JP6019911B2 - Packaging material made by laminating printing ink and adhesive for heat-shrinkable film - Google Patents

Description

The present invention relates to a packaging material in which a heat-shrinkable film used for packaging an article is laminated with a design printing layer made of printing ink for heat-shrinkable film and an adhesive layer made of hot-melt adhesive for heat-shrinkable film.

In recent years, beverage containers such as polyethylene terephthalate bottles (hereinafter referred to as PET bottles) have been used in various shapes for the purpose of improving design properties, and plastic film labels have been used. In addition, a packaging material is used for a so-called multipack in which a plurality of articles are packaged together with a label of a single dry battery, and further with a dry battery, a health drink, and other beverage containers. Moreover, the packaging material is used so that the lid | cover of a pharmaceutical container and a drink container may be covered for the purpose of foreign material mixing prevention.

In the packaging material including the label as described above, a heat shrink film is used as the packaging material in order to wrap articles having various shapes. A thermosetting adhesive was used for the heat shrinkable film, but the market demanded environmental measures such as reducing the use of solvents and reducing carbon dioxide emissions, and reducing costs. Therefore, in general label applications, hot melt adhesives that satisfy the above requirements have been studied. However, a packaging material with an adhesive layer in which a thermoplastic printing type hot melt adhesive is applied to a design printing layer made of a heat shrinkable film or a heat shrinkable film printing ink is mounted on an article. Later, when heated for shrinkage, the adhesive layer softens and flows, which causes problems such as contamination of the article by the adhesive and removal of the packaging material from the article.

Therefore, a method has been proposed in which the hot melt adhesive is made into an ultraviolet curable type so that the adhesive layer does not flow even when the packaging material is heated for heat shrinkage (see Patent Document 1).

However, the ultraviolet curable hot melt adhesive disclosed in Patent Document 1 has a problem in that the heat shrinkage of the heat shrinkable film and the cure shrinkage of the adhesive layer do not match, and the packaging material is wrinkled. Moreover, when the printing layer was formed in the packaging material, there existed a problem that an ultraviolet-ray did not reach an adhesive layer but hardening became inadequate. Moreover, since the ultraviolet curable hot melt adhesive requires an ultraviolet curable resin and a photopolymerization initiator as raw materials, there is a sanitary problem with food-related articles as packaging materials. In addition, the UV curable type has a problem that it requires an ultraviolet light source for curing and requires a new production facility.

Furthermore, when the hot melt adhesive is applied directly to the heat shrinkable film, the hot melt adhesive is repelled and cannot be applied uniformly, resulting in a problem that the adhesive strength of the packaging material is lowered.

JP 2008-145498 A

The present invention is such that the adhesive layer does not flow even at a temperature at which the heat-shrinkable film is heated and shrunk, it is difficult for wrinkles to enter the packaging material even after heat-shrinking, good hygiene, and requires extra production equipment such as an ultraviolet light source The adhesive layer is made of a hot-melt adhesive for heat-shrinkable film that can be used to produce packaging materials, and has good hygiene and can improve coating suitability without repelling the hot-melt adhesive. It aims at providing the packaging material formed by laminating | stacking the design printing layer which consists of printing ink for shrinkable films on a heat shrink film.

The present invention is a packaging in which a heat-shrinkable film is laminated with a design printing layer made of a printing ink for heat-shrinkable film (A) and an adhesive layer made of a hot-melt adhesive for heat-shrinkable film (B). The heat-shrinkable film printing ink (A) includes one or more resins selected from the group consisting of urethane resins, acrylic resins, nitrocellulose resins, and vinyl chloride / vinyl acetate copolymer resins. And it is related with the packaging material characterized by being the following (B1)-(B4) in 100 weight part of hot-melt-adhesives for heat-shrinkable films (B).
(B1) a styrenic error scan Tomah 10 to 25 parts by weight (B2) tackifier 25-40 parts by weight (B3) a process oil 20-40 parts by weight (B4) softening point 125 ° C. and a polystyrene and rubber midblock 15 to 35 parts by weight of polypropylene wax at 165 ° C. or lower

Furthermore, the present invention is the above packaging, characterized in that the design print layer is provided on at least one surface of the heat-shrinkable film, and the adhesive layer is provided on at least one end of the film. Regarding materials.

Furthermore, this invention relates to the manufacturing method of the articles | goods with a packaging material which has the process of attaching the said packaging material to the outer periphery of articles | goods, and then shrinking a heat-shrinkable film by heating.

Further, in the present invention, the step of mounting the packaging material includes forming one cylindrical packaging material by overlapping one end of the packaging material on the other end, and mounting the cylindrical packaging material on the outer periphery of the article. It is a process to do, It is related with the manufacturing method of the said article | item with a packaging material characterized by the above-mentioned.

Further, according to the present invention, the step of attaching the packaging material includes the step of attaching one end of the packaging material to the article, and then winding the packaging material around the outer periphery of the article, The present invention relates to a method for manufacturing an article with a packaging material in the previous period, characterized by comprising a step of pasting so that both ends of the material overlap.

According to the present invention, the design printing layer comprising the printing ink for heat-shrinkable film has a urethane resin, acrylic resin, nitrocellulose resin, and vinyl chloride / vinyl acetate having high affinity with the hot-melt adhesive for heat-shrinkable film. Since it contains one or more resins selected from any of polymer resins, it prevents repelling when UV curable hot melt adhesives are applied, and as a result, prevents a decrease in adhesive strength of the packaging material It becomes possible.

Furthermore, when the hot-melt adhesive for heat-shrinkable film contains a specific polypropylene wax, when the hot-melt adhesive is heated and melted and applied, that is, the temperature of the hot-melt adhesive decreases from a high temperature to a low temperature. Sometimes the viscosity of a hot melt adhesive is low. And when heating to shrink the heat-shrinkable film on which the adhesive layer is formed, that is, when the temperature of the hot melt adhesive rises from a low temperature to a high temperature, the adhesive layer does not flow, so the film comes off, The effect that no deviation occurs is obtained.

Furthermore, the printing ink for heat-shrinkable film and the hot-melt adhesive for heat-shrinkable film of the present invention are a polyfunctional monomer such as a photopolymerization initiator and an acryloyl group contained in an ultraviolet curable ink, a hot-melt adhesive or the like. Etc. are not included. Accordingly, when handling the skin, it is difficult to cause skin irritation and the like, so that it is excellent in hygiene.

By completing the present invention, the adhesive layer does not flow even at a temperature at which the heat-shrinkable film is heat-shrinked, it is difficult for wrinkles to enter the packaging material even after heat-shrinking, hygiene is good, and extra production equipment such as an ultraviolet light source is provided. Adhesive layer made of hot-melt adhesive for heat-shrinkable film that can produce packaging materials without need, and good hygiene, making it possible to improve coating suitability without repelling hot-melt adhesive The packaging material which laminates | stacks the design printing layer which consists of printing ink for heat-shrinkable films can be provided.

Viscosity temperature curve of hot melt adhesive for heat shrinkable film An example of packaging material An example of packaging material

First, the printing ink (A) for heat-shrinkable film used for the packaging material of the present invention will be described.

The printing ink for heat-shrinkable film (A) contains at least one resin selected from a urethane resin, an acrylic resin, a nitrocellulose resin, and a vinyl chloride / vinyl acetate copolymer resin as a main binder. These resins have a high affinity with hot-melt adhesives for heat-shrinkable films and prevent repelling when hot-melt adhesives are applied. As a result, they can prevent a decrease in the adhesive strength of packaging materials. It becomes possible.

Because of its flexibility and low crystallinity, urethane resin has excellent processability when creating packaging materials due to its ability to relieve stress due to thermal history, can reduce residual solvent in the film, and dissolves well in highly polar solvents. Have sex. On the other hand, the acrylic resin is easy to manufacture and various monomers can be selected, so that it can be dissolved in various solvents including water and the pigment dispersibility can be improved. Furthermore, since the nitrocellulose resin and the vinyl chloride / vinyl acetate copolymer resin generally have high pigment dispersibility, it is possible to increase the smoothness of the design print layer and further suppress the repellency of the hot melt adhesive.

From the viewpoint of adhesiveness and film formability, it is preferable to use the nitrocellulose resin and the vinyl chloride / vinyl acetate copolymer resin in combination with a urethane resin or an acrylic resin, rather than being used alone.

The urethane resin is synthesized by reacting a polymer polyol and diisocyanate at a temperature of 10 to 150 ° C. using a solvent inert to an isocyanate group, if necessary, and using a urethanization catalyst if necessary. The prepolymer method in which a prepolymer having an isocyanate group is produced and then a urethane resin is obtained by reacting the prepolymer with a chain extender and a terminal terminator, or a polymer polyol, a diisocyanate and a chain extender in one step. It can be produced by a known method such as a one-shot method in which a urethane resin is obtained by reaction.

Examples of the polymer polyol include polyester polyol, polyether polyol, and acrylic polyol. In the present invention, it is desirable to use one or more of polyester polyol and polyether polyol.

The polyester polyol is a polyester polyol containing a hydroxyl group at the terminal and / or side chain, and is obtained by dehydration condensation or polymerization of a hydroxyl group-containing compound such as glycol or polyol and a polyvalent carboxylic acid or an anhydride thereof. can get. In the present invention, more specifically, a polyester diol composed of a compound containing two hydroxyl groups and a divalent carboxylic acid is preferred.

Examples of the hydroxyl group-containing compound used for the synthesis of the polyester polyol include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, pentanediol, and 2-methyl-1,3-propane. Diol, neopentyl glycol, 3-methyl-1,5-pentanediol, hexanediol, octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 1,4-butynediol, 2 , 2,4-Trimethyl-1,3-pentanediol, 1,4-cyclohexanedimethanol, 2-butyl-2-ethyl-1,3-propanediol, 3-methyl 1,5-pentanediol, diethylene glycol, triethylene Glycol, polypropylene glycol, dipropylene glycol Call. Moreover, the low molecular polyol which has 3 or more of hydroxyl groups, such as glycerol, a trimethylol propane, a trimethylol ethane, 1,2, 6-hexane triol, 1,2, 4- butane triol, sorbitol, a penta esitol, is also mentioned. .

Moreover, as a high molecular weight hydroxyl group-containing compound, a saturated or unsaturated low molecular diol (2), a polymer or copolymer polyether diol (3) such as ethylene oxide, propylene oxide, and tetrahydrofuran is also included. It can be used together as a raw material for polyester diol.

Furthermore, it is preferable to use a hydroxyl group-containing compound having an alkyl side chain as a monomer for the polyester polyol. By using the polyester polyol, the crystallinity of the urethane resin is greatly lowered, and the alkyl side chain is hydrocarbon and hydrophobic, so that the adhesion to the polyolefin film is improved. Furthermore, hydrolysis resistance improves compared with the case where a hydroxyl-group containing compound does not have an alkyl side chain.

Polycarboxylic acid monomers used for the synthesis of polyester diol include adipic acid, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, glutaric acid, pimelic acid, speric acid, Examples thereof include polycarboxylic acids such as azelaic acid, sebacic acid, trimellitic acid and pyromellitic acid, and anhydrides (4) thereof. Among these, it is preferable to use adipic acid from the viewpoint of solubility in a non-toluene solvent, and it is more preferable to use 50% by weight or more in the polyvalent carboxylic acid monomer.

The number average molecular weight of the polyester diol used for the urethane resin is appropriately determined in consideration of the solubility, drying property, blocking resistance and the like of the obtained urethane resin, and is usually in the range of 700 to 100,000, preferably 1000 to 6000. It is good to do. If the number average molecular weight is less than 700, the printability tends to be inferior due to a decrease in solubility due to an increase in the amount of hard segments. There exists a tendency for blocking property to fall.

The acid value of the polyester diol is preferably 1.0 mgKOH / g or less, and more preferably 0.5 mgKOH / g or less. This is because if the acid value is larger than 1.0 mg KOH / g, the tendency of the printing ink to increase in viscosity increases.

Polyester diol is superior to other polymer polyols in blocking resistance, and further can prevent deterioration of film adhesion due to a plasticizer in a hot melt adhesive. Therefore, the polyester polyol is used in a total amount of 50% by weight or more in the polymer polyol. It is preferable.

It is also preferable to use a polyether polyol as the polymer polyol. For example, polyethylene glycol, polypropylene glycol, polytrimethylene glycol, polytetramethylene glycol and the like can be mentioned. Since these have excellent solubility in alcohol and can impart another solvent solubility to the polyester-based polyurethane, they are preferably used in combination in many applications. In order to develop these characteristics and not lower the water resistance, the polyether polyol molecular weight is preferably 700 to 3000 and 50% by weight or less in the polymer polyol.

Examples of the diisocyanate used for the synthesis of the urethane resin include various known aromatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates that are generally used in the production of urethane resins. For example, 1,5-naphthylene diisocyanate, 4,4′-diphenylmethane diisocyanate (MDI), 4,4′-diphenyldimethylmethane diisocyanate, 4,4′-dibenzyl isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1 , 3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, Cyclohexane-1,4-diisocyanate, xylylene diisocyanate, isophorone diisocyanate Nate, dimethylene diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, 1,3-bis (isocyanate methyl) cyclohexane, methylcyclohexane diisocyanate, norbornane diisocyanate, m-tetramethylxylylene diisocyanate, 4,4-diphenylmethane diisocyanate, tri Examples thereof include diisocyanate, dimerisocyanate obtained by converting a diisocyanate carboxyl group into diisocyanate, bis-chloromethyl-diphenylmethane-diisocyanate, 2,6-diisocyanate-benzyl chloride, and a dimer acid carboxyl group. These diisocyanate compounds can be used alone or in admixture of two or more.

A chain extender may be used for the synthesis of the urethane resin. For example, in addition to 2-butyl-2-ethyl-1,3-propanediol, the saturated or unsaturated low molecular polyols (1), ethylenediamine, In addition to propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, isophoronediamine, dicyclohexylmethane-4,4'-diamine, 2-hydroxyethylethylenediamine, 2-hydroxyethylpropyldiamine, 2-hydroxyethylpropylenediamine, di 2-hydroxyethylethylenediamine, di-2-hydroxyethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypyrroleethylenediamine, di-2-hydroxypyrroleethylenediamine, di-2- Amines having a hydroxyl group in the molecule, such as mud propyl ethylene diamine may also be used. These chain extenders can be used alone or in admixture of two or more.

A monovalent active hydrogen compound can also be used as a terminal terminator for the purpose of terminating the reaction. Examples of such compounds include compounds having primary and secondary amino groups, dialkylamines such as di-n-butylamine, amino alcohols having a hydroxyl group, and alcohols such as ethanol and isopropyl alcohol. Furthermore, amino acids such as glycine and L-alanine can be used as a reaction terminator particularly when it is desired to introduce a carboxyl group into the urethane resin. Among these, amino alcohols having primary and secondary amino groups need to be controlled so as to react only with amino groups while avoiding reaction at high temperature when used as a terminal terminator. These end terminators can be used alone or in admixture of two or more. Here, when an amino group is used as a chain extender, it reacts with an isocyanate group to form a urea bond, so that the resulting resin is a polyurethane / urea resin. In the present invention, these resins are also urethane resins. To do.

Furthermore, in the present invention, a water-soluble urethane resin can also be used. In the case of synthesizing a water-soluble urethane resin, an anionic group-containing compound having an active hydrogen group, a cationic group-containing compound, a nonionic group-containing compound, or the like is used in addition to the polymer polyol and diisocyanate. In the present invention, from the viewpoints of solubility of the water-soluble urethane resin, physical properties of the coating film, etc., it is preferable to use an anionic group-containing compound and use a nonionic group-containing compound in combination as necessary.

As an anionic group-containing compound having an active hydrogen group, a compound having a carboxyl group is generally known, and 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2-dimethylolbutyric acid, 2, Dimethylolalkanoic acid such as 2-dimethylolvaleric acid, glutamine, asparagine, lysine, diaminopropionic acid, ornithine, diaminobenzoic acid, diamine type amino acids such as diaminobenzenesulfonic acid, glycine, alanine, glutamic acid, taurine, aspartic acid, Monoamine type amino acids such as aminobutyric acid, valine, aminocaproic acid, aminobenzoic acid, aminoisophthalic acid, sulfamic acid and the like can be mentioned.

The anionic group incorporated in the urethane resin forms a salt by neutralization and dissolves in water. Examples of the neutralizing agent used in this case include ammonia, monoethylamine, diethylamine, trimethylamine, triethylamine, triisopropylamine, tributylamine, triethanolamine, methyldiethanolamine, and monoethanolamine. Ammonia is preferred because it does not easily remain in the film and does not impair the physical properties of the coating.

Examples of the cationic group-containing compound having an active hydrogen group include compounds having an amino group, an ammonium base, a sulfonium base and the like. However, the cationic group incorporated in the urethane resin dissolves in water by neutralization, but there are many cases where an inorganic ion such as sodium ion or lithium ion must be used as a neutralizing agent, Since the additive remains, it is not preferable from the viewpoint of physical properties of the coating film.

As the nonionic group-containing compound, it is preferable to use an ethylene oxide repeating unit-containing compound such as ethylene glycol or polyethylene glycol. Since nonionic groups are poorly soluble in water, it is difficult to dissolve a urethane resin in water with only nonionic groups. However, in order to adjust the stability of the resin, the suitability of the coating film, etc. It can be used in combination with a functional group-containing compound.

In the production of the prepolymer which is an intermediate of the urethane resin, the amount of the polymer polyol and the diisocyanate is the ratio of the number of moles of the isocyanate group of the diisocyanate and the total number of moles of the diol containing the polymer polyol and the hydroxyl group of the polyol. It is preferable that a certain NCO / OH ratio is in the range of 1.1 to 3.0. When this ratio is less than 1.1, there is a tendency that sufficient alkali resistance cannot be obtained, and when it is more than 3.0, the solubility of the resulting prepolymer tends to be lowered.

Furthermore, a catalyst can also be used for this urethanation reaction. Examples of catalysts that can be used include tertiary amine catalysts such as triethylamine and dimethylaniline; metal catalysts such as tin and zinc. These catalysts are used in the range of 0.001 to 1 mol% with respect to the hydroxyl group-containing compound including the polymer polyol.

The prepolymer having an isocyanate group at the terminal obtained above and a diol, diamine, triol or the like as a chain extender are reacted at 10 to 80 ° C. to obtain a urethane resin containing an active hydrogen group at the terminal.

When using an end-stopper, the end-stopper and chain extender may be used together to carry out a chain extension reaction. Thus, an end termination reaction may be performed. On the other hand, the molecular weight can be controlled without using a terminal terminator, but in this case, a method of adding a prepolymer to a solution containing a chain extender is preferable in terms of reaction control.

End terminators are used to control molecular weight. As the amount used increases, the molecular weight of the urethane resin obtained decreases. This varies depending on the reactivity of the chain extender and end terminator to the prepolymer, but in general, the ratio of the number of moles of amino groups and hydroxyl groups of the chain extender to the number of moles of amino groups and hydroxyl groups of the end terminator is A range of 0.5 to 5.0 is preferred. When this ratio exceeds 5.0, the polymer has a high molecular weight, so that the suitability for dry lamination tends to deteriorate. When it is less than 0.5, the molecular weight and the initial adhesive force tend to decrease.

The ratio of the total number of moles of amino groups and hydroxyl groups of the chain extender and terminal terminator to the equivalent of isocyanate groups in the prepolymer is 1.1 to 3.0, preferably 1.5 to 2.0. To react. When this ratio is large and the amount of chain extender or terminal terminator used is large, they remain unreacted and odor tends to remain.

The urethane resin preferably has a weight average molecular weight of 20,000 to 100,000. If it is smaller than 20000, it is difficult to ensure blocking resistance in the printed matter, and if it is larger than 100,000, it is difficult to ensure the printing effect because the solubility in a solvent is poor.

The amine value of the urethane resin is preferably 0.5 to 20.0 mgKOH / g. When the amine value is lower than 0.5, it is difficult to ensure adhesion to the polyolefin film, and when it is greater than 20.0, it is difficult to ensure ink stability when an isocyanate curing agent is added.

Solvents used for urethane resins used in printing inks for heat-shrinkable films (A) include ester solvents such as ethyl acetate, n-propyl acetate, isopropyl acetate, isobutyl acetate, propylene glycol monoethyl ether acetate, and methanol. Alcohol solvents such as ethanol, n-propanol, isopropanol and n-butanol, aromatic solvents such as benzene, toluene and xylene, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, and known solvents such as water , Single or multiple use.

The acrylic resin that can be used in the present invention can be produced by a conventionally known method, and the production method is not particularly limited. The acrylic resin can be obtained by polymerizing a monomer having a carbon-carbon unsaturated double bond in one molecule in a solvent using a polymerization initiator. Here, examples of the monomer having a carbon-carbon unsaturated double bond in one molecule include a (meth) acrylic acid derivative, and an aromatic vinyl monomer and an olefinic hydrocarbon monomer as necessary. , Vinyl ester monomers, vinyl halide monomers, and vinyl ether monomers can be used.

Examples of (meth) acrylic acid derivatives include alkyl (meth) acrylates such as (meth) acrylonitrile, (meth) acrylate, methyl (meth) acrylate, butyl (meth) acrylate, ethylhexyl (meth) acrylate, stearyl (meth) acrylate, etc. ) Acrylate, benzyl (meth) acrylate, and the like.

As monomers that can be used in combination, examples of aromatic vinyl monomers include styrene, methylstyrene, ethylstyrene, chlorostyrene, monofluoromethylstyrene, difluoromethylstyrene, trifluoromethylstyrene, and other olefinic hydrocarbon monomers. Examples of the body include ethylene, propylene, butadiene, isobutylene, isoprene, 1,4-pentadiene, etc., examples of vinyl ester monomers include vinyl acetate, etc., examples of vinyl halide monomers include vinyl chloride, Examples of vinyl ether monomers such as vinylidene chloride include vinyl methyl ether.

Moreover, the monomer which has a carbon-carbon unsaturated double bond in 1 molecule can use the monomer which has a crosslinkable functional group. Examples of the monomer having a functional group include a monomer having a hydroxyl group, a monomer having an isocyano group, and a monomer having an epoxy group.

Examples of monomers having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 1-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol Examples include mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polytetramethylene glycol mono (meth) acrylate, and hydroxystyrene.

Examples of the monomer having an isocyanate group include (meth) acryloyloxyethyl isocyanate, (meth) acryloyloxypropyl isocyanate, etc., as well as 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and the like. Examples thereof include those obtained by reacting a hydroxyalkyl (meth) acrylate with a polyisocyanate such as toluene diisocyanate or isophorone diisocyanate.

Examples of the monomer having an epoxy group include glycidyl methacrylate, glycidyl cinnamate, glycidyl allyl ether, glycidyl vinyl ether, vinylcyclohexane monoepoxide, 1,3-butadiene monoepoxide, and the like.

Depending on the required performance, one of these monomers having a carbon-carbon unsaturated double bond can be used, or a mixture of two or more monomers can be used. Includes styrene, methyl (meth) acrylate, butyl (meth) acrylate, ethylhexyl (meth) acrylate, and the like.

The acrylic resin can be obtained using the polymerization initiator in the presence or absence of a solvent for the monomer. Examples of the polymerization initiator include conventional peroxides or azo compounds such as benzoyl peroxide, di-t-butyl peroxide, t-butyl perbenzoate, t-butyl peroctoate, cumene hydroxy peroxide, azoisobutyl valenonitrile. Azobisisobutyronitrile, etc. are used. As the solvent for the urethane resin, ethyl acetate, isopropanol, ethanol, methyl ethyl ketone, and the like are used as in the case of the urethane resin.

The polymerization temperature is 50 to 140 ° C, preferably 70 to 140 ° C. The weight average molecular weight of the obtained polymer is preferably 8000 to 200000, more preferably 8000 to 60000. If it is less than 8000, the film is brittle and blocking occurs, and if it exceeds 60000, the resin viscosity increases, which is not preferable. The glass transition temperature (Tg) of the acrylic resin is preferably 20 to 130 ° C. If the glass transition temperature is less than 20 ° C, the heat resistance of the printed layer may be reduced or blocking may occur easily. If the glass transition temperature exceeds 130 ° C, the solubility in a solvent may be reduced or the ink stability may be reduced. is there.

The vinyl chloride / vinyl acetate copolymer resin usable in the present invention is obtained by copolymerizing a vinyl chloride monomer and a vinyl acetate monomer. The vinyl chloride / vinyl acetate copolymer having a hydroxyl group can further use vinyl alcohol in the copolymerization or saponify a part of vinyl acetate. In the vinyl chloride / vinyl acetate copolymer having a hydroxyl group, the properties of the resin film and the resin dissolution behavior are determined by the monomer ratio of vinyl chloride, vinyl acetate and vinyl alcohol. That is, vinyl chloride imparts toughness and hardness of the resin coating, vinyl acetate imparts adhesion and flexibility, and vinyl alcohol imparts good solubility in polar solvents. In the present invention, from the viewpoint of ensuring solubility in various solvents, the vinyl chloride / vinyl acetate copolymer resin preferably has a hydroxyl group, and the salt hydroxyl value is preferably 60 to 170 mgKOH / g.

As the nitrocellulose resin that can be used in the present invention, a nitrogen content of 10 to 13% by weight and an average degree of polymerization of 35 to 90 are preferably used, more preferably a nitrogen content of 10.7 to 12.2% by weight and an average. The degree of polymerization is 45-70.
A commercially available product may be used as the nitrocellulose resin used in the present invention, for example, “HIG1 / 2GKCNC, 1 / 4G, 1 / 8G, 1 / 16G” manufactured by KOREA CNC.

The printing ink for heat-shrinkable film (A) is dispersed in one or more resins selected from urethane resin, acrylic resin, nitrocellulose resin, and vinyl chloride / vinyl acetate copolymer resin, as needed. It can be produced by dissolving or dispersing a colorant in an organic solvent by a known method using a combination of a colorant and a resin other than the above resin. Preferably, a pigment dispersion is produced using a colorant and a resin, and if necessary, a dispersant, and the resin and necessary additives are further mixed and stirred.

As the dispersant, anionic, nonionic, cationic, amphoteric surfactants can be used. The dispersant is preferably contained in the ink in an amount of 0.05% by weight or more based on the total weight of the ink from the viewpoint of the storage stability of the ink and 5% by weight or less from the viewpoint of the suitability for lamination. Furthermore, it is more preferable that it is contained in the range of 0.1 to 2% by weight.

  Examples of the solvent used in the printing ink for heat-shrinkable film (A) include the solvents described in the urethane resin used in the printing ink for heat-shrinkable film (A).

In the printing ink for heat-shrinkable film (A), the dilution solvent used at the time of printing is controlled by adjusting the viscosity and controlling the printing effect and printed matter density. It can select suitably from the solvent used for printing ink (A) for heat-shrinkable film.

The printing ink (A) for heat-shrinkable film can be used in combination with various resins depending on the application and the substrate. Examples of resins used include chlorinated polypropylene resins, vinyl acetate resins, polyamide resins, polyester resins, alkyd resins, polyvinyl chloride resins, rosin resins, rosin modified maleic resins, terpene resins, phenol modified terpene resins, ketones Examples thereof include resins, cyclized rubbers, chlorinated rubbers, butyrals, petroleum resins, and modified resins thereof. These resins can be used alone or in combination of two or more, and the content thereof is preferably 5 to 25% by weight based on the total weight of the ink.

In the printing ink for heat-shrinkable film (A), known inorganic pigments and organic pigments can be used.

Examples of inorganic pigments include titanium oxide, zinc oxide, zinc sulfide, barium sulfate, calcium carbonate, chromium oxide, and silica. Titanium oxide is preferably used for the white ink pigment from the viewpoint of coloring power, hiding power, chemical resistance, and weather resistance.

Examples of inorganic pigments other than white pigments include carbon black, aluminum, mica (mica) and the like. Aluminum is in the form of powder or paste, but is preferably used in the form of paste from the viewpoint of handling and safety, and whether to use leafing or non-leafing is appropriately selected from the viewpoint of brightness and concentration.

Organic pigments include azo, phthalocyanine, anthraquinone, perylene, perinone, quinacridone, thioindigo, dioxazine, isoindolinone, quinophthalone, azomethine azo, dictopyrrolopyrrole, isoindoline, etc. Pigments. Indigo ink is copper phthalocyanine, and transparent yellow ink is C.I. I. Pigment No Yellow 83 is preferably used.

The pigment is preferably contained in an amount sufficient to ensure the concentration and coloring power of the printing ink (A) for heat-shrinkable film, that is, 1 to 50% by weight based on the total weight of the printing ink. These pigments can be used alone or in combination of two or more.

For the pigment dispersion, known roller mills, ball mills, pebble mills, attritors, sand mills and the like can be used.

The ink viscosity produced by the above method is in the range of 10 mPa · s or more from the viewpoint of preventing the pigment from settling and being appropriately dispersed, and 1000 mPa · s or less from the viewpoint of workability efficiency during ink production or printing. preferable. In addition, the said viscosity is a viscosity measured at 25 degreeC with the Tokimec B-type viscometer.

The printing ink (A) for heat-shrinkable film can be printed on the heat-shrinkable film by a known printing method such as gravure printing, flexographic printing, and ink jet printing. Gravure printing and flexographic printing are preferred.

The design printing, etc., printed using the printing ink for heat-shrinkable film (A) has a thickness of 0.5 to 3 μm, and is formed on the entire surface or part of the heat-shrinkable film depending on the application. .

Next, the hot melt adhesive (B) for heat shrinkable film will be described.
The hot-melt adhesive for heat-shrinkable film (B) comprises a styrene elastomer having polystyrene and a rubber intermediate block, a tackifier, a process oil, and a polypropylene wax having a softening point of 125 ° C. or higher and 165 ° C. or lower. It is preferable to contain 35% by weight. In the present invention, the adhesive is a concept including an adhesive.

Elastomers are used to impart cohesive strength to hot melt adhesives. And since an adhesive agent is a hot-melt type, a thermoplastic elastomer is preferable. This elastomer preferably has heat-melting property and moderate condensing power. For example, olefin-based elastomer, vinyl chloride-based elastomer, polyester-based elastomer, polyurethane-based elastomer, nylon-based elastomer elastomer, acrylic-based, or styrene-based polymer is preferable. . Among these, styrenic elastomers are more preferable from the viewpoint of the balance between adhesive strength and cohesive strength.

The styrenic elastomer used in the present invention generally has a polystyrene block and a rubber intermediate block. The polystyrene block forms a physical cross-link (domain) as a hard segment to serve as a bridging point, and the rubber intermediate block functions as a soft segment. Soft segments include polybutadiene (B), polyisoprene (I), and polyolefin elastomers (ethylene propylene, EP). Depending on the arrangement of the hard segment with polystyrene (S), linear (linear type) And radial (radical type). In the present invention, styrene / butadiene block copolymer (SB, diblock), (SBSS, triblock), styrene / isoprene block copolymer (SI, diblock), (S- IS, triblock) and styrene / butadiene-isoprene block copolymers (SB, I, diblock), (SB / IB, triblock) and hydrogenated products of these block copolymers For example, hydrogenated styrene / butadiene / styrene block copolymer (SBS), hydrogenated styrene / isoprene / styrene block copolymer (SEPS), styrene / hydrogenated poly (isoprene / butadiene) / styrene ( SEEPS), styrenic elastomer modified with carboxylic acid, and styrene in the styrene block And copolymers of aromatic vinyl compounds such as α-methylstyrene. Among these, a styrene-ethylene / butylene-styrene block polymer copolymer (SEBS) is more preferable from the viewpoint of thermal stability because it is difficult to thermally decompose.

The elastomer preferably has a melt viscosity of 1 Pa · s to 10 Pa · s. When the melt viscosity of the elastomer is 1 Pa · s or more, the adhesive layer is difficult to be softened even at the heat shrink temperature of the film, so that the film is hardly detached from the article. On the other hand, when the melt viscosity of the elastomer is 10 Pa · s or less, the viscosity when the hot melt adhesive is applied becomes appropriate, and an adhesive layer is easily formed. In the present invention, the melt viscosity is a viscosity measured with a B-type viscometer at 25 ° C. in a solution of 25% by weight of an elastomer dissolved in toluene.

The elastomer is preferably contained in an amount of 10% to 25% by weight, more preferably 15% to 20% by weight, in 100% by weight of the hot melt adhesive. When the amount of the elastomer is 10% by weight or more, it becomes easy to balance the cohesive force and the adhesive force, and the heat shrinkage property is further improved. On the other hand, when the amount of the elastomer is 25% by weight or less, the viscosity at the time of applying the hot melt adhesive becomes more appropriate, so that the adhesive layer is easily formed. The heat shrinkage property means that a heat-shrinkable plastic film coated with a hot melt adhesive is attached to a PET bottle and immersed in warm water at 90 ° C. for 3 seconds to shrink the film. Sometimes the label does not peel off or shift from the PET bottle.

A tackifier is used in order to improve adhesive force. As tackifiers, phenol resins, modified phenol resins, terpene phenol resins, xylene phenol resins, xylene resins, cyclopentadiene-phenol resins, aliphatic resins, alicyclic resins, aromatic resins, etc., hydrogenated fats Aromatic, alicyclic and aromatic petroleum resins, phenol-modified petroleum resins, rosin ester resins, acid-modified rosin resins, hydrogenated rosin resins, hydrogenated rosin ester resins, low molecular weight polystyrenes Resins, terpene resins, hydrogenated terpene resins and the like are preferable. A tackifier may be used independently or 2 or more types may be used together.

The tackifier is preferably contained in an amount of 25% by weight to 40% by weight in 100% by weight of the hot melt adhesive. Adhesive force improves more because the quantity of a tackifier becomes 25 weight% or more. On the other hand, when the amount of the tackifier is 40% by weight or less, the cohesive force of the adhesive layer is easily maintained, and the adhesive layer is not easily softened even at the heat shrink temperature of the film, so that the film is hardly detached from the article.

The plasticizer is used for the purpose of obtaining an appropriate adhesive force when a hot melt adhesive is used for a heat-shrinkable film and the film is attached to an article in a low-temperature atmosphere. The plasticizer is not particularly limited as long as it satisfies the above characteristics, and liquid rubber ester plasticizers such as liquid polyisoprene, vegetable oil, liquid polybutene, or process oil are preferable. Among these, process oil is preferable from the viewpoint of physical property balance and price. The process oil used in the present invention is produced in petroleum refining and the like, and examples thereof include paraffinic process oil, naphthenic process oil, and aromatic process oil. The process oil is a mixture of the above-mentioned oils. Generally, the process oil contains 30% by weight or more of aromatic carbon in the total carbon, and the process oil contains 35 to 45% by weight of naphthenic ring carbon. Process oils and those containing 50% by weight or more of paraffin chain carbon can be classified as paraffinic process oils. In the present invention, since the adhesive layer easily maintains cohesive force, naphthenic process oil and paraffinic process oil are more preferable from the viewpoint of adhesive residue during manual peeling.

The plasticizer has a problem of penetrating into the design print layer and embrittles the ink coating film. In the present invention, the problem is solved by using a urethane resin.

The plasticizer is preferably contained in an amount of 25 wt% to 40 wt% in 100 wt% of the hot melt adhesive. By containing the plasticizer in an amount of 25 wt% to 40 wt%, it becomes easy to balance the adhesive force between the low temperature atmosphere and the heat shrink temperature.

It is important that the polypropylene wax has a softening point of 125 ° C. or higher and 165 ° C. or lower. Polypropylene wax is used for the purpose of increasing the difference between the viscosity when the temperature of the hot melt adhesive is raised and the viscosity when the temperature is lowered.

When the softening point of the polypropylene wax is 125 ° C. or higher, it is easy to balance the adhesive force and the cohesive force at the heat shrink temperature. On the other hand, when the softening point is 165 ° C. or lower, the viscosity of the adhesive is high, so that coating becomes difficult. The softening point was measured according to JIS K-2207 (petroleum asphalt) 6.4 softening point test method (ring and ball method).

A typical synthesis method of polypropylene is 30 to 70 in a solvent (n-heptane or the like) in which propylene gas having a purity of 95% or more is added to a catalyst (Ziegler-Natta catalyst, for example, triethylenealuminum and titanium trichloride). When it is blown at a temperature, the polymerization reaction proceeds. After the polymerization, an alcohol is added to dissolve and remove the catalyst, whereby the polymer is obtained in the form of a white powder. Polymerization is carried out between normal pressure and 8 MPa, and the content of the isotactic polymer in the product varies depending on the type and concentration of the catalyst, the molar ratio of triethylaluminum to titanium trichloride, the reaction temperature, the time, and the like.

The polypropylene wax preferably has a viscosity average molecular weight of 5,000 to 15,000, more preferably 6,000 to 8,000. When the viscosity average molecular weight is 5,000 or more, it is easy to maintain the cohesive strength of the adhesive even at the heat shrink temperature of the film. On the other hand, when the viscosity average molecular weight is 15,000 or less, it becomes easy to maintain the coating suitability of the adhesive.

The viscosity average molecular weight was measured by a viscosity method. The fiscal year method is a measurement method utilizing the fact that the viscosity η of the polymer solution is a function of the average molecular weight as follows. Generally, the average molecular weight is called the viscosity average molecular weight and is obtained by the following formula 1. It is done.
<Formula 1> η = kMα
(Where k and α are constants specific to the polymer)

The polypropylene wax preferably contains 15 wt% or more and 35 wt% or less in 100 wt% of the hot melt adhesive. When the hot melt adhesive is 15% by weight or more, it becomes easy to obtain heat shrinkage characteristics. On the other hand, application becomes easier when the hot-melt adhesive is 30% by weight or less.

The hot melt adhesive for heat-shrinkable film (B) is characterized in that the viscosity behavior during heating is different from the viscosity behavior during cooling. For example, when a hot melt adhesive is heated to 160 ° C. and then cooled to 25 ° C., the viscosity of the adhesive at 120 ° C. is 200 Pa · s to 50,000 Pa · s when heated, and 110 when cooled. The viscosity of the adhesive at 0 ° C. is preferably 0.1 Pa · s to 150 Pa · s. First, when applying a hot melt adhesive to a heat-shrinkable film, the adhesive is applied after being heated to 150 ° C. or higher and melted. In this case, the temperature of the adhesive is cooled from a high temperature to a low temperature, but coating is easy because of the low viscosity. On the other hand, when a packaging material in which a hot melt adhesive is applied to a heat-shrinkable film is attached to an article and the film is shrunk by heating, the temperature of the adhesive is heated from a low temperature to a high temperature. Since the viscosity maintains a high viscosity, the adhesive does not flow with heat. That is, the packaging material does not come off from the article and does not shift.

The viscosity behavior of the above hot-melt adhesive for heat-shrinkable film (B) will be described with reference to FIG.
When the hot melt adhesive is cooled from a high temperature state (130 ° C. or higher in FIG. 1), the viscosity increases by following one path and showing two inflection points A and B. Next, when the hot melt adhesive is heated from a low temperature (80 ° C. or lower in FIG. 1), the two paths are followed, that is, the path different from that during cooling is followed. The inflection points C and D are shown and the viscosity of the hot melt adhesive is lowered. Thus, hot melt adhesives have different viscosity behaviors during cooling and heating, and the difference between them is large. That is, when a hot melt adhesive is applied, the adhesive is melted by heating once, the temperature of the adhesive is greatly reduced, and an adhesive layer can be formed on the heat shrinkable film in a low viscosity state. On the other hand, when heating to heat shrink the film, the temperature of the adhesive is raised, but its viscosity is difficult to decrease, so when the film is used as a packaging material for goods, packaging An excellent effect that the material does not come off is obtained. In addition, the viscosity at the time of the said temperature fall and temperature rise is measured with the rheometer (The dynamic viscosity viscoelasticity measuring apparatus Rheosol-G3000 UBM company make).

For the hot-melt adhesive for heat-shrinkable film (B), for example, a plasticizer and an elastomer are put into a container, heated and dissolved, and then a tackifier is added. It can be manufactured by adding polypropylene wax after confirming that all of these have dissolved. When dissolving, it is preferable to use a propeller-type stirrer, and the rotation speed is preferably 200 to 500 rpm.

The packaging material of the present invention has a design printing layer made of the above-described printing ink for heat-shrinkable film on at least one surface of the heat-shrinkable film, and at least one of the two right and left ends of the film. The adhesive layer which consists of a hot-melt-adhesive agent (B) for heat-shrinkable films is laminated | stacked on the edge part.

For example, as shown in FIG. 2, the design print layer is entirely or partially on one side of the thermoplastic film (2-1), and is bonded to one end of the same side so as to overlap the design print layer. A case where the layer (2-2) is formed is considered.

Further, as shown in FIG. 3, the design print layer is entirely or partially on one side of the thermoplastic film (3-1), and is placed on both ends of the thermoplastic film so as to overlap the design print layer on the same side. An adhesive layer (3-2, 3-3) is formed. Then, at least one of the adhesive layers in FIG. 3 needs to be an adhesive layer formed by the hot-melt adhesive for heat-shrinkable film according to the present invention.

On the other hand, the other adhesive layer may be a hot-melt adhesive for a heat-shrinkable film according to the present invention, or other general hot-melt adhesive. Although details will be described later, this is because the adhesive layer is not a part for adhering to the thermoplastic film but a part for directly adhering to an article such as a PET bottle. The general hot melt adhesive is selected from acrylic, rubber, and urethane adhesives. For example, a re-peelable hot melt adhesive label melt P-708J manufactured by Toyo Adre is adhesive. From the viewpoint of recyclability and the like.

Any heat-shrinkable film may be used as long as it has heat-shrinkability. In the present invention, a plastic film is preferred. The plastic film is more preferably a stretched polyester film, a stretched polystyrene film, a stretched polyolefin film, a polylactic acid film, a foamed polyolefin film, a stretched polyester-polystyrene coextruded film or a foamed polystyrene film. The plastic film may be provided with a vapor deposition film such as silicon oxide, aluminum oxide, or aluminum. The plastic film may be a non-woven fabric or a laminated film in which two or more films are bonded.

The stretching includes uniaxial stretching and biaxial stretching. In the present invention, uniaxial stretching is preferred. The stretching direction of the uniaxially stretched film may be longitudinal uniaxial stretching or transverse uniaxial stretching.

5-50 micrometers is preferable and, as for the thickness of a heat-shrinkable film, 10-30 micrometers is more preferable. Moreover, as for the thickness in the case of using the said laminated | multilayer film, 5-300 micrometers is preferable.

The shrinkage temperature of the heat-shrinkable film is not limited because it is determined by the shrinkage temperature of the film, but generally 70 to 140 ° C is preferable.

The shrinkage ratio of the heat shrink film is preferably 5 to 85%. When the film shrinks to the above range, the article can be easily packaged. In addition, the heat shrinkage rate in this invention is a heat shrinkage rate when immersed in 100 degreeC warm water, Comprising: The heat shrinkage rate of an extending | stretching direction shall follow the following formula 2. Therefore, in the case of a longitudinally uniaxially stretched film, since the shrinking direction is the film flow direction, the thermal shrinkage rate in the flow direction is 5 to 85%, and in the case of a laterally uniaxially stretched film, the film shrinks in the film width direction. The heat shrinkage ratio in the film width direction is 5 to 85%. In the case of a biaxially stretched film, the thermal shrinkage rate is preferably within the above range with respect to any stretching method.
<Formula 2> Thermal contraction rate (%) = (Dimension before heating−Dimension after heating) / (Dimension before heating) × 100

In addition, various additives such as a lubricant, a filler, a heat stabilizer, an antioxidant, an ultraviolet absorber, an antistatic agent, a flame retardant, and a colorant may be added to the heat-shrinkable film as necessary. Good. Further, the surface of the base film layer may be subjected to conventional surface treatment such as corona discharge treatment, plasma treatment, flame treatment, acid treatment, etc. in order to improve printability.

In order to form an adhesive layer by applying hot-melt adhesive to a heat-shrinkable film or design printing layer, a method of directly applying to the heat-shrinkable film, or a hot-melt adhesive applied to a release sheet There is a method of transferring to a heat-shrinkable film (hereinafter also referred to as transfer coating). The latter is preferred in the present invention.

As a direct coating method, slit coating, curtain spray, spiral spray, dot or bead coating is preferable, and slit coating is more preferable.

As a transfer coating method, roll coating and slit coating are preferred. Specifically, for example, after the hot melt adhesive is applied to the release sheet using a hand applicator, the formed adhesive layer can be transferred to a heat-shrinkable film or a design printing layer.

The hot melt adhesive is preferably heated to 130 to 200 ° C. and melted for coating. And 90-150 degreeC is preferable and, as for coating temperature, 110-140 degreeC is more preferable. When the coating temperature is less than 90 ° C., the hot melt adhesive has a high viscosity and is difficult to obtain stably. On the other hand, when the temperature is 150 ° C. or higher, the heat-shrinkable film shrinks during coating.

The thickness of the adhesive layer is preferably 10 to 200 μm. Moreover, when packaging a PET bottle, 10-200 g / m <2> is more preferable.

The width of the adhesive layer is preferably 1 to 100 mm, and more preferably 3 to 100 mm. The width of the adhesive layer is the length of the adhesive layer in the direction in which the packaging material is wound around the article.

The packaging material of the present invention is preferably used after packaging an article. The packaging aspect can package the entire article. It is also preferable to wrap a part of the article so as to wrap a part of the article, for example a cap part of a beverage bottle. Moreover, it is also preferable to use it as what is called a multipack which packages many articles collectively.

The packaging material of the present invention can be produced by attaching the packaging material to the article and heating it. That is, it is preferable to have a step of attaching a packaging material to the outer periphery of the article, and then a step of shrinking the heat-shrinkable film by heating.
Although various methods can be considered as a method for attaching the packaging material, the following can be exemplified as typical methods.
1) A method of making the packaging material cylindrical in advance and attaching it to the article
2) A method in which one end of the packaging material is attached in advance to the article, and then the packaging material is wrapped around the outer periphery of the article, so that both ends of the packaging material are overlapped.

In the above method (2), the adhesive for preliminarily attaching the article and the end of the packaging material is not limited to the hot melt adhesive of the present application, and various known adhesives may be used. I can do it. For example, a re-peelable hot melt adhesive label melt P-708J manufactured by Toyo Adre is suitable from the viewpoints of adhesiveness, recyclability, and the like.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these Examples. In the present invention, “parts” and “%” represent “parts by weight” and “% by weight” unless otherwise noted.

<Method of measuring amine value>
Weigh 0.5-2 g of sample accurately. (Sample amount: Sg) 30 mL of neutral ethanol (BDG neutral) is added to a precisely weighed sample and dissolved. The obtained solution is titrated with a 0.2 mol / L ethanolic hydrochloric acid solution (titer: f). The point at which the color of the solution changed from green to yellow was taken as the end point, and the amine value was determined by the following (Formula 1) using the titration amount (AmL) at this time.
(Formula 1) Amine number = (A × f × 0.2 × 56.108) / S

<Number average molecular weight (Mn), weight average molecular weight (Mw)>
The measurement of v number average molecular weight (Mn) and weight average molecular weight (Mw) used GPC (gel permeation chromatography) "ShodexGPC System-21" by Showa Denko KK. GPC is liquid chromatography that separates and quantifies substances dissolved in a solvent based on the difference in molecular size. Tetrohydrofuran is used as a solvent, and weight average molecular weight (Mn) is determined in terms of polystyrene.

<Hydroxyl value (OHV)>
About 1 g of a sample is accurately weighed in a stoppered Erlenmeyer flask and dissolved by adding 100 ml of a toluene / ethanol (volume ratio: toluene / ethanol = 2/1) mixed solution. Further, exactly 5 ml of an acetylating agent (a solution in which 25 g of acetic anhydride was dissolved in pyridine to make a volume of 100 ml) was added and stirred for about 1 hour. To this, phenolphthalein reagent is added as an indicator and lasts for 30 seconds. Thereafter, the solution is titrated with a 0.1N alcoholic potassium hydroxide solution until the solution becomes light red.
The hydroxyl value was determined by the following formula. The hydroxyl value was a numerical value in the dry state of the resin (unit: mgKOH / g).
Hydroxyl value (mgKOH / g) = [{(ba) × F × 28.25} / S] / (Non-volatile content concentration / 100) + D
Where S: Amount of sample collected (g)
a: Consumption of 0.1N alcoholic potassium hydroxide solution (ml)
b: Consumption of 0.1N alcoholic potassium hydroxide solution in the empty experiment (ml)
F: Potency of 0.1N alcoholic potassium hydroxide solution
D: Acid value (mgKOH / g)

<Acid value (AV)>
About 1 g of sample compound (B) was accurately weighed in a stoppered Erlenmeyer flask, and dissolved by adding 100 ml of a toluene / ethanol (volume ratio: toluene / ethanol = 2/1) mixed solution. To this was added a phenolphthalein test solution as an indicator, which was held for 30 seconds, and then titrated with a 0.1N alcoholic potassium hydroxide solution until the solution turned light red.
The acid value (mgKOH / g) was determined by the following equation as the value of the resin in the dry state.
Acid value (mgKOH / g) = {(5.611 × a × F) / S} / (Nonvolatile content concentration / 100)
Where S: Amount of sample collected (g)
a: Consumption of 0.1N alcoholic potassium hydroxide solution (ml)
F: Potency of 0.1N alcoholic potassium hydroxide solution

<Measurement method of viscosity of hot melt adhesive>
The viscosity of the obtained hot melt adhesive was measured using a plate type rheometer. The measurement method and measurement conditions are as follows. The measurement results are shown in Table 1.・ Measuring device: Dynamic viscosity viscoelasticity measuring device Rheosol-G3000 (manufactured by UBM Co., Ltd. ・ Measurement mode: temperature dependence ・ Chuck: parallel plate ・ Waveform: sine wave ・ Parallel diameter: 19.99 mm
・ Cap: 1mm
-Temperature drop viscosity start temperature: 180 ° C Measurement end temperature: 30 ° C
・ Starting temperature measurement temperature: 30 ° C Measurement end temperature: 180 ° C
・ Cooling rate: 3 ° C./min ・ Cooling rate: 3 ° C./min ・ Rotation width: 2 Hz, 3 deg

<Measurement method of softening point (° C)>
The softening point was measured in accordance with 6.4 K-2207 (petroleum asphalt) 6.4 softening point test method (ring and ball method).

<Production example of heat shrinkable film ink>
(Synthesis example of polyester diol)
In a round bottom flask equipped with a stirrer, a thermometer, a water separator and a nitrogen gas introduction tube, 56.846 parts of 2-butyl-2-ethyl-1,3-propanediol (hereinafter abbreviated as BEPG) and 43. adipic acid. 152 parts and 0.002 part of tetrabutyl titanate were charged, and esterification was carried out for 8 hours while removing water produced by condensation at 230 ° C. under a nitrogen stream. After confirming that the acid value of the polyester was 15 or less, the degree of vacuum was gradually raised with a vacuum pump to complete the reaction. As a result, a polyester diol having a hydroxyl value of 56.1 mgKOH / g (number average molecular weight 2000 calculated from the hydroxyl value) and an acid value of 0.3 mgKOH / g was obtained.

(Urethane resin synthesis example 1)
A four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas inlet tube is charged with 22.226 parts of the polyester diol, 5.434 parts of isophorone diisocyanate, and 7.500 parts of ethyl acetate. The mixture was reacted at 120 ° C. for 6 hours under a stream of air, and 7.500 parts of ethyl acetate was added and cooled to obtain 42.663 parts of a solution of a terminal isocyanate prepolymer. Next, 42.663 parts of the solvent solution of the obtained terminal isocyanate prepolymer was added to a mixture of 2.203 parts of isophoronediamine, 0.138 parts of di-n-butylamine, 20.000 parts of ethyl acetate and 20.000 parts of ethanol. Gradually add at room temperature, then react at 50 ° C. for 1 hour, add 15.000 parts of ethanol, add polyester urethane with solid content 30.0%, weight average molecular weight 24000, amine number 4.0 mg KOH / resin 1 g. Obtained.

(Urethane resin synthesis example 2)
In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas introduction tube, 1041.6 parts of polypropylene glycol (PPG2000, manufactured by NOF Corporation) having a number average molecular weight (hereinafter referred to as Mn) of 2000, isophorone diisocyanate 266 .7 parts, stannous 2-ethylhexylate and 200 parts of ethyl acetate were added, reacted at 85 ° C. for 3 hours under a nitrogen stream, cooled by adding 366.0 parts of ethyl acetate, and terminal isocyanate prepolymer 1874.6 parts of a solvent solution was obtained. Next, 91.3 parts of isophoronediamine, 1.54 parts of di-n-butylamine, 6.2 parts of aminoethylethanolamine, 1200 parts of ethyl acetate and 1120 parts of isopropyl alcohol were mixed with the resulting terminal isocyanate prepolymer 1581. .1 part was gradually added at room temperature and then reacted at 50 ° C. for 1 hour to obtain a polyetherurethane having a solid content of 30% and a weight average molecular weight of 35,000.

(Acrylic resin polymerization example 1)
A four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube was charged with 10 parts of methacrylic acid, 33 parts of methyl methacrylate, 21 parts of butyl methacrylate, 36 parts of styrene and 200 parts of methyl ethyl ketone, and nitrogen. In an air stream, the temperature was raised to 90 ° C. with stirring, 2 parts of azobisisobutyronitrile was added, the polymerization reaction was carried out for 2 hours, 50 parts separated and purified, 34 parts ethyl acetate and isopropyl alcohol 16 The acrylic resin 1 having a solid content of 50%, an acid value of 60, a Tg of 110 ° C., and a weight average molecular weight of 4000 was obtained.

(Acrylic resin polymerization example 2)
In a four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube, 24 parts of methacrylic acid, 60 parts of methyl methacrylate, 6 parts of 2-ethylhexyl acrylate, 10 parts of styrene and 200 parts of methyl ethyl ketone The mixture was heated to 90 ° C. with stirring in a nitrogen stream, and 2 parts of azobisisobutyronitrile was added to carry out a polymerization reaction for 2 hours. 16 parts of isopropyl alcohol was added to obtain an acrylic resin 2 having a solid content of 50%, an acid value of 140, a Tg of 90 ° C., and a weight average molecular weight of 10,000.

(Preparation of nitrocellulose resin)
60 parts of nitrocellulose resin (HIG1 / 8GKCNC, manufactured by KOREACNC) was mixed and dissolved in 20 parts of ethyl acetate and 20 parts of isopropyl alcohol to obtain a nitrocellulose resin varnish.

(Preparation of vinyl chloride / vinyl acetate copolymer resin)
25 parts of vinyl chloride / vinyl acetate copolymer resin (Solvain TA5R manufactured by Nissin Chemical Co., Ltd.) was mixed and dissolved in 75 parts of ethyl acetate to obtain a vinyl chloride / vinyl acetate copolymer resin varnish. Hydroxyl value 166.3 KOHmg / g.

(Ink 1)
30.0 parts of Titanic JR-805 (manufactured by Teica), 20.0 parts of polyester urethane, 5.0 parts of ethyl acetate and 5.0 parts of ethanol were stirred and mixed in a sand mill, and then 30.0 parts of polyester urethane. Parts, ethyl acetate 5.0 parts and ethanol 5.0 parts were stirred and mixed to obtain white printing ink (W1 was obtained. To 100 parts of the obtained white printing ink (W1), fatty acid amide P (manufactured by Kao Corporation) was added. 5 parts, 50 parts of an ethyl acetate / ethanol mixed solvent (weight ratio 50/50) having the same solvent composition as W1 was added and mixed as a diluent solvent to obtain a white diluted printing ink (ink 1).

(Ink 2-6)
White printing inks (W2 to 6) and white diluted printing inks (inks 2 to 6) were obtained in the same manner as ink 1 with the charging ratio shown in Table 1. In addition, the solvent type before and after wrought meat and the amount of solvent are the same as in the production example of ink 1.

The raw materials used for the hot-melt adhesive for heat-shrinkable film are as follows.

<Elastomer>
Kraton G1650 (manufactured by Kraton Polymer Co., Ltd.) (hereinafter abbreviated as “G1650”), composition: styrene-ethylene-butylene-styrene block polymer (SEBS), diblock amount: 0%, melt viscosity * 1: 8 Pa s
Kraton G1652 (manufactured by Kraton Polymer Co., Ltd.) (hereinafter abbreviated as “G1652”), composition: styrene-ethylene-butylene-styrene block polymer (SEBS), diblock amount: 0%, melt viscosity * 1; 350 Pa · s
Kraton G1730 (manufactured by Kraton Polymer Co., Ltd.) (hereinafter abbreviated as “G1730”), composition: styrene-hydrogenated polybutadiene-styrene block polymer (SEPS), melt viscosity * 1; 2.0 Pa · s

The melt viscosity * 1 is a melt viscosity at 25 ° C. of a toluene solution having a thermoplastic elastomer concentration of 25% by weight. The melt viscosity was measured using a B-type viscometer RB80L (manufactured by Toki Sangyo Co., Ltd.). 3 was measured.

<Tackifier>
· Haritac F (manufactured by Harima Chemicals), composition: hydrogenated rosin, acid value: 175 mgKOH / g, softening point: 72 ° C
YS Polystar T30 (manufactured by Yasuhara Chemical Co., Ltd.) (hereinafter abbreviated as “T30”) Composition: terpene phenol resin, softening point: 30 ° C.

<Plasticizer>
Diana Fresia N90 (made by Idemitsu Kosan Co., Ltd.) (hereinafter abbreviated as “N90”) Composition: Paraffinic process oil

<Polypropylene wax>
NP-030 (Mitsui Chemicals, Inc.) molecular weight 5,800, softening point 153 ° C
NP-055 (Mitsui Chemicals, Inc.) molecular weight 7,000, softening point 148 ° C
NP-056 (Mitsui Chemicals, Inc.) molecular weight 7,000, softening point 131 ° C

<Removable hot melt adhesive>
Label melt P-708J (manufactured by Toyo Adre)

<Production example of hot melt adhesive for heat shrinkable film>
(Adhesive 1)
A stainless beaker equipped with a stirrer was charged with 30 parts by weight of a plasticizer (N90), 15 parts by weight of an elastomer (G1652) and 5 parts by weight of a tackifier (T30), and heated to melt. Heating was performed with care so that the contents would not be below 130 ° C and above 150 ° C. After melting, stirring is performed to obtain a uniform molten solution, and while maintaining the temperature below 150 ° C. and continuing stirring, 35 parts by weight of a tackifier: Haritac F is gradually added to the melt, and after completion of the addition, 15 parts by weight of polypropylene wax (NP-030) was added to obtain a homogeneous melt mixture, and cooled to obtain an adhesive 1.

(Adhesive 2-5)
Each raw material was changed as described in Table 2, and adhesives 2 to 5 were obtained in the same manner as adhesive 1.

(Adhesive 6-8)
Each raw material was changed as described in Table 3, and adhesives 6 to 8 were obtained in the same manner as adhesive 1.

<Paraffin wax>
-HNP-9 (Nippon Seiwa Co., Ltd.) molecular weight 500, softening point 75 ° C

Next, a method for creating printed materials and packaging materials will be described.
In the following description, the design print layer formed by the ink n (n = 1 to 6) is the design print layer n, the print having the design print layer n is the print n, and the adhesive m (m = 1 to 8) is The adhesive layer to be formed is expressed as an adhesive layer m, and the adhesive layer formed by the re-peelable hot melt adhesive (label melt P-708J) is expressed as an article adhesive layer.

[Example 1]
<How to create printed matter>
An NBR (nitrile butadiene rubber) rubber hardness 80Hs impression cylinder, a blade thickness of 60 μm (base material thickness 40 μm, one side ceramic layer thickness 10 μm), a chrome hardness 1050 Hv made by Toyo Prepress Co., Ltd. Electronic engraving plate (stylus angle 130 degrees, for color ink: 175 lines / inch, for white ink: 175 lines / inch), and ink 1 were set on a gravure printing machine manufactured by Fuji Machine Industry Co., Ltd., doctor pressure 2 kg / cm ^2, printing pressure 2 kg / cm ^2, printing speed 60 m / min, under the conditions of a drying temperature 60 ° C., was printed in the MD direction uniaxially stretched polyethylene terephthalate film having a thickness of 20 [mu] m (manufactured by Toyobo Co., Ltd.), having a design printed layer 1 Print 1 was obtained.

<Method of making packaging material 1 for shrink aptitude test (S1)>
The adhesive layer 1 was formed by heating the adhesive 1 to 150 ° C., melting it, and coating the release sheet with a hand applicator to a coating thickness of 60 μm and a width of 15 mm. Next, the adhesive layer 1 is transferred to one end of the printed surface 1 and the horizontally long direction of the printed material 1 that has been cut to a size of 17 cm in length and 22 cm in width, and laminated to form a packaging material 1 for shrink aptitude test (S1 )

<Method for creating packaging material 1 (T1) for coating suitability test>
In the coating suitability test, a coating method different from the coating method of the shrinkage suitability packaging material 1 was used. Specifically, using a melter series 3400 (slit coater method) manufactured by Nordson Co., under the conditions of a coating machine temperature of 140 ° C., a hose temperature of 140 ° C., a head temperature of 110 ° C., and a coating speed of 20 to 150 m / min. 1 was coated with adhesive 1. Furthermore, the coating was separately stopped for 1 hour and then coated again. These series of test samples were designated as sample 1 for coating suitability test (T1).

[Examples 2 to 10]
As described in Table 4, inks 1 to 6 and adhesives 1 to 5 were printed and laminated in the same manner as in Example 1, and packaging materials for shrink aptitude test 2 to 10 (S2 to S10), coating Aptitude test samples 2 to 10 (T2 to T10) were obtained.

[Example 11]
A hot melt adhesive (product name: Toyomelt P-708K, manufactured by Toyo Atole) was heated to 150 degrees and melted. The article adhesive layer was formed by coating the release sheet with a hand applicator so that the coating thickness was 30 μm and the width was 15 mm. The article adhesive layer was transferred to the other end of the shrink suitability test packaging material 1 where the adhesive layer 1 was not formed and laminated to obtain a shrink suitability test packaging material 11 (S11).
Example 11 is different from Examples 1 to 10 in that one end of the packaging material is attached in advance to the article, and then the packaging material is wrapped around the outer periphery of the article so that both ends of the packaging material are attached. It is an Example for evaluating the method to overlap. Accordingly, the coating suitability test sample is not prepared because it is the same as the coating suitability test sample 1 (T1).

[Comparative Examples 1-3]
Ink 1 and adhesives 6 to 8 were printed and laminated in the same manner as in Example 1 as described in Table 4, and packaging suitability test materials 12 to 14 (S12 to S14) and coating suitability test were conducted. Samples 12 to 14 (T12 to T14) were obtained.

[Comparative Example 4]
By cutting MD direction uniaxially stretched polyethylene terephthalate film (manufactured by Toyobo Co., Ltd.) to a size of 17 cm in length and 22 cm in width, and transferring the adhesive 3 to the end of the film in the same manner as in Example 1, The packaging material 15 for shrink aptitude test (S15) and the packaging material 15 for coating aptitude test (T15) which do not have a design printing layer were obtained.

The description of Table 4 is as follows.
○: Applicable ink and adhesive are printed and laminated.
Blank or “None”: The corresponding ink or adhesive is not used.
If Example 3 is taken and demonstrated, the packaging material which laminated | stacked the adhesive agent 3 on the printed matter 1 which printed the ink 1 is created. Furthermore, two types of packaging material 3 for shrinkability test (S3) and packaging material 3 for coating aptitude test (T3) are created according to the difference in the adhesive lamination method.
Moreover, if it demonstrates also about the comparative example 4, the printed material is not used and the packaging material which laminated | stacked only the adhesive agent 3 on the polyethylene terephthalate film is created.

[Sample 1 for shrinkability test]
The packaging material 1 for shrink suitability test is bonded to the cylindrical packaging material processed product 1 with the adhesive portion 1 facing inward so that all portions of the adhesive portion overlap the other end of the packaging material 1. Created. A sample 1 (SS1) for shrink aptitude test was obtained by mounting the processed packaging material 1 on the barrel of a cylindrical PET bottle having a circumference of 200 mm.

[Samples 2 to 10 for shrinkability test]
The shrink aptitude test samples 2 to 10 (SS1 to SS10) were obtained by mounting the shrink aptitude test packaging materials 2 to 10 on the trunk of the PET bottle in the same manner as the test sample 1.

[Shrink aptitude test sample 11]
The article adhesive layer of the shrink aptitude test packaging material 11 was attached to the body of a cylindrical PET bottle having a circumference of 200 mm. Next, the sample 11 (SS11) for shrink aptitude test is obtained by wrapping around the outer periphery of the PET bottle so that all portions of the adhesive layer 1 of the packaging material 11 overlap the other end of the packaging material 11. It was.

[Shrink aptitude test samples 12-15]
The shrink aptitude test samples 12 to 15 (SS12 to SS15) were obtained by mounting the shrink aptitude test packaging materials 12 to 15 on the trunk of the PET bottle in the same manner as the test sample 1.

<Shrink aptitude test>
The obtained shrink aptitude test samples 1 to 15 (SS1 to SS15) were immersed in a hot water bath heated to 90 ° C. to shrink the heat-shrinkable film, and the appearance was visually evaluated. Evaluation criteria are as follows: ○: The deviation of the adhesive part 1 is 2 mm or less, and the packaging material does not peel off.
X: The shift | offset | difference of the adhesion part 1 was larger than 2 mm, or the packaging material peeled.

<Coating suitability test>
As described above, the coating aptitude test samples 1 to 10 and 12 to 15 (T1 to T10 and T12 to T15) were prepared using the Nordson Melter Series 3400 (slit coater method). The evaluation criteria are as follows.
A: The coated surface was extremely smooth and uniform, and the coating could be performed without problems.
○: The coated surface was uniform and coating was possible without problems.
Δ: Coating was completed, but the coated surface was uneven.
X: Re-coating was not possible. Or, during re-coating, stringing of the adhesive occurred.

Claims (5)

A heat-shrinkable film , a design printing layer made of printing ink for heat-shrinkable film (A), and a packaging material laminated in the order of an adhesive layer made of hot-melt adhesive for heat-shrinkable film (B),
The printing ink for heat-shrinkable film (A) contains at least one resin selected from the group consisting of urethane resin, acrylic resin, nitrocellulose resin and vinyl chloride / vinyl acetate copolymer resin, and heat shrink A packaging material, which is the following (B1) to (B4) in 100 parts by weight of the hot melt adhesive (B) for adhesive film.
(B1) Styrenic elastomer having polystyrene and rubber intermediate block 10-25 parts by weight (B2) Tackifier 25-40 parts by weight (B3) Process oil 20-40 parts by weight (B4) Softening point is 125 ° C. or higher and 165 ° C. 15 to 35 parts by weight of polypropylene wax at ℃ or lower   The packaging material according to claim 1, wherein the heat-shrinkable film has the design print layer on at least one surface, and the adhesive layer is provided on at least one end of the film.   A method for producing an article with a packaging material, comprising: a step of mounting the packaging material according to claim 1 on the outer periphery of the article; and a step of shrinking the heat-shrinkable film by heating.   The process of mounting the packaging material according to claim 3 is a process of forming a cylindrical packaging material by overlapping one end of the packaging material on the other end and mounting the cylindrical packaging material on the outer periphery of the article. The method for producing an article with a packaging material according to claim 3.   The step of attaching the packaging material according to claim 3 includes a step of attaching one end of the packaging material to the article, and then winding the packaging material around the outer periphery of the article, The method for producing an article with a packaging material according to claim 3, comprising a step of pasting so that end portions of the packaging material overlap.

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