JP5296309B2 - Active energy ray-curable resin composition for plastic film and plastic label - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coating agent having excellent printability by gravure printing, flexography or the like because of low viscosity and thixotropic properties, and excellent productivity because of rapid curing rate, and providing a resin-cured product layer having excellent adhesiveness to a plastic film base material, and excellent toughness after curing, and to provide a plastic label obtained by using the resin composition, and having excellent scratch resistance and rubbing resistance of the surface. <P>SOLUTION: The active energy ray-curable resin composition for the plastic film contains an oxetane compound, an epoxy compound and an organic acid having a structure in which one hydrogen atom of a benzene ring is substituted with a carboxy group, wherein the content of the organic acid is 0.1-10 wt.% based on the whole weight of the resin composition. <P>COPYRIGHT: (C)2008,JPO&amp;INPIT

Description

  The present invention relates to an active energy ray-curable resin composition used for a plastic film and a plastic label formed by applying the resin composition to a plastic film.

  Currently, plastic bottles such as PET bottles and metal bottles such as bottle cans are widely used as containers for beverages such as tea and soft drinks. In many cases, these containers are coated with a resin composition such as an ink or a coating agent for the purpose of displaying the contents and imparting various functions such as decorativeness, scratch resistance, and slipperiness. A label made of a plastic film (a so-called shrink label or stretch label) is attached.

  These resin compositions are required to have processability suitable for each label processing step, and the cured resin layer (hereinafter sometimes referred to as a resin cured product layer) is rubbed in the distribution process of the product for decoration. Toughness that does not deteriorate the performance and functionality is required. In recent years, in particular, in the beverage field, complicated and highly three-dimensionally molded containers are frequently used, and the required performance related to workability such as conformability to the container shape of a film to be mounted, particularly a shrink film, is Increasingly. In order to achieve both of these high workability and toughness, high adhesion of the cured resin layer to the film substrate is essential.

  By the way, when these resin compositions are applied to a substrate as a printing ink or the like, gravure printing is generally used. However, gravure ink usually contains a large amount of organic solvent. It is necessary to evaporate. In recent years, from the viewpoint of reducing the environmental burden, recovery and decomposition treatment of such a solvent has been made obligatory, and the capital investment and equipment maintenance cost for this have become a new burden on the gravure printing industry. On the other hand, in the case of water-based inks that do not use organic solvents or use a small amount of organic solvents, drying takes longer than solvent-based gravure inks, so printing speed is slow and productivity is unavoidable. It was.

  In light of these circumstances, development of coating agents based on epoxy resins that are substantially solvent-free is underway. Among them, epoxy compounds and oxetane are used as coating agents that impart flexibility to relatively brittle epoxy resins. A resin composition in which a compound is mixed (see, for example, Patent Documents 1 and 2) is known. However, in these resin compositions, (1) the curing speed is not sufficient for use in high-speed gravure printing or flexographic printing, (2) a solvent is required because the viscosity is not sufficiently low, and (3) low thixotropic properties From the viewpoint, there were unsolved problems such as insufficient gravure printability.

JP-A-11-140279 JP 2006-89722 A

  An object of the present invention is a resin composition that does not substantially use a solvent, and has low viscosity and thixotropy, so that it has good printability (coating property) when used for gravure printing, and is also curable. Active energy ray curable resin for plastic film that forms a cured resin layer that is excellent in productivity because it is good and, after curing, has excellent adhesion to plastic film, toughness and followability to shrink processing, etc. It is to provide a composition. It is another object of the present invention to provide a plastic label excellent in surface scratch resistance, resistance to fringing, and the like, which is obtained by coating the resin composition on a plastic film.

  As a result of intensive studies to achieve the above object, the present inventors have dramatically improved coating properties, adhesion, and curing speed by blending at least three components of an oxetane compound, an epoxy compound, and a specific organic acid. It has been found that a resin composition having improved productivity and excellent properties and properties of the cured resin layer (processability, scratch resistance, etc.) and a plastic label having the properties can be obtained. Was completed.

That is, the present invention is a resin composition comprising an oxetane compound, an epoxy compound, and an organic acid having a structure in which one hydrogen atom of a benzene ring is substituted with a carboxyl group, the oxetane compound in the resin composition And the weight ratio of the epoxy compound is 2: 8 to 8: 2, the total content of the oxetane compound and the epoxy compound is 30 to 99% by weight based on the total amount of the resin composition, and the solvent content in the resin composition For plastic film, characterized in that the amount is 0 to 5% by weight, the organic acid is contained in an amount of 0.1 to 5% by weight , and a photopolymerization initiator is further contained relative to the total weight of the resin composition. An active energy ray-curable resin composition is provided.

Furthermore, the present invention provides the active energy ray-curable resin composition for a plastic film, wherein the content of the photopolymerization initiator is 0.5 to 7% by weight based on the total weight of the resin composition. To do.

Furthermore, the present invention is pigment, relative to the total weight of the resin composition, to provide the plastic film for the active energy ray-curable resin composition containing 0.1 to 50 wt%.

  Furthermore, this invention provides the said active energy ray-curable resin composition for plastic films containing 0.1-30 weight part of silicone compounds with respect to 100 weight part of total amounts of an oxetane compound and an epoxy compound. .

  Furthermore, this invention provides the plastic label which has the resin cured material layer formed by apply | coating and hardening | curing the said active energy ray curable resin composition for plastic films to the at least single side | surface of a plastic film.

  The active energy ray-curable resin composition for a plastic film of the present invention has a low viscosity, and the thixotropy is lowered in a pigment-added system, so that the coating property to a plastic film by gravure printing or flexographic printing is good. In addition, since the curing speed is high, the production efficiency of the plastic label is improved. Moreover, since it is excellent in adhesiveness with a plastic film, the resin layer after hardening has good followability with respect to deformation of the base film during shrink processing, and is also excellent in scratch resistance and rub resistance. For this reason, the resin composition of the present invention is particularly useful as a printing ink for plastic labels. The plastic label coated with the resin composition is particularly useful as a label for use in plastic containers such as glass bottles and PET bottles, metal containers such as bottle cans, and the like.

  Hereinafter, the active energy ray resin composition for plastic film of the present invention (hereinafter simply referred to as a resin composition) will be described in more detail.

  The resin composition of the present invention is an active energy ray-curable composition that can be cured by active energy rays such as visible light, ultraviolet rays, and electron beams. Unlike the case of thermosetting, it is also preferably used for a base material that easily deforms due to heat, such as a shrink film. Among the active energy rays, ultraviolet curable and near ultraviolet curable are particularly preferable. A preferable absorption wavelength is 200 to 460 nm.

  The resin composition of the present invention includes an oxetane compound (hereinafter referred to as component A), an epoxy compound (hereinafter referred to as component B), and an organic acid having a structure in which one hydrogen atom of a benzene ring is substituted with a carboxyl group (Hereinafter referred to as component C) as an essential constituent. When the three components are not included, the effect of the present invention cannot be obtained. Further, the resin composition of the present invention preferably contains a silicone compound (hereinafter referred to as component D) from the viewpoint of curability. Furthermore, when using as printing ink, it is preferable to contain a pigment. In addition, the said component A and component B shall not contain the silicone which has an oxetanyl group and an epoxy group.

  In addition to the above components, the resin composition of the present invention preferably contains a polymerization initiator (hereinafter referred to as a photopolymerization initiator) in order to develop active energy ray curability. Also, for the purpose of imparting other functions, other resin components, sensitizers, dispersants, antioxidants, fragrances, deodorants, stabilizers, lubricants, color separation inhibitors, etc. are impaired. You may add to such an extent that it does not exist.

  Component A of the present invention is a compound having at least one oxetanyl group in the molecule and may be either a monomer or an oligomer. For example, oxetane compounds described in JP-A-8-85775 and JP-A-8-134405 can be used, and among them, compounds having one or two oxetanyl groups in one molecule are preferable. As a compound having one oxetanyl group in one molecule, 3-ethyl-3-[(phenoxy) methyl] oxetane, 3-ethyl-3- (hexyloxymethyl) oxetane, 3-ethyl-3- (2- Ethylhexyloxymethyl) oxetane, 3-ethyl-3- (hydroxymethyl) oxetane, 3-ethyl-3- (chloromethyl) oxetane, and the like. Examples of the compound having two oxetanyl groups in one molecule include 1,4-bis [[(3-ethyloxetane-3-yl) methoxy] methyl] benzene, bis [(3-ethyloxetane-3-yl) methyl. ] Ether etc. are mentioned. Among these, 3-ethyl-3- (hydroxymethyl) oxetane and bis [(3-ethyloxetane-3-yl) methyl are particularly preferable from the viewpoint of coating processability and the curability of the coating layer. ] Ether.

  Component A of the present invention can be prepared according to known methods with oxetane alcohols and halides (eg, xylene dichloride) prepared from trimethylolpropane and dimethyl carbonate. In addition, as the component A, an existing oxetane compound may be used. For example, “Aron Oxetane OXT-101, 121, 211, 221, 212” manufactured by Toagosei Co., Ltd. is commercially available.

  As component B of the present invention, a known epoxy compound having at least one epoxy group in the molecule can be used. For example, an aliphatic epoxy compound, an alicyclic epoxy compound, or an aromatic epoxy compound can be used. Among these, from the viewpoint of high reaction rate, a compound having a glycidyl group or a compound having an epoxycyclohexane ring is preferable, and an epoxy compound having two or more epoxy groups is preferable. For example, examples of the aliphatic epoxy compound include propylene glycol glycidyl ether. Examples of the alicyclic epoxy compound include 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate and bis- (3,4-epoxycyclohexyl) adipate. Examples of the aromatic epoxy compound include bisphenol A glycidyl ether, glycidyl ether condensate of bisphenol A, and epichlorohydrin modified products of novolac resin and cresol resin.

  Component B of the present invention can be synthesized by a general method such as synthesis from epichlorohydrin and bisphenol A. For example, “Celoxide 2021”, “Celoxide 2080” manufactured by Daicel Chemical Industries, Ltd., “Epolide GT400” and “UVR6110” manufactured by Dow Chemical Co., Ltd. are commercially available.

  The blending ratio (weight ratio) of component A and component B in the resin composition of the present invention is preferably 2: 8 to 8: 2 (component A / component B is 0.25 to 4), and gravure and flexographic printing. Is preferably 4: 6 to 8: 2 (component A / component B is 2/3 to 4), more preferably 5: 5 to 8: 2 (component A / component B is 1 to 4). It is. If the amount of component A is larger than the above range, the starting speed of the curing reaction of the resin composition is slowed down, so that it takes time to cure, and productivity may be reduced, or it may be uncured in a normal curing process. is there. In addition, when the amount of component B is larger than the above range, the viscosity of the resin composition becomes so large that it becomes difficult to apply uniformly by a coating method such as gravure printing or flexographic printing, or there is a reaction to stop the curing reaction. This is likely to occur, resulting in a low molecular weight cured product, and the cured resin cured layer may be fragile.

  The total amount of component A and component B of the present invention is preferably from 30 to 99% by weight based on the total amount of the resin composition from the viewpoints of coatability and curability. Especially, when the resin composition of this invention is a transparent coating agent, 60 to 99 weight% is preferable, More preferably, it is 70 to 90 weight%. Moreover, when the resin composition of this invention is printing ink containing a pigment, 30 to 90 weight% is preferable, More preferably, it is 40 to 80 weight%.

  Component C of the present invention is an organic acid having a structure in which one hydrogen atom of the benzene ring is substituted with a carboxyl group. Component C only needs to be a compound containing the above structure in the molecule, and may be benzoic acid having no substituent other than the carboxyl group, or other hydrogen atoms other than those substituted with the carboxyl group. Or a compound having a naphthalene ring. Among these, from the viewpoint of reducing thixotropy, a compound in which the ortho position or the meta position is substituted with another substituent with respect to the carboxyl group is preferable. Such component C is typically a compound represented by the following formula.

  In the formula, X represents a substituent. Although it does not specifically limit as a substituent used for the component C of this invention, A carboxyl group, a hydroxyl group, an acetyl group, a nitro group, a substituted or unsubstituted alkyl carboxyl group, an alkoxyl group etc. are illustrated. Among these, a carboxyl group, a hydroxyl group, and a nitro group are particularly preferable.

  Specific examples of the component C include benzoic acid, m-hydroxybenzoic acid, salicylic acid, phthalic acid, isophthalic acid, and m-nitrobenzoic acid.

  The carboxyl group in Component C of the present invention is not preferred when it is protected with a vinyl ether group or a methyl group because the effects of the present invention cannot be obtained. For example, methyl salicylate cannot exhibit the effects of thixotropy and viscosity reduction.

  Moreover, the component C of this invention needs to be not a strongly acidic compound. When component C is strongly acidic, heat is generated when mixed to obtain a resin composition, or polymerization (gelation) occurs and stability is lowered. In addition, the thixotropic reduction effect cannot be obtained.

  Content of the component C of this invention is 0.1 to 10 weight% with respect to the total weight of a resin composition, Preferably it is 0.1 to 5 weight%, More preferably, it is 0.1 to 3 weight% Particularly preferred is 0.2 to 2% by weight. When the content of component C is less than 0.1% by weight, the effect of addition of component C is small, the curing speed, the adhesion of the resin cured layer, the toughness is reduced, and the thixotropy is increased. Decreases. On the other hand, when the amount exceeds 10% by weight, the amount of components A and B is insufficient and the curability is lowered, or when the component C and other components are mixed, polymerization due to heat generation is caused, and the resin composition is easy to handle. descend.

  The silicone compound (silicone oil) which is Component D of the present invention is a polysiloxane having a main chain composed of a siloxane bond, and a straight silicone compound having no substituent other than a methyl group and a phenyl group (dimethylsilicone, methylphenylsilicone, Methyl hydrogen silicone, etc.), or a modified silicone compound having a substituent other than a methyl group or a phenyl group at the side chain or terminal.

  Among the above, Component D of the present invention is preferably a modified silicone compound from the viewpoint of curability. The silicone used as the base of the modified silicone compound may be a polysiloxane having a main chain composed of a siloxane bond. For example, all side chains, dimethyl silicone having a terminal methyl group, and a phenyl group in a part of the side chain Examples thereof include methylphenyl silicone and methyl hydrogen silicone in which a part of the side chain is hydrogen. Among these, dimethyl silicone is preferable. The bonding position of the substituent in the modified silicone compound is not particularly limited, and has at both ends of the main chain (both ends type: the following structural formula (1)) or one end (one end type: the following structural formula (2)). It may be included in the side chain (side chain type: Structural formula (3) below), and is represented by the following structural formula, for example. Furthermore, you may have a substituent in a side chain and the terminal (both terminal, one terminal).

In the formula, X ¹ and X ² are substituents (other than methyl group and phenyl group). R ¹ , R ² , and R ³ in the formula are hydrogen atoms or hydrocarbon groups, and may contain an oxygen atom, a nitrogen atom, or a sulfur atom. A hydrogen atom, a methyl group, and a phenyl group are preferable, and a methyl group is particularly preferable. Further, m and n in the formula are integers of 1 or more.

  Examples of the substituent in the modified silicone include an epoxy group, a fluorine atom, an amino group, a carboxyl group, an aliphatic hydroxyl group (alcoholic hydroxyl group), an aromatic hydroxyl group (phenolic hydroxyl group), and a (meth) acryloyl group. Examples include a substituent and a substituent containing a polyether chain. Examples of the modified silicone having these substituents include epoxy-modified silicone, fluorine-modified silicone, amino-modified silicone, (meth) acryl-modified silicone, polyether-modified silicone, carboxyl-modified silicone, carbinol-modified silicone, phenol-modified silicone, Examples include diol-modified silicone. Among these, polyether-modified silicone, phenol-modified silicone, and carboxyl-modified silicone are particularly preferable.

  Component D may contain an organic group such as an alkyl group and / or an aralkyl group in addition to the substituents listed above.

なお、式中のＲ⁴、Ｒ⁵は水素原子または炭化水素基であり、酸素原子、窒素原子、硫黄原子を含んでいてもよい。上記エポキシ変性シリコーンにおけるエポキシ基の官能基当量は、硬化性の観点から、３００〜５０００が好ましく、より好ましくは、４００〜４０００である。 When component D of the present invention is an epoxy-modified silicone, the epoxy group as a substituent may be one in which the oxygen atom does not contain a cyclic aliphatic skeleton (left figure: referred to as an aliphatic epoxy group). Alternatively, it may be one in which an oxygen atom of an epoxy group is formed including a cyclic aliphatic skeleton (right figure: referred to as an alicyclic epoxy group).

R ⁴ and R ⁵ in the formula are a hydrogen atom or a hydrocarbon group, and may contain an oxygen atom, a nitrogen atom, or a sulfur atom. From the viewpoint of curability, the functional group equivalent of the epoxy group in the epoxy-modified silicone is preferably 300 to 5000, and more preferably 400 to 4000.

When Component D of the present invention is a fluorine-modified silicone, the substituent is not particularly limited. For example, a fluorinated alkyl group such as [—R ⁶ CF ₃ ] is preferable. Specifically, —CH ₂ CH ₂ CF ₃ , —C ₃ H ₆ CF _{3 and the} like are exemplified. R ⁶ is a hydrocarbon group and may contain an oxygen atom, a nitrogen atom, or a sulfur atom. The fluorine-modified silicone has a viscosity (23 ± 2 ° C.) of preferably 100,000 mPa · s or less, more preferably 50000 mPa · s or less. When the viscosity exceeds 100,000 mPa · s, the viscosity of the resin composition becomes high, and the coatability may be lowered.

When Component D of the present invention is an amino-modified silicone, the substituent is a substituent containing an amino group, and is not particularly limited, but [-R ⁷ NH ₂ ], [—R ⁸ NH—R ⁹ NH ₂ ], [- it is preferable, R ¹⁰ NHC ₆ H _11] aminoalkyl group represented by like, specifically, -C ₃ H ₆ NH _2, such as -C ₃ H ₆ NHC ₆ H ₁₁ is illustrated . R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are hydrocarbon groups and may contain an oxygen atom, a nitrogen atom or a sulfur atom. The amino-modified silicone has a viscosity (23 ± 2 ° C.) of preferably 100000 mPa · s or less, more preferably 50000 mPa · s or less. When the viscosity exceeds 100,000 mPa · s, the viscosity of the resin composition becomes high, and the coatability may be lowered. Moreover, the functional group equivalent (unit: g / mol) of amino-modified silicone is 500 or more (for example, 500-60000), More preferably, it is 700-60000. When the functional group equivalent is less than 500, curing inhibition may occur and the curing reaction may not proceed sufficiently. When the functional group equivalent exceeds 60000, the addition effect (adhesion and curing speed improvement) is obtained. There may not be.

When Component D of the present invention is a (meth) acryl-modified silicone, the substituent is a substituent containing a (meth) acryloyl group, and is not particularly limited, but [-R ¹¹ OCOCH═CH ₂ ], [ —R ¹² OCOC (CH ₃ ) ═CH ₂ ] and the like are preferable, and specifically, —C ₃ H ₆ OCOC (CH ₃ ) ═CH ₂ , —C ₃ H ₆ OCOCH═CH _{2 and the} like are exemplified. R ¹¹ and R ¹² are hydrocarbon groups and may contain an oxygen atom, a nitrogen atom, or a sulfur atom. The functional group equivalent (unit: g / mol) of the (meth) acryl-modified silicone is 20000 or less (for example, 50 to 20000), more preferably 100 to 15000. When the functional group equivalent exceeds 20000, the effect of addition may not be obtained.

When Component D of the present invention is a polyether-modified silicone, the substituent is a substituent containing two or more repeating units containing an ether bond, and is not particularly limited, but [-R ¹³ (C ₂ H ₄ O) _a R ¹⁴ ], [—R ¹⁵ (C ₃ H ₆ O) _b R ¹⁶ ], [—R ¹⁷ (C ₂ H ₄ O) _c (C ₃ H ₆ O) _d R ¹⁸ ] Organic groups mainly composed of ethylene oxide and propylene oxide units are preferred. ^{Incidentally, R 13, R 14, R} 15, R 16, R 17, R 18 is a hydrocarbon group, a, b is 6 to 30, c, d is from 1 to 20 approximately an integer. The polyether-modified silicone has a viscosity (23 ± 2 ° C.) of preferably 100000 mPa · s or less, more preferably 50000 mPa · s or less. When the viscosity exceeds 100,000 mPa · s, the viscosity of the resin composition becomes high, and the coatability may be lowered. Moreover, although the HLB value (Hydrophile-Lipophile Balance) of polyether modified silicone is not specifically limited, 0-12 are preferable from a compatible viewpoint, More preferably, it is 0-10. When the HLB value exceeds 12 and the hydrophilicity is high, the compatibility may decrease.

When Component D of the present invention is carbinol-modified silicone, the substituent is represented by [—R ¹⁹ OH], specifically, for example, —C ₃ H ₆ OC ₂ H ₄ OH, —C ₃ H _6. Examples include OH. In the case of a diol-modified silicone, the introduced substituent is

で表されるアルコール性ジオールなどが好ましく、具体的には、

Are preferred, and specifically,

Etc. are exemplified. In the case of phenol-modified silicone, the substituent is represented by, for example, [—R ²⁵ —C ₆ H ₄ —OH], specifically, —C ₂ H ₄ —C ₆ H ₄ —OH, _{-C 3 H 6 -C 6 H 4} -OH and the like. Note that R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , and R ²⁵ are aliphatic hydrocarbon groups and may contain an oxygen atom, a nitrogen atom, or a sulfur atom. R ²⁴ is a hydrogen atom, a methyl group, an ethyl group or a propyl group. The hydroxyl value (unit: mg KOH / g) of these aliphatic or aromatic hydroxyl-modified silicones is preferably 5 to 150, more preferably 10 to 140. When the functional group equivalent is less than 5, the effect of addition (particularly adhesion) may not be sufficient, and when it exceeds 150, curing inhibition may occur and the curing reaction may not proceed sufficiently. In addition, although the said hydroxyl value can be measured based on JISK5601-2-1, it calculates from functional group equivalent [functional group equivalent (g / mol) = 56000 / hydroxyl value (mgKOH / g)]. (Especially in the case of phenol-modified silicone).

When component D of the present invention is carboxyl-modified silicone, the substituent is not particularly limited, but is preferably represented by [—R ²⁶ COOH], specifically, for example, —C ₂ H ₄ COOH. , -C ₃ H ₆ COOH and the like. The above R ²⁶ is an aliphatic hydrocarbon group and may contain an oxygen atom, a nitrogen atom, or a sulfur atom. The functional group equivalent (unit: g / mol) of the carboxyl-modified silicone is 6000 or less (for example, 500 to 6000), more preferably 100 to 5000. When the functional group equivalent exceeds 6000, the effect of component D addition may not be obtained. In addition, the said functional group equivalent is an equivalent of a carboxyl group (COOH part).

  As the component D of the present invention, a commercially available product can be used. For example, as the epoxy-modified silicone, “KF-101, KF-102, KF-105, KF-1001, XF manufactured by Shin-Etsu Silicone Co., Ltd.” -22-163A, X-22-163B, X-22-163C, X-22-169AS, X-22-169B, X-22-173DX, X-22-2000 "and the like. As the fluorine-modified silicone, “FL-5, FL-100-100cs, FL-100-450cs, FL-100-1000cs, FL-100-10000cs, X-22-821, X-manufactured by Shin-Etsu Chemical Co., Ltd. 22-822 "," FS1265 "manufactured by Toray Dow Corning Co., Ltd., and the like. Examples of the amino-modified silicone include “KF-8005, KF-859, KF-8008, X-22-3820W, KF-857, KF-8001, KF-861” manufactured by Shin-Etsu Chemical Co., Ltd. Examples of the modified silicone include “X-22-2426, X-22-164A, X-22-164C, X-22-2404, X-24-8201” manufactured by Shin-Etsu Chemical Co., Ltd. (above, methacrylic modification), “X-22-2445, X-22-1602” manufactured by Shin-Etsu Chemical Co., Ltd., “TEGO Rad 2400, 2500, 2600, 2700” (manufactured by acrylic modification) manufactured by Degussa Co., Ltd., and the like. As the polyether-modified silicone, “KF-351A, KF-352A, KF-353, KF-354L, KF-355A, KF-615A, KF-945, KF-640, KF-642 manufactured by Shin-Etsu Chemical Co., Ltd. , KF-643, KF-6020, KF-6004, KF-6011, KF-6012, KF-6015, KF-6017, X-22-6191, X-22-4515, X-22-2516 “FZ-2110, FZ-2122, FZ-7006, FZ-2166, FZ-2164, FZ-2154, FZ-2191, FZ-7001, FZ-2120, FZ-2130, FZ-720 manufactured by Dow Corning Co., Ltd. , FZ-7002, FZ-2123, FZ-2104, FZ-77, FZ-2105, FZ-2118, FZ 7604, FZ-2161, FZ-2162, FZ-2203, FZ-2207, FZ-2208, SH-8400, SH-8700, SH-3746, SH-3771, SF-8491 ", and the like. Examples of the carbinol-modified silicone include “X-22-160AS, KF6001, KF6002, KF6003, X-22-4015, X-22-4039, X-22-170DX” manufactured by Shin-Etsu Chemical Co., Ltd., and the like. Examples of the diol-modified silicone include “X-22-176DX, X-22-176D, X-22-176F” manufactured by Shin-Etsu Chemical Co., Ltd. Examples of the phenol-modified silicone include “X-22-1821, X-22-165B” manufactured by Shin-Etsu Chemical Co., Ltd., “BY16-752, BY16-150S” manufactured by Toray Dow Corning Co., Ltd., and the like. As the carboxyl-modified silicone, “X-22-162C, X-22-3701E, X-22-3710” manufactured by Shin-Etsu Chemical Co., Ltd., “BY16-750, BY16-880” manufactured by Toray Dow Corning Co., Ltd. Etc.

  The addition amount of component D of the present invention is preferably 0.1 to 30 parts by weight, more preferably 0.2 to 15 parts by weight, based on the total amount of component A and component B (100 parts by weight). is there. When the amount of component D added is less than 0.1 parts by weight, the effect of component D addition is small, and the curing speed, the adhesion of the resin cured layer, and the toughness may decrease. On the other hand, when the amount exceeds 30 parts by weight, the content of component A or component B decreases, the curability decreases, the resin composition becomes highly viscous and the coating property decreases, Fading may occur.

  When the resin composition of the present invention is used as a printing ink, a pigment can be added. As pigments, organic and inorganic coloring pigments can be used, such as white pigments such as titanium oxide (titanium dioxide), indigo (blue) pigments such as copper phthalocyanine blue, red pigments such as condensed azo pigments, azo lake pigments, etc. Yellow pigments, carbon black, aluminum flakes, mica (mica), etc. can be selected and used according to the application. In addition, extender pigments such as alumina, calcium carbonate, barium sulfate, silica, and acrylic beads can also be used as pigments for the purpose of adjusting gloss. Among the above pigments, in particular, in the case of a pigment that interacts with the organic acid that is Component C, the effect of reducing thixotropy by adding Component C is large, which is preferable. As such a pigment, a pigment having a polar group is preferable, and titanium oxide and copper phthalocyanine blue are particularly preferable.

  The content of the pigment can be arbitrarily designed depending on the type of pigment, the concentration of the target color, etc., but is preferably about 0.1 to 70% by weight, more preferably 1 to 70% by weight based on the total weight of the resin composition. 50% by weight.

  Among these, when the resin composition of the present invention is used as a white printing ink, titanium oxide is preferably used as the pigment. As the titanium oxide, any of rutile type (tetragonal high temperature type), anatase type (tetragonal low temperature type), and brookite type (orthorhombic type) may be used. For example, titanium oxide particles manufactured by Ishihara Sangyo Co., Ltd. “Taipeke”, Teika Co., Ltd. titanium oxide “JR Series”, etc. are available. Moreover, the average particle diameter of the titanium oxide particles (in the case where an aggregate is formed, the particle diameter of the aggregate, so-called secondary particle diameter) is, for example, 0.01 to 1 μm, preferably 0.1 to 0.00. It is 5 μm, more preferably 0.2 to 0.5 μm. When the average particle size is less than 0.01 μm, the white density is lowered and the concealability is insufficient. If it exceeds 1 μm, so-called “plate fogging” (printing failure due to defective ink scraping of portions other than the image line portion of the plate) occurs during gravure printing. Further, the content of titanium oxide in the white printing ink of the present invention is preferably 20 to 60% by weight, more preferably 30 to 20% by weight based on the total weight of the resin composition from the viewpoint of concealability and suppression of coarse protrusion formation. 55% by weight.

  When the resin composition of the present invention is used as a blue printing ink, copper phthalocyanine is preferably used as the pigment. As such a pigment, Pigment Blue (for example, Pigment Blue 15: 4) is preferably exemplified. Examples of commercially available products include “IRGALITE BLUE GLVO, NGL, GLNF” manufactured by Ciba Specialty Chemicals Co., Ltd. and “Cyanine Blue 4940, 4933GN-EP” manufactured by Dainichi Seika Co., Ltd. The content of the copper phthalocyanine is preferably 0.5 to 30% by weight, more preferably 1 to 20% by weight, based on the total weight of the resin composition.

  In the present invention, component A has a characteristic of forming a tough resin cured product layer having a high molecular weight because it is difficult to stop the curing reaction. On the other hand, since the initiation reaction is difficult to proceed, the curing process takes time and productivity is increased. There is a drawback that the resin composition is not cured or the toughness of the cured resin layer is insufficient when the curing time is short or short. On the other hand, although the component B has a fast initiation reaction and a high production rate, the reaction is likely to stop. Therefore, the cured product has a low molecular weight, and the toughness of the cured resin layer is insufficient. By mixing both of these, a certain degree of curing rate (productivity) and toughness can be obtained, but when the process speed is increased, sufficient toughness of the cured resin layer can be obtained. It was impossible. In the present invention, by further adding a predetermined amount of component C, the curing rate is dramatically improved as compared with the case of only component A and component B. For this reason, since hardening of a resin hardened material layer advances by irradiation of active energy rays for a short time, the process speed can be increased and productivity is improved. Furthermore, since the termination reaction is suppressed, high molecular weight can be achieved and high toughness can be achieved. That is, it is possible to achieve both productivity and toughness at a high level. Note that in the case of a two-component system in which the component C is added to the component A or the component B alone, the above effect cannot be obtained, and a three-component mixed system is required. Addition of component D is preferable because a higher effect can be obtained.

  Moreover, the adhesiveness to the plastic film base material of a resin composition improves dramatically by adding the component C. Although the details of the mechanism of the manifestation of these effects are unclear, there is a possibility that protons supplied by the carboxyl group of component C contribute to the reaction.

  Furthermore, in the pigment addition system, it is possible to effectively reduce the thixotropy of the resin composition (ie, printing ink) by using the component C of the present invention. Moreover, when printing ink consists only of component A, component B, and a pigment, although a viscosity is high, the viscosity reduction effect is acquired by adding the component C. For this reason, it is preferable because gravure printing characteristics and flexographic printing characteristics are improved. The details of the above are unknown, but the surface condition of the pigment is improved by the interaction between the carboxyl group of component C and the polar group of the pigment surface and the steric hindrance effect due to the benzene ring of component C. This is presumed to suppress an increase in viscosity due to aggregation in the installed state. The above effect is the highest when component C has another substituent at the ortho or meta position of the carboxyl group. Since Component C has a benzene ring, the flexibility of the molecule is low, and the substituents at the ortho-position or meta-position are fixed in the same direction, so they coordinate to the same pigment particle. This is presumably because the pigment particles become easy to prevent aggregation of the pigment particles. When it has a substituent at the para position of the carboxyl group, it may act to bind a plurality of pigment particles, and the effect of reducing thixotropy may be reduced.

  In the present invention, by mixing components A, B, and C, the curing rate is remarkably increased, and in the pigment addition system, the effects of reducing viscosity and reducing thixotropy are also added, so that the printing processability and productivity are improved. In addition, the adhesiveness is improved by improving the curability, and the toughness is also improved. Therefore, the followability of the cured resin layer to the deformation of the shrink film during the shrink processing is improved, and the cured resin layer after the processing. Scratch resistance and rub resistance are improved. Furthermore, effects such as slipperiness, water repellency, oil repellency and low odor are also obtained.

  It is preferable to add a photopolymerization initiator to the resin composition of the present invention in order to exhibit active energy ray curability. Although it does not specifically limit as a photoinitiator of this invention, A photocationic polymerization initiator is preferable. Although it does not specifically limit as a photocationic polymerization initiator, For example, a diazonium salt, a diaryl iodonium salt, a triaryl sulfonium salt, a silanol / aluminum complex, a sulfonic acid ester, an imide sulfonate etc. are mentioned. Of these, diaryl iodonium salts and triarylsulfonium salts are particularly preferable from the viewpoint of reactivity. Although content of a photoinitiator is not specifically limited, 0.5-7 weight% is preferable with respect to the total weight of a resin composition, More preferably, it is 1-5 weight%.

  Moreover, it is preferable to add a sensitizer to the resin composition of this invention as needed from a viewpoint of improving production efficiency. This is particularly effective when the titanium oxide pigment is used. In this case, the sensitizer can be selected from existing sensitizers in consideration of the type of active energy ray used. For example, (1) amine sensitizers such as amines containing nitrogen in the ring, such as aliphatic, aromatic amines, piperidine, (2) urea sensitizers such as allyl, o-tolylthiourea, (3) sodium Sulfur compound sensitizers such as diethyldithiophosphate, (4) anthracene sensitizers, (5) nitrile sensitizers such as N, N-disubstituted-p-aminobenzonitrile compounds, (6) tri -Phosphorus compound sensitizers such as n-butylphosphine, (7) Nitrogen compound sensitizers such as N-nitrosohydroxylamine derivatives and oxazolidine compounds, (8) Chlorine compound sensitizers such as carbon tetrachloride, etc. Sensitizers. Also in the above, in particular, anthracene sensitizers are preferred because of their strong sensitizing action. Of these, thioxanthone and 9,10-dibutoxyanthracene are preferably used. Moreover, it is although it does not specifically limit as content of a sensitizer, 0.1 to 5 weight% is preferable with respect to the total weight of a resin composition, Most preferably, it is 0.3 to 3 weight%.

  Moreover, the resin composition of this invention may contain a lubricant as needed. Examples of the lubricant herein include various waxes such as polyolefin wax such as polyethylene wax, fatty acid amide, fatty acid ester, paraffin wax, polytetrafluoroethylene (PTFE) wax and carnauba wax.

  In the resin composition of the present invention, the content of the solvent mainly used as a dispersant without participating in the reaction is preferably 5% by weight or less, more preferably 1% by weight or less, Most preferably, it contains substantially no solvent. The solvent here refers to, for example, organic solvents such as toluene, xylene, methyl ethyl ketone, ethyl acetate, methyl alcohol, ethyl alcohol, and water. In gravure and flexographic printing inks, coating processability and coating agents are used. It is generally used for the purpose of improving the compatibility and dispersibility of each component therein, and does not include a reactive diluent incorporated into the cured resin composition. Since the resin composition of the present invention can exhibit excellent coating properties and dispersibility between components even without a solvent, the amount of the solvent can be extremely reduced, so that removal of the solvent is unnecessary, and speeding up and cost reduction are achieved. In addition, it is possible to reduce the environmental load.

  Although the viscosity (23 ± 2 ° C.) of the resin composition of the present invention is not particularly limited, for example, when applied by gravure printing, 10 to 200 mPa · s is preferable, and 20 to 150 mPa · s is more preferable. It is. When the viscosity exceeds 200 mPa · s, the gravure printability is deteriorated, and “decrease” or the like is generated, and the decorating property may be deteriorated. On the other hand, when the viscosity is less than 10 mPa · s, the storage stability may be deteriorated, for example, the pigment or the additive may easily settle. The viscosity of the resin composition can be controlled by the mixing ratio of components A, B, and C, a thickener, a thickener, and the like. In the present specification, “viscosity” is JIS Z unless otherwise specified, using an E-type viscometer (conical plate-type rotational viscometer) under the conditions of 23 ± 2 ° C. and cylinder rotation speed of 50 rotations. The value measured according to 8803 is meant.

  The resin composition of the present invention preferably has a low thixotropy, and the thixotropic index (TI value) is preferably less than 20, more preferably less than 10, and still more preferably less than 5. When the TI value is 20 or more, the gravure and flexographic printability may decrease, and the productivity may decrease.

  The resin composition of the present invention is preferably applied by gravure printing, flexographic printing, or inkjet printing from the viewpoints of cost, productivity, printing decoration, and the like. Among these, a gravure printing method is particularly preferable.

  Since the resin composition of the present invention has an excellent effect of reducing thixotropy when a pigment is added, it can be preferably used as a printing ink for imparting decorativeness. Further, it can also be used as a transparent coating agent (sliding medium) for improving the slipperiness of the label surface, a matting coating agent (matte varnish) for matting the label, and the like. Since the cured resin layer of the resin composition of the present invention has excellent scratch resistance, the cured resin layer such as surface printing and surface medium is the outermost layer of the label (the outermost layer opposite to the adherend side such as a container). It is also suitable for applications provided on the surface layer, and may be used as a lower layer in the case of laminating a plurality of ink layers.

  The resin composition of the present invention is used for plastic label applications, specifically, stretch labels, shrink labels, stretch shrink labels, in-mold labels, tack labels, roll labels (wrap-type glued labels), heat-sensitive adhesives. It can be used for labels and the like. Among these, from the viewpoints of adhesion of the resin composition of the present invention and followability during shrink processing, it is particularly preferably used as a shrink label.

  By applying the resin composition of the present invention to at least one surface of a plastic film and curing with an active energy ray, a plastic label having the cured resin layer of the present invention can be obtained. The cured resin layer of the present invention may be provided on the outermost layer (for example, the outermost layer or the innermost layer) of the label, or may be provided as a lower layer of another ink layer. When the cured resin layer of the present invention is used as the outermost layer, an effect of imparting scratch resistance to the label is obtained, and an effect of preventing peeling of the overcoated ink is obtained as the lower layer. In particular, when used for shrink label applications, it is preferable because the effect of preventing shrinkage whitening, shrinkage peeling, and shrinkage cracking (ink cracking) can be obtained, reflecting good adhesion and followability to shrinking processing.

  The type of plastic film used for the plastic label of the present invention can be appropriately selected according to the required physical properties, application, cost, etc., and is not particularly limited. For example, polyester, polyolefin, polystyrene, polyvinyl chloride Polyamide, aramid, polyimide, polyphenylene sulfide, acrylic resin and the like can be used. Among these, a polyester film, a polyolefin film, a polystyrene film, and a polyvinyl chloride film are preferable, and a polyester film and a polyolefin film are more preferable. As the polyester, polyethylene terephthalate (PET) or poly (ethylene-2,6-naphthalenedicarboxylate) (PEN) can be used, and as the polyolefin, polypropylene, polyethylene, cyclic olefin, or the like can be used. is there.

  The plastic film may be a single-layer film or a laminated film in which a plurality of film layers are laminated according to required physical properties, applications, and the like. In the case of a laminated film, film layers made of different resins may be laminated. For example, it may be a three-layer laminated film composed of a central layer and a surface layer portion (inner layer, outer layer), a film in which the central layer is composed of a polyolefin resin or a polystyrene resin, and a surface layer is composed of a polyester resin. Moreover, you may use any of an unstretched film, a uniaxially oriented film, and a biaxially oriented film according to a required physical property, a use, etc. In particular, when the plastic label is a shrink label, a uniaxial or biaxially oriented film is often used, and in particular, a film (substantially oriented) in the film width direction (direction that becomes the label circumferential direction). A film uniaxially stretched in the width direction is generally used.

  The plastic film can be produced by a conventional method such as melt film formation or solution film formation. It is also possible to use a commercially available plastic film. The surface of the plastic film may be subjected to conventional surface treatment such as corona discharge treatment or primer treatment, if necessary.

  The heat shrinkage rate (90 ° C., 10 seconds) of the plastic film is not particularly limited. For example, in the case of shrink label use, the longitudinal direction is −3 to 15% and the width direction from the viewpoint of shrink workability. Is preferably 20 to 80%.

  Although the thickness of the said plastic film changes with uses and is not specifically limited, 10-200 micrometers is preferable, for example, in the case of a shrink label use, 20-80 micrometers is preferable, More preferably, it is 30-60 micrometers.

  The resin layer thickness in the case of applying the resin composition of the present invention varies depending on the use and is not particularly limited, but is preferably 0.1 to 15 μm, and particularly preferably 0.5 to 10 μm. When the thickness of the resin layer is less than 0.1 μm, it may be difficult to provide the resin layer uniformly. When used as a printing layer, partial “fading” may occur. , Decorativeness may be impaired, or printing as designed may be difficult. In addition, when the resin layer thickness exceeds 15 μm, a large amount of the resin composition is consumed, which increases the cost, makes it difficult to apply uniformly, and makes the cured resin layer brittle. , Easy to peel off. Among them, when the resin cured product layer of the present invention is a white ink layer, the thickness is preferably 3 to 10 μm from the viewpoint of concealment, and when it is a transparent coating layer, it is 0 from the viewpoint of transparency. .2 to 3 μm is preferable. In addition, the thickness of the cured resin layer of the present invention hardly changes before and after curing.

  The cured resin layer of the present invention can be used as various layers such as a top coat layer and an anchor coat layer in addition to a printing ink layer, and in particular, a surface printing ink layer, a top coat layer and others that require scratch resistance. As an anchor coat layer for the ink layer, an excellent effect can be exhibited.

  In addition, the plastic label of the present invention may be provided with a printed layer different from the cured resin layer of the present invention. In this case, the other printing layer can be formed by a conventional printing method such as gravure printing or flexographic printing. The printing ink used for forming the printing layer is composed of, for example, a pigment, a binder resin, and a solvent. Examples of the binder resin include acrylic, urethane, polyamide, vinyl chloride-vinyl acetate copolymer, cellulose, and nitro. Common resins such as cellulose can be used. The thickness of the printing layer is not particularly limited and is, for example, about 0.1 to 10 μm.

  In addition, the plastic label of the present invention may be provided with other layers such as an anchor coat layer, a primer coat layer, a nonwoven fabric, and paper, which are different from the cured resin layer of the present invention, as necessary.

  The plastic label of the present invention is generally mounted on a container and used as a labeled container. Such containers include, for example, soft drink bottles such as PET bottles, milk containers for home delivery, food containers such as seasonings, alcohol beverage bottles, pharmaceutical containers, containers for chemical products such as detergents and sprays, cups, etc. This includes noodle containers. Also, the material of the container includes plastic such as PET, glass, metal and the like. In addition, the plastic label of this invention may be used for adherends other than a container.

  Below, an example of the process which mounts the resin composition of this invention, the manufacturing method of a plastic label, and a plastic label to a container is demonstrated. In addition, although the example of the cylindrical shrink label using the shrink film shrink | contracted in the width direction as a plastic film is shown here, a manufacturing method and a processing method are not limited to this.

  In the following description, the original film before providing the cured resin layer is referred to as a “plastic film”, and the one provided with the cured resin layer of the present invention is referred to as a “(long) plastic label”. Furthermore, in the mounting process to the container, the long plastic label that has been processed into a cylindrical shape while being long is referred to as a “long cylindrical plastic label”.

[Preparation of resin composition]
The above-mentioned component A, component B, component C and, if necessary, component D, pigment, photopolymerization initiator and the like are mixed to produce a resin composition. Furthermore, when using other additives, such as a sensitizer, it mixes simultaneously. For mixing, a mixer such as a butterfly mixer, a planetary mixer, a pony mixer, a dissolver, a tank mixer, a homomixer, and a homodisper, a mill such as a roll mill, a sand mill, a ball mill, a bead mill, and a line mill, and a kneader are used. The mixing time (retention time) during mixing is preferably 10 to 120 minutes. The obtained resin composition may be used after being filtered, if necessary.

[Production of plastic labels]
The resin composition of the present invention is applied to a plastic film (for example, gravure, flexographic printing, etc.) to form a resin layer (before curing). The coating may be provided by an in-line coat that is applied during the plastic film manufacturing process (for example, after unstretched or longitudinally uniaxially stretched), or may be provided by an off-line coat that is applied after film formation, Although not particularly limited, off-line coating is preferable from the viewpoint of productivity and workability including curing treatment.

Next, the resin layer is cured. Curing is preferably performed in a coating step and a series of steps from the viewpoint of productivity. Curing is performed by active energy ray curing using an ultraviolet (UV) lamp, an ultraviolet LED, an ultraviolet laser, or the like, and the active energy ray to be irradiated varies depending on the composition of the resin composition and is not particularly limited, but from the viewpoint of curability. UV light having a wavelength of 200 to 460 nm (near ultraviolet light) is preferable, the irradiation intensity is preferably 150 mJ / cm ^{2 to} 1000 mJ / cm ² , and the irradiation time is preferably 0.1 to 3 seconds.

  The long plastic label obtained as described above is slit into a predetermined width and wound into a roll to form a plurality of rolls.

[Processing of long plastic labels]
Next, while feeding out one of the rolls, the long plastic film is formed into a cylindrical shape so that the width direction is the circumferential direction. Specifically, a long plastic label is formed into a cylindrical shape, and a solvent or adhesive such as tetrahydrofuran (THF) or the like (hereinafter referred to as “THF”) is formed on one side edge of the label in a band shape in the longitudinal direction. Solvent etc.) is applied to the inner surface, rolled up into a cylindrical shape, and the solvent applied portion is overlapped at a position of 5-10 mm from the other side edge and adhered to the outer surface (center seal). To obtain a long cylindrical plastic label. In addition, it is preferable that the resin cured material layer is not provided in the part which apply | coats said solvent etc., and the part to adhere | attach.

  In the case where a perforation for label excision is provided, a perforation having a predetermined length and pitch is formed in the longitudinal direction. The perforation can be applied by a conventional method (for example, a method of pressing a disk-shaped blade having a cut portion and a non-cut portion repeatedly formed around it, a method using a laser, or the like). The process stage for perforating can be appropriately selected after the printing process and before and after the cylindrical processing process.

[Container with label]
Finally, after cutting the long cylindrical plastic label obtained above, it is attached to a predetermined container, and the label is contracted by heat treatment, and a container with a label is prepared by closely contacting the container. The above long cylindrical plastic label is supplied to an automatic label mounting device (shrink labeler), cut to the required length, and then externally fitted into a container filled with the contents, and a hot air tunnel or steam tunnel at a predetermined temperature is attached. Passed or heated with radiant heat such as infrared rays to cause heat shrinkage and adhere to the container to obtain a labeled container. Examples of the heat treatment include treatment with steam at 80 to 100 ° C. (passing through a heating tunnel filled with steam and steam).

[Methods for measuring physical properties and methods for evaluating effects]

(1) Gravure printing suitability According to the printing conditions in Examples and Comparative Examples, the printing state after gravure printing is visually observed, and when printing can be performed according to the plate surface, gravure printing property is good (○), printing is performed according to the plate surface. The case where it was not able to be performed was judged as the gravure printability defect (x).

(2) Curability (initial tackiness)
In Examples and Comparative Examples, curing treatment is performed at an ultraviolet irradiation process speed of 70, 100, and 120 m / min. Immediately after the treatment, the surface of the cured resin layer is touched with a finger, and whether or not the finger is inked is visually observed. Judgment was made based on the following criteria.
A: Ink is not applied at 120 m / min. O: Ink is not applied at 100 m / min, but ink is applied at 120 m / min.
Δ: Ink is not applied at 70 m / min, but ink is applied at 100 m / min.
X: Ink is applied even at 70 m / min.

(3) Adhesiveness (tape peeling test)
The test was conducted in accordance with JIS K 5600, except that the cross cut of the grid was not made. Nichiban tape (width 18 mm) was applied to the surface of the resin label side of the plastic label obtained in the examples and comparative examples, peeled in the direction of 90 degrees, and the remaining area of the resin layer in the region of 5 mm × 5 mm Observed and judged according to the following criteria.
90% or more: Good adhesion (○)
80% or more and less than 90%: Adhesiveness is slightly poor but usable level (△)
Less than 80%: poor adhesion (×)

(4) Scratch resistance A sample piece having a length of 100 mm and a width of 100 mm was collected from the plastic labels obtained in Examples and Comparative Examples. Hold both ends of the sample piece with both hands and hold it 10 times. When the remaining area of the cured resin layer on the surface of the cured resin layer is visually observed, if the remaining area is 90% or more, the resistance to cracking is good (◯), and if the remaining area is less than 90%, the resistance to scratching is poor ( X).

(5) Scratch resistance Sample pieces having a length of 100 mm and a width of 100 mm were collected from the plastic labels obtained in Examples and Comparative Examples. Place the sample on a smooth table, observe the surface after rubbing the surface of the side where the resin cured material layer is provided 10 times in the back of the nail of the hand (20 mm in the longitudinal direction). Judged by criteria.
The cured resin layer is not peeled off at all. : Good scratch resistance (○)
Partial peeling is observed in the cured resin layer. : Scratch resistance is slightly poor but usable level (△)
The cured resin layer is significantly peeled off. : Scratch resistance failure (×)

(6) Viscosity and thixotropy Using an E-type viscometer (“RE115L” manufactured by Toki Sangyo Co., Ltd.), measurement was performed at 23 ± 2 ° C. according to JIS Z 8803.
When the viscosity was 200 mPa · s or less at a rotation speed of 50 rpm, it was judged as “Good” (good), and when exceeding 200 mPa · s, it was judged as “Poor” (bad).
Also, the value obtained by dividing the viscosity at the rotation speed of 1 rpm by the viscosity at the rotation speed of 100 rpm is the thixo index (TI value), and the TI value is less than 5 (excellent properties for gravure printing etc.) 5 or more and less than 10 ○ (Good), 10 or more and less than 20 were judged as Δ (usable), and 20 or more were judged as × (defect).

(7) Film layer thickness, resin cured product layer thickness The film thickness was measured using a stylus type thickness gauge. The thickness of the cured resin layer is determined by using a three-dimensional microscope (VK8510 manufactured by Keyence Corporation) as the level difference between the portion where the resin cured layer is provided (coated surface) and the portion where the resin cured material layer is not provided (non-coated surface). And measured.

(8) Plastic film heat shrinkage (90 ° C)
A rectangular sample piece having a length of 200 mm (mark interval 150 mm) and a width of 10 mm is prepared from the plastic film in the measurement direction (longitudinal direction or width direction).
The sample piece is heat-treated in warm water at 90 ° C. for 10 seconds (under no load), the difference between the marked lines before and after the heat treatment is read, and the thermal contraction rate is calculated by the following formula.
Thermal shrinkage (%) = (L ₀ −L ₁ ) / L ₀ × 100
L ₀ : Mark interval before heat treatment L ₁ : Mark interval after heat treatment

  EXAMPLES Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

Example 1
Component A is bis [(3-ethyloxetane-3-yl) methyl] ether (manufactured by Toagosei Co., Ltd., trade name “Aron Oxetane OXT-221”), and component B is an epoxy monomer (manufactured by Daicel Chemical Industries, Ltd.). , Trade name “Celoxide 2021P”), salicylic acid (manufactured by Wako Pure Chemical Industries, Ltd.) as component C (C1), polyether-modified silicone (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “X-22-2516”) as component D )), Photopolymerization initiator (manufactured by Dow Chemical Co., Ltd., trade name “UVI-6992”), white pigment (pigment 1) as titanium dioxide (trade name “JR-809”, trade name “JR-809”), increase Dibutoxyanthracene (manufactured by Kawasaki Kasei Kogyo Co., Ltd.) as a sensitizer and silica particles (manufactured by Tosoh Silica Co., Ltd., trade name “E-1030”), anti-blocking agent Agent), Fischer-Tropsch wax (manufactured by Sazol Co., Ltd., trade name “SPRAY 105”, lubricant) according to the blending amount (parts by weight) shown in Table 1, and active energy ray-curable resin composition (white) Ink) was obtained. No solvent was used. The obtained resin composition had good properties as a printing ink.
A polyester-based shrink film (Toyobo Co., Ltd.) was prepared using a table gravure printing machine (manufactured by Nissho Gravure Co., Ltd., trade name “GRAVO PROOF MINI”) and a gravure plate with 90 lines and a plate depth of 30 μm. Gravure printing (resin layer thickness: 4 μm) was performed on one side of a product name “Space Clean S7042”: film thickness 45 μm) at a process speed of 50 m / min to evaluate gravure printability.
Subsequently, the shrink film coated with the above resin composition was converted into 240 W / W using an ultraviolet irradiation device (product name “LIGHT HAMMER 10” manufactured by Fusion UV Systems Japan Co., Ltd .: output 100%, D bulb). Irradiation was performed under conditions of cm, and the curability was evaluated. The irradiation intensity (measured by the trade name “UV Power Pack” manufactured by EIT Co., Ltd.) is 55 mJ / cm ² (UVC), 515 mJ / cm ² (UVB), 1550 mJ when the conveyor speed is 10 m / min. / Cm ² (UVA) and 955 mJ / cm ² (UVV).
The obtained plastic label (produced at a conveyor speed of 70 m / min, resin cured product layer thickness: 4 μm) was evaluated for adhesion, resistance to scratching, and scratch resistance.
As shown in Table 1, the obtained resin composition and plastic label had low viscosity and thixotropy, excellent gravure printability and curability, and good adhesion, resistance to scratching, and scratch resistance.

Examples 2-15
As shown in Table 1, the resin composition and the plastic label were obtained in the same manner as in Example 1 except that the amount and type of component C and pigment were changed.
The obtained resin composition and plastic label have good properties, low viscosity and thixotropy, excellent gravure printability and curability, and good adhesion, resistance to scratching, and scratch resistance. It was.

Comparative Example 1
As shown in Table 2, a resin composition and a plastic label were obtained in the same manner as in Example 1 except that Component C was not used.
The obtained resin composition had high viscosity and thixotropy and was poor in gravure printing suitability.

Comparative Example 2
As shown in Table 2, a resin composition was obtained in the same manner as in Example 1 except that components A and C were not used.
The obtained resin composition had high viscosity and thixotropy, was suitable for gravure printing, had a low curing rate, and was inferior in productivity. Since the curability was remarkably bad, the adhesion and the like could not be evaluated.

Comparative Example 3
As shown in Table 2, a resin composition was obtained in the same manner as in Example 1 without using Component B and Component C.
The obtained resin composition was agglomerated with component D and could not be used as a printing ink. Furthermore, thixotropy was also high.

Comparative Example 4
As shown in Table 2, a resin composition and a plastic label were obtained in the same manner as in Example 1 without using Component C and Component D.
The obtained resin composition had “bubbles” and was inferior in properties as a printing ink. Moreover, thixotropy was high and productivity was inferior.

Comparative Example 5
As shown in Table 2, the amount of component C was reduced, and a resin composition and a plastic label were obtained in the same manner as in Example 1.
The obtained resin composition had high thixotropy and poor productivity.

Comparative Example 6
As shown in Table 2, the resin composition was obtained in the same manner as in Example 1 by increasing the compounding amount of Component C.
The obtained resin composition was an unstable composition that generated heat, and could not be used as a printing ink. Furthermore, thixotropy was also high.

Comparative Examples 7-9
As shown in Table 2, a resin composition and a plastic label were obtained in the same manner as in Example 2 except that adipic acid, citric acid, and hydrochloric acid were used instead of Component C of the present invention.
The obtained resin composition had high thixotropy and poor productivity. Furthermore, the resin composition obtained in Comparative Example 9 was an unstable composition that generated heat, and could not be used as a printing ink.

  Moreover, about the plastic label obtained in the said Examples 1-15, the container with a label was produced using this label. The obtained plastic label is formed in a cylindrical shape so that the printing surface is the inner surface, and the length in the circumferential direction is adjusted so as to be attached to the body of the PET bottle after being heat-shrinked by 20%. Welded to obtain a cylindrical plastic label. Further, the container was attached to a 500 ml PET bottle, and the label was shrunk by a steam tunnel having an atmospheric temperature of 90 ° C. to obtain a labeled container. The resulting labeled container had an excellent finish.

Components A to D, pigments and other additives used in Tables 1 and 2 are as follows. The unit of the blending amount in the table is “parts by weight”.
Component A: Product name “Aron Oxetane OXT-221” manufactured by Toagosei Co., Ltd.
Component B: Product name “Celoxide 2021P” manufactured by Daicel Chemical Industries, Ltd.
Component C (Wako Pure Chemical Industries, Ltd.)
C1: salicylic acid C2: m-hydroxybenzoic acid C3: phthalic acid C4: isophthalic acid C5: benzoic acid C6: adipic acid C7: citric acid C8: hydrochloric acid component D: manufactured by Shin-Etsu Chemical Co., Ltd., trade name “X-22 -2516 "
Pigment (Pigments 1-3 are titanium dioxide, Pigment 4 is copper phthalocyanine)
Pigment 1: Product name “JR-809” manufactured by Teika Co., Ltd.
Pigment 2: Made by Ishihara Sangyo Co., Ltd., trade name “Taipeke R-830”
Pigment 3: manufactured by DuPont Co., Ltd., trade name “Tai Pure R-960”
Pigment 4: “IRGALITE BLUE GLVO” manufactured by Ciba Specialty Chemicals Co., Ltd.
Photopolymerization initiator: trade name “UVI-6992” manufactured by Dow Chemical Co., Ltd.
Sensitizer: manufactured by Kawasaki Kasei Kogyo Co., Ltd., dibutoxyanthracene blocking inhibitor: manufactured by Tosoh Silica Co., Ltd., trade name “E-1030” (silica particles)
Lubricant: Product name “SPRAY 105” (Fischer Tropsch Wax), manufactured by Sazol Co., Ltd.

Claims (5)

A resin composition comprising an oxetane compound, an epoxy compound, and an organic acid having a structure in which one hydrogen atom of a benzene ring is substituted with a carboxyl group, wherein the weight ratio of the oxetane compound to the epoxy compound in the resin composition Is 2: 8 to 8: 2, the total content of the oxetane compound and the epoxy compound is 30 to 99% by weight with respect to the total amount of the resin composition, and the content of the solvent in the resin composition is 0 to 5% by weight. The active energy ray-curable resin for plastic film, wherein the organic acid is contained in an amount of 0.1 to 5% by weight , and a photopolymerization initiator is further contained relative to the total weight of the resin composition. Composition. The active energy ray-curable resin composition for a plastic film according to claim 1, wherein the content of the photopolymerization initiator is 0.5 to 7 % by weight based on the total weight of the resin composition.   Furthermore, the active energy ray curable resin composition for plastic films of Claim 1 or 2 which contains a pigment 0.1 to 50weight% with respect to the total weight of a resin composition.   Furthermore, 0.1-30 weight part of silicone compounds are contained with respect to 100 weight part of total amounts of an oxetane compound and an epoxy compound, Active energy ray hardening property for plastic films in any one of Claims 1-3 Resin composition.   A plastic label having a cured resin layer formed by applying and curing the active energy ray-curable resin composition for a plastic film according to any one of claims 1 to 4 on at least one surface of the plastic film.