Synthesis of dipentaerythritol 10EO adduct acrylate)

254 g (1.0 mol) of dipentaerythritol (OH 1324, manufactured by Hiroe Kagaku Kogyo Co., Ltd.), 36 g of distilled water and 0.3 g of KOH were charged into an autoclave having a capacity of 1 liter equipped with a stirrer, The temperature was raised and stirred to obtain a slurry-like liquid. Subsequently, the mixture was heated to 130 占 폚, and 484 g (11 mol) of ethylene oxide was gradually introduced into the autoclave for reaction. With the introduction of ethylene oxide, the temperature in the autoclave rose. Cooling was applied at any time, and the reaction temperature was maintained at 140 캜 or lower. After the reaction, the pressure was reduced to 140 mmHg or lower at 10 mmHg to remove excessive ethylene oxide and ethylene glycol as a by-product. Thereafter, the mixture was neutralized with acetic acid to adjust the pH to 6-7. The OH value of the obtained dipentaerythritol 10EO adduct was 485.

694 g (1 mol) of the obtained ethylene glycol-modified dipentaerythritol (OH 485), 583 g (8.1 mol) of acrylic acid, 64 g of paratoluene sulfonic acid, 1000 g of toluene and 1.3 g of hydroquinone were charged into a glass four- , And a heating reaction was carried out while blowing air. The water formed in the reaction was removed at any time from the system by azeotropic distillation with toluene. The reaction temperature was 100 to 110 ° C, and the reaction product removed from the system at the completion of the reaction was 113 g. After the reaction, the reaction mixture was washed with water and water, and the toluene layer of the upper layer was separated. The toluene was distilled off under reduced pressure to obtain 865 g (yield 85%) of dipentaerythritol 10EO adduct acrylate represented by the general formula (I) &Lt; / RTI &gt;

On the other hand, when the hydroxyl value was measured and analyzed by ¹ H-NMR, ¹³ C-NMR, HPLC, and LC-MS, it became clear that dipentaerythritol 10 EO adduct acrylate. Hereinafter, the results of NMR analysis and LC-MS analysis are shown, and the titles of NMR peaks are indicated by the above numbers.

&Lt; Dipentaerythritol 10EO adduct acrylate &gt; ( ¹³ C-NMR analysis (400 MHz), InCDCl3)

45 ppm: derived from (2), 60 ppm derived from (3), 61 to 63 ppm derived from ethylene oxide, 68 to 73 ppm derived from ethylene oxide added to (3), 77 to 79 ppm : Derived from chloroform in a medium, 128 to 131 ppm: derived from an ester-bonded acrylic acid, 165 to 167 ppm:

&Lt; Dipentaerythritol 10EO adduct acrylate &gt; ( ¹ H-NMR analysis (400 MHz), In CDCl 3)

3.3 to 4.1 ppm (16 H): derived from (3), 3.6 to 4.4 ppm (24 H): derived from ethylene oxide added to OH in (3), 5.7 to 6.4 ppm (18 H) , 7.3 ppm: derived from deuterated chloroform

&Lt; Dipentaerythritol 10EO adduct acrylate &gt; (LC-MS analysis)

8.8 to 11.5 minutes: ethylene oxide polymer diacrylate, 14 to 16 minutes: dipentaerythritol ethylene oxide modified monoacrylate, 16 to 20 minutes: dipentaerythritol ethylene oxide modified hexaacrylate

[Synthesis Example 8]

(Synthesis of dipentaerythritol 12EO adduct acrylate)

254 g (1.0 mol) of dipentaerythritol (OH 1324, manufactured by Hiroe Kagaku Kogyo Co., Ltd.), 36 g of distilled water and 0.3 g of KOH were charged into an autoclave having a capacity of 1 liter equipped with a stirrer, The temperature was raised and stirred to obtain a slurry-like liquid. Then, the mixture was heated to 130 DEG C, and 572 g (13 mol) of ethylene oxide was gradually introduced into the autoclave and reacted. With the introduction of ethylene oxide, the temperature in the autoclave rose. Cooling was applied at any time, and the reaction temperature was maintained at 140 캜 or lower. After the reaction, the pressure was reduced to 140 mmHg or lower at 10 mmHg to remove excessive ethylene oxide and ethylene glycol as a by-product. Thereafter, the mixture was neutralized with acetic acid to adjust the pH to 6-7. The OH value of the obtained dipentaerythritol 12EO adduct was 430.

783 g (1 mol) of the obtained ethylene glycol-modified dipentaerythritol (OH 430), 612 g (8.4 mol) of acrylic acid, 69 g of para-toluenesulfonic acid, 1100 g of toluene and 1.4 g of hydroquinone were poured into a glass four- , And a heating reaction was carried out while blowing air. The water formed in the reaction was removed at any time from the system by azeotropic distillation with toluene. The reaction temperature was 100 to 110 ° C, and the reaction product removed from the system at the completion of the reaction was 113 g. After the reaction, the reaction mixture was washed with water and water, and the toluene layer in the upper layer was separated. The toluene was distilled off under reduced pressure to obtain 929 g (yield: 84%) of dipentaerythritol 12EO adduct acrylate represented by the general formula (I) &Lt; / RTI &gt;

On the other hand, the measurement of the hydroxyl value and the analysis by ¹ H-NMR, ¹³ C-NMR, HPLC, and LC-MS revealed that it was dipentaerythritol 12 EO adduct acrylate. Hereinafter, the results of NMR analysis and LC-MS analysis are shown, and the titles of NMR peaks are indicated by the above numbers.

&Lt; Dipentaerythritol 12EO adduct acrylate &gt; ( ¹³ C-NMR analysis (400 MHz), InCDCl3)

45 ppm: derived from (2), 60 ppm derived from (3), 61 to 63 ppm derived from ethylene oxide, 68 to 73 ppm derived from ethylene oxide added to (3), 77 to 79 ppm : Derived from chloroform in a medium, 128 to 131 ppm: derived from an ester-bonded acrylic acid, 165 to 167 ppm:

&Lt; Dipentaerythritol 12EO adduct acrylate &gt; ( ¹ H-NMR analysis (400 MHz), In CDCl 3)

3.3 to 4.1 ppm (16 H): derived from (3), 3.6 to 4.4 ppm (24 H): derived from ethylene oxide added to OH in (3), 5.7 to 6.4 ppm (18 H) , 7.3 ppm: derived from deuterated chloroform

&Lt; Dipentaerythritol 12EO adduct acrylate &gt; (LC-MS analysis)

8.8 to 11.5 minutes: ethylene oxide polymer diacrylate, 14 to 16 minutes: dipentaerythritol ethylene oxide modified monoacrylate, 16 to 20 minutes: dipentaerythritol ethylene oxide modified hexaacrylate

[Adjustment of resin composition for embossing molding]

Table 1 shows examples of formulations using the alkylene oxide-modified dipentaerythritol acrylate obtained in Synthesis Examples 1 to 8 and other polyfunctional monomers. Further, in order to cope with various coating methods such as screen printing, dilution with methyl ethyl ketone was carried out to adjust the viscosity to 100 to 1,000 mPa · s / 25 ° C.

* 1: New Frontia R-1603 (6-functional urethane acrylate manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.)

* 2: Irgacure 184 (an alkylphenone-based photo polymerization initiator manufactured by BASF)

* 3: ACEMATT3600 (silica-based luster remover manufactured by EVONIK DEGUSSA)

* 4: KAYARAD DPHA (dipentaerythritol penta / hexaacrylate mixture, manufactured by Nippon Yakusho Co., Ltd.)

* 5: KAYARAD PET-30 (pentaerythritol tri / tetraacrylate mixture manufactured by Nippon Yakusho Co., Ltd.)

* 6: New Frontia TMPTA (trimethylolpropane triacrylate manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.)

[Evaluation of resin composition for embossing molding]

Various evaluation methods were carried out according to the following methods.

The evaluation results are shown in Table 1 below.

[Viscosity]

Measurement was carried out in accordance with JIS K 5600-2-3.

[Optical Sensitivity]

The samples obtained in Formulation Examples 1 to 31 were coated on a glass substrate with a spin coater at a dry film thickness of 5 占 퐉 and dried at 80 占 폚 to perform a solvent. The uncalcined product was shaded with a step tablet (25 steps, manufactured by RIston Corporation) and cured at 200 mJ under a nitrogen atmosphere with a parallel light type exposure device (SX-UID501H UVQ) manufactured by Ushio Co., .

[Adhesion]

The samples were adjusted in the same manner as the items of light sensitivity and cured at 200 mj / cm 2 using an ABS, PMMA, PC, PET (easy-to-adhered surface) substrate as a substrate with a belt conveyor type UV curing device equipped with a metal halide lamp , And subjected to a cross-cut test according to JIS-K5400, and the remaining scale number was determined as adhesion.

[Pencil hardness]

A cured film was prepared by the same method as that of the adhesion, and the film hardness on PET was measured according to JIS K 5600-5-4.

[My Steel Steel]

A cured film was produced by the same method as that of the adhesion property on the PET film (easy-to-adhere treated surface), and the state of the coated film when 100 times of polishing with a load of 1 kg was applied with 00 steel wool was visually observed, Respectively.

◎: No wounds

○: Two or three wounds on the test piece can be confirmed

△: 10 pieces of wounds can be confirmed on the test piece

X: Multiple wounds can be identified

[Curling]

A cured film was produced in the same manner as in the item of adhesion by using as a base a PET film (easy-to-adhere treated surface) cut into a square of 150 占 퐉 in thickness and 6 cm in one side. One point of four corners of the film was fixed on a flat surface, and the height of the other three points at that time was measured, and the average value was made curl.

[Flexibility]

A cured film was produced by the same method as that of the adhesion property on the PET film (easy-to-adhere treated surface). The produced film was wound around a cylinder of each diameter so that the cured layer was outside, and the diameter of the cylinder when the film was cracked was recorded.

[Polymerization Ratio]

Samples adjusted in the same manner as in the item of adhesion were applied to a steel sheet with a dry film thickness of 5 占 퐉, dried at 80 占 폚, and a solvent was removed. This specimen was cured under the same conditions as the items of photosensitivity and with an integrated illumination of 200 mJ. The test piece was measured by the ATR-IR method, and the peak derived from the ester bond in the vicinity of 1740 cm ^-1 and the peak derived from the double bond in the vicinity of 810 cm ^-1 were compared to find the loss of peak around 810 cm ^-1 And the integrated intensity was confirmed, the polymerization rate was calculated.

[Finishability (Thickness)]

A sample adjusted in the same manner as in the item of adhesion was applied at a dry film thickness of 5 mu m and dried at 80 DEG C to remove the solvent. This specimen was cured under the same conditions as those of the light sensitivity items and at an integrated intensity of 200 mJ. The thickness of the cured product was visually judged.

◎: Excellent

○: Good

△: Normal

Poor: Poor

[Gloss measurement (60 ° reflection)]

A cured film was produced by the same method as that of the adhesion property on the PET film (easy-to-adhere treated surface). The specular surface glossiness was measured by a gloss meter VG2000 (manufactured by Nippon Denshoku Kogyo) according to JIS Z 8741 (60-degree specular gloss).

[Gloss value change (%)]

(60 占 reflection) after various coatings were formed on the base of the base with the cured coating prepared by the gloss measurement (60 占 reflection) on the base of the base against the gloss measurement (60 占 reflection) of the base.

[Sharpness]

A cured film was produced by the same method as that of the adhesion property on the PET film (easy-to-adhere treated surface). The sharpness of the cured coating was measured with a sharpness gloss meter (PGD system) manufactured by Nippon Color Research Laboratories.

Formulation Examples 29 to 31 in which the molar number of addition of alkylene oxide is low and Formulation Examples 22 and 23 in which commercially available dipentaerythritol acrylate having no alkylene oxide is used were diluted by solvent .

With respect to this solvent dilution, the larger the dilution amount, the more solvent is volatilized after coating, and the decrease in the film thickness becomes large.

The lowering of the viscosity due to the modification of the alkylene oxide leads to a reduction in the amount of the diluting solvent or to the elimination of the solvent, which is a good finish material.

In addition, the curable resin composition containing the alkylene oxide-modified dipentaerythritol (meth) acrylate of the present invention is superior in the cured resin composition of the present invention, as compared with unmodified dipentaerythritol hexaacrylate and the like, It is considered that the improvement of the reactivity of the group, that is, the curability is improved, and the improvement of the flexibility (flexibility) by the copper structure is also confirmed, and it is considered to be effective for suppressing the defects of the transfer foil during edging molding.

It was also found that the resin composition for decorative molding of the present invention had a luster of the cured coating film stronger than that of the alkylene oxide-containing structure used in Comparative Examples 1 to 7. Compared with the blend system of dipentaerythritol acrylate of the comparative example, the incorporation of the alkylene oxide chain makes it possible to obtain a good compatibility with the gloss reducing agent based on inorganic fine particles such as silica, , It is a suitable material for making a curable resin composition capable of adjusting an arbitrary luster from a high gloss to a low gloss in that it is stabilized at an arbitrary ratio.

Regarding the change of the gloss value, it is an advantage that the glossiness of the base material is not inhibited when overcoating the substrate or coating layer containing a light-bright material such as glass or aluminum.

Industrial availability

The resin composition for decorative molding of the present invention can be suitably used as a coating film, a coating agent and a film for decorative and protection purposes. For example, it is possible to use a resin composition for decoration for electricity, such as a cellular phone, a wrist watch, a compact disk, an audio device, Electronic equipment, electronic parts such as touch panel, anti-reflection plate of cathode ray tube, electric appliance parts such as refrigerator, vacuum cleaner, microwave oven, interior trim of automobile meter panel, dashboard, Spoilers, door knobs, handles, headlamps, gasoline tanks for motorcycles, automotive parts such as aluminum foil and door mirrors with plating, deposition and sputtering; carport roofs, mining roofs; polyvinyl chloride, acrylic resin, polyethylene terephthalate Plastic molded articles such as phthalates, polycarbonates, and ABS resins, films, and sheets; stairs, floors, desks, chairs, chests, Old woodworking products such as; such as cloth, the surface of the sheet substrate such as paper, especially in areas that require abrasion resistance. It is also useful as a coating agent for electric and electronic parts.

Claims (3)

A resin composition for edging molding, characterized by containing a compound represented by the following general formula (I).
[Chemical Formula 1]

In formula (I), - (AO) _(k) -R, - (AO) _(l) -H, -H and -R are each independently bonded and - ( _{AO) (k)} is the number of -R _{m, - (AO) (l} ) is the number of n number of -H, -H is the number of o, -R denotes a p, wherein R is formula (II) , AO represents -CH ₂ CH ₂ O-, -CH ₂ CH (CH ₃ ) O-, -CH (CH ₃ ) CH ₂ O-, -CH ₂ CH ₂ CH ₂ CH ₂ O-, Or an alkylene oxide unit represented by -CH ₂ CH (C ₂ H ₅ ) O-, -CH (C ₂ H ₅ ) CH ₂ O-, and k and l are each an integer from 0 to And the average value of m, n, o, and p is 6, and the average value of m, n, o, and p is 6, n is more than 2 and not more than 20, and in the general formula (II), R ² represents a hydrogen atom or a methyl group.
(2)

The method according to claim 1,
Wherein the total of k x m and l x n in the compound represented by the general formula (I) is 3 or more and 12 or less. A layered product comprising a layer containing a cured product of the resin composition for edging molding according to claim 1 or 2 and a mirror polished layer.