JPH0242474A - Label - Google Patents

Abstract

PURPOSE:To improve printability, processability and post processability by providing a resin layer which consists essentially of a copolymer formed by grafting a compd. having an unsatd. bond with a hydrophilic group-contg. polyester resin and a crosslinking binder and has a specific grafting ratio of the copolymer. CONSTITUTION:A tacky adhesive agent layer, a polyester film and the resin layer which consists essentially of the copolymer formed by grafting the compd. having the unsatd. bond with the hydrophilic group-contg. polyester resin and the crosslinking binder and has 0.5-600% grafting rate of the copolymer are laminated in this order. The printability, processability and post processability are improve in this way.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to labels, specifically labels using polyester film, particularly printed labels, more preferably labels printed using U-curing ink. , or a label provided with a heat-sensitive coloring layer.

[Conventional technology] Conventional labels using polyester film include:
Films in which various easy-to-print layers are provided on a polyester film (for example, Japanese Patent Laid-Open No. 62-297147) have been known.

[Problems to be Solved by the Invention] However, the above conventional film has the following problems.

In other words, problems such as ■ lack of high-speed printing properties, ■ blocking of the easy-to-print layer, and ■ poor printability when various surface treatments (hairline processing, sandblasting, etc.) are applied to change the surface gloss. We have it.

The present invention improves these problems and improves printability, processing suitability,
The purpose is to provide labels with excellent post-processability.

[Means for Solving the Problems] The present invention provides: (1) Adhesive 1! A, a copolymer (c) obtained by grafting a compound (b) having an unsaturated bond to a polyester film B and a hydrophilic group-containing polyester resin (a), and a crosslinking agent as main components, and grafting of the copolymer. rate is 0
．． A label characterized by laminating resin layers C of 5 to 600% in this order, (2) the center line roughness of the resin layer C is 0.2 to 0.8 μm, and the gloss is 60% or less 2. The label according to claim 1, characterized in that:

In the present invention, the polyester constituting the polyester film B is a well-known polyester, specifically, for example, terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, bis-α, β(2-chlorophenoxy)ethane-4,4- Polycondensation of at least one difunctional carboxylic acid such as dicarboxylic acid, adipic acid, and sebacic acid and at least one glycol such as ethylene glycol, triethylene glycol, tetramethylene glycol, hexamethylene glycol, and decamethylene glycol. Examples include polyesters obtained by In addition, the polyester may be blended or copolymerized with other polymers within a range that does not impede the purpose of the present invention, and may contain antioxidants, heat stabilizers, lubricants, pigments, ultraviolet absorbers, etc. It may be The intrinsic viscosity of the polyester (measured in orthochlorophenol at 25 DEG C.) is from Oo.4 to 2.0, preferably from 0.5 to 1.0.

The present invention includes polyesters such as polyethylene terephthalate, polyethylene-2,6-naphthalate, polyethylene-α, β-bis(2-chlorophenoxy)ethane-
Particularly excellent effects are obtained when 4,4°-dicarboxylate is used.

The hydrophilic group-containing polyester resin (a) (hereinafter referred to as resin (a)) as used in the present invention refers to hydrophilic groups or hydrophilic components in the molecule, such as hydroxyl groups, carboxyl groups, carbonyl groups, cyano groups, amino It is a polyester copolymer into which at least one of a group, a methyl carbonyl group, a polyethylene glycol group, a carboxylic acid group, a phosphate ester salt, a quaternary ammonium salt, a sulfuric ester salt, a sulfonate, etc. is introduced. Among these, typical polyester copolymers having the following compositions are useful. That is, polycondensates of aromatic dicarboxylic acids and/or non-aromatic dicarboxylic acids, ester-forming sulfonic acid alkali metal salt compounds, and glycols may be mentioned. Specifically, aromatic dicarboxylic acids include, for example, terephthalic acid, isophthalic acid, phthalic acid, 2,5-dimethylterephthalic acid, 2,6-naphthalenedicarboxylic acid, biphenyldicarboxylic 2-bis(phenoxy)ethane-p ．． 0'-dicarboxylic acids and their ester-forming derivatives; non-aromatic dicarboxylic acids include, for example, oxalic acid, malonic acid, succinic acid, geltaric acid, adipic acid, sebacic acid, 1.2
-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid and ester-forming derivatives thereof. Among these, it is preferable that aromatic dicarboxylic acids and/or their ester-forming derivatives account for 40 mol% or more of the total dicarboxylic acid components in terms of heat resistance, film strength, and water resistance of the resin, and within this range, More than one type of dicarboxylic acid may be used in combination.

Examples of ester-forming sulfonic acid alkali metal salt compounds include sulfoterephthalic acid, 5-sulfoisophthalic acid, 4-sulfophthalic acid, and 4-sulfonaphthalene-2.
．． 7-dicarboxylic acid, sulfo-〇-xylylene glycol, 2-sulfo-1,4-bis(hydroxyethoxy)
Examples include alkali metal salts such as benzene (alkali metal salts of sulfonic acids) and ester-forming derivatives thereof, and 5-sulfoisophthalic acid, sodium sulfoterephthalic acid, and their ester-forming derivatives are more preferably used.

Next, the glycol component is an aliphatic glycol having 2 to 8 carbon atoms or an alicyclic glycol having 6 to 12 carbon atoms,
For example, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,2-propylene glycol, neopentyl glycol, 1,4-cyclohexane dimetatool, 1,6-hexanediol, 1,3-
Cyclohexane dimetatool, 1.

Preferably used are 2-cyclohexane dimetatool, xylylene glycol, diethylene glycol, triethylene glycol, and the like.

In some cases, polyethers may be copolymerized.

Polyether here refers to a hydrophilic polymer having ether bonds as the main bond chain, and particularly preferred are aliphatic polyethers, such as polyethylene glycol, polypropylene glycol, glycerin ether,
Polyethylene glycol ether and the like are preferably used.

The resin (a) may be water-soluble or water-dispersible, and its solubility depends on the type and blending ratio of the copolymer components, the presence or absence of addition of a hydrophilic organic compound used as a dispersion stabilizing agent, and its type. The hydrophilic organic compound is preferably added in a small amount as long as it does not impair dispersion stability, although it varies depending on the amount of the hydrophilic organic compound added. In addition, hydrophilic organic compounds include aliphatic and alicyclic alcohols, esters, ethers, and ketones. For example, alcohols include methanol, ethanol, isopropanol, n-butanol, and glycols include ethylene glycol and propylene. Examples of glycols include derivatives thereof such as methyl cellulone, ethyl cellosolve, and n-butyl cellosolve, esters such as ethyl acetate, ethers such as dioxane and tetrahydrofuran, and ketones such as methyl ethyl ketone. The hydrophilic organic compounds may be used alone or in combination of two or more as necessary. Among the hydrophilic organic compounds, butyl cellosolve and ethyl cellosolve are particularly preferred in view of dispersion performance, dispersion stability, coating properties, and the like. Furthermore, in the case of resin (a), an increase in the amount of components that particularly contribute to hydrophilicity, such as the ester-forming alkali metal sulfonate compound in the copolymerization composition, significantly deteriorates the water resistance of the applied modified layer. A small amount is preferable as long as solubility, dispersion stability, etc. are not impaired.

The glass transition temperature (Tq) of the resin (a) in the present invention is not particularly limited, but is preferably in the range of 0 to 80'C1, more preferably 30 to 75C. This is because water resistance, alkali resistance, and heat resistance are improved.

Resin (a) can usually be manufactured using conventional polyester manufacturing techniques. That is, the desired polymer is obtained by melt polycondensing the acid component and glycol component described above using a reaction catalyst such as an esterification or transesterification catalyst or a polymerization catalyst. Furthermore, solution polycondensation can also be applied. At this time, various modifiers, stabilizers, etc. may be added to the extent that they do not adversely affect the grafting reaction.

Furthermore, the presence of the hydrophilic organic compound is necessary to obtain an aqueous dispersion of resin (a) lacking in water solubility. Usually resin (
It is produced by mixing a) with a hydrophilic organic compound and adding water while stirring, preferably heating and stirring, or by adding the above mixture to water under stirring. In addition, when the solid content concentration of the resulting aqueous dispersion becomes high, the fine particles of the resin (a) tend to re-agglomerate, making the uniform dispersion system unstable and making the grafting reaction difficult.

Compound (b) having an unsaturated bond as used in the present invention (hereinafter referred to as
The compound (b) is a compound that is grafted onto the resin (a), and specifically includes vinyl esters such as vinyl propionate, vinyl stearate, higher tertiary vinyl esters, Vinyl chloride, vinyl bromide, unsaturated carboxylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate,
Butyl methacrylate, butyl maleate, octyl maleate, butyl fumarate, octyl fumarate, glycidyl acrylate, glycidyl methacrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxypropyl acrylate, methacrylic acid Dimethylaminoethyl, dimethylaminoethyl acrylate, ethylene glycol dimethacrylate, ethylene glycol diacrylate, polyethylene glycol dimethacrylate, polyethylene glycol diacrylate, unsaturated carboxylic acid amides such as acrylamide,
Methacrylamide, methylol acrylamide, butoxymethylol acrylamide, unsaturated nitriles such as acrylonitrile, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, maleic acid! Acidic esters, fumar I1M esters, itacone 1ull esters, acrylic compounds such as allyl acetate, allyl glycidyl ether, allyl methacrylate, allyl acrylate,
Diallyl itaconate, nitrogen-containing compounds such as vinylpyridine, vinylimidazole, hydrocarbons such as ethylene, propylene, hexene, octene, styrene, vinyltoluene, butadiene, vinylsilane compounds such as dimethylvinylmethoxysilane, dimethylethylethoxysilane , methylvinyldimethoxysilane, methylvinyljethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, and at least one selected from these is particularly applicable. It is not limited.

The grafted copolymer (c) in the present invention (hereinafter referred to as
The polymer (c) is obtained by grafting the compound (b) onto the resin (a). Incidentally, the polymer (c) is produced by a conventional graft polymerization method. That is, the reaction is carried out by adding the compound (b) in the presence of a water-soluble or water-dispersible polymerization initiator in an aqueous medium system containing the resin (a). Examples of polymerization initiators used include ceric ammonium nitrate, potassium persulfate, ammonium persulfate, hydrogen peroxide, azobisisobutyronitrile, and benzoyl peroxide.
) It is preferable to use an organic peroxide such as benzoyl peroxide in terms of graft polymerization reactivity to The graft polymerization reaction is usually carried out under cooling or heating, and the reaction temperature is 5 to 50% depending on the reaction rate, stability of the polymerization system, properties of the polymer (c), etc.
The temperature is 100°C, preferably 10-80°C.

In the present invention, the grafting rate of compound (b) to resin (a) is 0.5 to 600%, preferably 5 to 300%.
, more preferably in the range of 10 to 100%. If the grafting rate is less than 0.005%, water resistance deteriorates, which is not preferable.

If the grafting rate exceeds 600%, it is not preferable because the coatability deteriorates and the adhesion between the modified layer and the substrate base decreases.

The crosslinking agent used in the present invention refers to a crosslinking agent that undergoes a thermal crosslinking reaction with a functional group present in the resin (a) or polymer (c), such as a hydroxyl group, a carboxyl group, a glycidyl group, an amide group, etc., and finally forms a tertiary It is a crosslinking agent for forming a modified layer having an original network structure, and is not particularly limited. In particular, it is preferable to use an isocyanate crosslinking agent, a melamine crosslinking agent, a urea crosslinking agent, or an epoxy crosslinking agent as the crosslinking agent because the crosslinking effect is large. As an epoxy crosslinking agent,
Specific examples include polyepoxy compounds, jepoxy compounds, monoepoxy compounds, etc. Examples of polyepoxy compounds include sorbitol, polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, Triglycidyl tris (
2-Hydroxyethyl> isocyanate, glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, and jepoxy compounds include, for example, neopentyl glycol diglycidyl ether, 1.
6-hexanesiol diglycidyl ether, resorcin diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether,
Examples of polypropylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, and monoepoxy compounds include allyl glycidyl ether, 2-ethylhexyl glycidyl ether, and phenyl glycidyl ether. Examples of the urea curing agent include dimethylol urea, dimethylol ethylene urea, dimethylol propylene urea, tetramethylol acetylene urea, and 4-methoxy-5-dimethylpropylene urea dimethylol. As the melamine-based crosslinking agent, compounds obtained by etherifying a methylolmelamine derivative obtained by condensing melamine and formaldehyde with lower alcohol such as methyl alcohol, ethyl alcohol, isopropyl alcohol, etc., and mixtures thereof are preferable. Examples of methylolmelamine derivatives include monomethylolmelamine, dimethylolmelamine, trimethylolmelamine, tetramethylolmelamine, pentamethylolmelamine, and hexamethylolmelamine. These crosslinking agents may be used alone, or in some cases, two or more types may be used in combination. The amount of crosslinking agent added is not particularly limited, but it is usually added to the resin (
0.001 to 60 parts by weight, preferably 0.0 parts by weight per 100 parts by weight of solid content in the mixture of a) and polymer (c)
It is 1 to 20 parts by weight.

When it is within this range, it is preferable because the coating properties and the moisture resistance of the coating film are excellent.

The polyester film constituting the film of the present invention is at least uniaxially oriented by a conventional method, but is preferably at least biaxially oriented in terms of mechanical strength, dimensional stability, rigidity, etc. Further, the thickness of the polyester film is not particularly limited, but is preferably from 2 to 500 μm, more preferably from 5 to 300 μm, and is excellent in practical handling as a base material.

The laminated thickness of the resin layer C constituting the film of the present invention is not particularly limited, but is usually in the range of 0.005 to 5.0 μm, preferably 0.01 to 1.0 μm. Especially resin layer C
It is preferable to stretch the polyester film provided on the polyester film in at least one axial direction or more, since the adhesiveness with the polyester film is further improved.

In addition, the resin layer C includes a known crosslinking catalyst, specifically salts,
By including inorganic substances, organic substances, acid substances, alkaline substances, etc., and known adhesion promoters, the advantages in post-processing can be increased. Furthermore, if necessary, known resin components and additives may be added in amounts that do not impair the effects of the present invention, such as antifoaming agents, coating properties improvers, thickeners, antistatic agents, antioxidants, etc.
It may contain ultraviolet absorbers, dyes, pigments, etc., or it may contain fine particles made of an inorganic or organic compound as a lubricant.

In the resin layer C, a hydrophilic group-containing polyester and/or a water-soluble or water-dispersible acrylic resin is further added within a range that does not impair the effects of the present invention, specifically less than 50% weight loss, preferably 3 to 35% by weight. % range is more suitable because the versatility of the easily bonding layer is further increased.

The hydrophilic group-containing polyester resin herein refers to hydrophilic groups or hydrophilic components in the molecule, such as hydroxyl groups, carboxyl groups, carbonyl groups, cyano groups, amino groups, methylcarbonyl groups, polyethylene glycol, carboxylates,
It is a polyester copolymer into which at least one of a phosphoric acid ester salt, a quaternary ammonium salt, a sulfuric acid ester salt, a sulfonate, etc. is introduced. Among these, typical polyester copolymers having the following compositions are useful.

That is, polycondensates of aromatic dicarboxylic acids and/or non-aromatic dicarboxylic acids, ester-forming sulfonic acid alkali metal salt compounds, and glycols may be mentioned. Specifically, aromatic dicarboxylic acids include, for example, terephthalic acid, isophthalic acid, phthalic acid, 2,5-dimethylterephthalic acid, 2,6-naphthalenedicarboxylic acid, biphenyldicarboxylic acid, and ester-forming derivatives thereof. Examples of non-aromatic dicarboxylic acids include glacial acid, malonic acid,
Succinic acid, geltaric acid, adipic acid, sebacic acid, 1
, 2-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid and ester-forming derivatives thereof. Among these, it is preferable that aromatic dicarboxylic acids and/or their ester-forming derivatives account for 40 mol% or more of the total dicarboxylic acid components in terms of heat resistance, film strength, and water resistance of the resin.
One or more dicarboxylic acids may be used in combination within this range.

Examples of ester-forming sulfonic acid alkali metal salt compounds include sulfoterephthalic acid, 5-sulfoisophthalic acid, 4-sulfophthalic acid, and 4-sulfonaphthalene-2.
, 7-dicarboxylic acid, sulfo-oxylylene glycol, alkali metal salts (alkali metal salts of sulfonic acid) such as 2-sulfo-1,4-bis(hydroxyethoxy)benzene, and ester-forming derivatives thereof, More preferably, 5-sulfoisophthalic acid, sodium sulfoterephthalic acid and ester-forming derivatives thereof are used.

Next, the glycol component is an aliphatic glycol having 2 to 8 carbon atoms or an alicyclic glycol having 6 to 12 carbon atoms,
For example, ethylene glycol, 1.3-propanediol, 1,4-butanediol, 1.2-propylene glycol, neopentyl glycol, 1.4-cyclohexane dimetatool, 1,6-hexanediol, 1.3
-cyclohexane dimetatool, 1°2-cyclohexane dimetatool, p-xylylene glycol, diethylene glycol, triethylene glycol and the like are preferably used.

In some cases, polyethers may be copolymerized.

The polyether here refers to a hydrophilic polymer having an ether bond as its main bond chain, and particularly preferred are aliphatic polyethers, such as polyethylene glycol, polypropylene gel IJ) -/L/, and glycerin ether. , polyethylene glycol ether, etc. are preferably used.

The resin may be water-soluble or water-dispersible, and its solubility depends on the type and blending ratio of the copolymer components, or the presence or absence of the addition of a hydrophilic organic compound used as a dispersion stabilizing agent, its type, and composition. Although it varies depending on the amount, it is preferable that the hydrophilic organic compound be added in a small amount as long as it does not impair dispersion stability. In addition, hydrophilic organic compounds include aliphatic and alicyclic alcohols, esters, ethers, and ketones. For example, alcohols include methanol, ethanol, isopropanol, n-butanol, and glycols include ethylene glycol and propylene. Glycols are derivatives such as methylcellosolve, ethylcellosolve, n-butylcellosolve, ethyl acetate as esters, dioxane as ethers,
Examples of tetrahydrofuran and ketones include methyl ethyl ketone. The hydrophilic organic compounds may be used alone or in combination of two or more as necessary. Among the hydrophilic organic compounds, Butyl Celnlup and Ethyl Celsolve are particularly preferred from the viewpoint of dispersion performance, dispersion stability, coating properties, and the like. Furthermore, in this resin, an increase in the amount of a component that contributes to hydrophilicity, such as an ester-forming alkali metal sulfonate compound in the copolymerization composition, significantly deteriorates the water resistance of the applied modified layer, so it is difficult to dissolve the resin. , a small amount is preferable as long as dispersion stability etc. are not impaired.

Furthermore, the water-dispersible or water-soluble acrylic resin (hereinafter abbreviated as acrylic resin) is not particularly limited, but representative examples include the following. That is, it contains alkyl acrylate or alkyl methacrylate as a main component, and the component 30 to
It is a water-soluble or water-dispersible resin containing 90 mol% and 70 to 10 mol% of a vinyl monomer component copolymerizable with these and having a functional group.

Preferred functional groups of vinyl monomers that are copolymerizable with acrylic acrylate or alkyl methacrylate and have a functional group include a carboxyl group or a salt thereof, an acid anhydride group, a sulfonic acid group or a salt thereof, an amide group, or an alkylol group. amide groups, amine groups (including substituted amino groups), alkylolated amino groups, salts thereof, hydroxyl groups, epoxy groups, etc. Particularly preferred are carboxyl groups or salts thereof, acid anhydride groups, and epoxy groups. Naturally, two or more types of these groups may be contained in the resin.

It is preferable that the alkyl acrylate or alkyl methacrylate in the acrylic resin is 30 mol % or more because coating formability, coating film strength, and blocking resistance are improved. When the amount of alkyl acrylate or alkyl methacrylate in the acrylic resin is 90 mol% or less, introducing a compound having a specific functional group into the acrylic resin as a copolymerization component makes it easier to water-solubilize and water-disperse the resin. It is preferable because the condition is stable for a long period of time, and furthermore, the adhesiveness between the coating layer and the polyester film layer can be improved, and the strength, water resistance, and chemical resistance of the coating layer can be improved by reaction within the coating layer.

Examples of alkyl groups in alkyl acrylates and alkyl methacrylates include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, 2-ethylhexyl group, lauryl group, stearyl group. , cyclohexyl group, etc.

As the vinyl monomer having a functional group copolymerizable with alkyl acrylate or alkyl methacrylate, the following compounds having functional groups such as a reactive functional group, a self-crosslinking functional group, and a hydrophilic group can be used.

Examples of compounds having a carboxyl group or a salt thereof, or an acid anhydride group include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, metal salts of these carboxylic acids with sodium etc., ammonium salts, Alternatively, maleic anhydride may be mentioned.

Examples of compounds having a sulfonic acid group or a salt thereof include vinyl sulfonic acid, styrene sulfonic acid, metal salts of these sulfonic acids with sodium, ammonium salts, and the like.

Examples of compounds having an amide group or an alkylolated amide group include acrylamide, methacrylamide, n-methylmethacrylamide, methylolated acrylamide, methylolated methacrylamide, ureido vinyl ether, β-ureido isobutyl vinyl ether,
Examples include ureidoethyl acrylate.

Examples of compounds having an amino group or an alkylolated amino group or a salt thereof include diethylaminoethyl vinyl ether, 3-aminopropyl vinyl ether, 2-aminobutyl vinyl ether, dimethylaminoethyl methacrylate, dimethylaminoethyl vinyl ether, and amino groups thereof. Examples include those obtained by methylolization of , and those obtained by 4@chlorination with alkyl halides, dimethyl sulfate, sultone, etc.

Examples of compounds having a hydroxyl group include β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate,
β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, β-hydroxy vinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether, polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, polypropylene glycol monoacrylate, polypropylene glycol monomethacrylate, etc. can be mentioned.

Examples of the compound having an epoxy group include glycidyl acrylate and glycidyl methacrylate.

Furthermore, in addition to the above compounds, the following compounds may be used in combination. That is, acrylonitrile, methacrylate trile,
Styrenes, butyl vinyl ether, mono- or dialkyl maleic acid esters, mono- or dialkyl fumaric acid esters, mono- or dialkyl itaconic acid esters, methyl vinyl ketone, vinyl chloride, vinylidene chloride, vinyl acetate, vinyl pyridine, vinyl pyrrolidone, vinyl trimethoxy Examples include, but are not limited to, silane.

The acrylic resin may contain a surfactant, but the low-molecular-weight surfactant contained in the acrylic resin may become concentrated during the film-thickening process and accumulate at the interface between particles. , may migrate to the interface of the coating layer, causing problems in the mechanical strength, water resistance, and adhesion to the laminate of the coating layer. In such a case, a polymer obtained by so-called soap-free polymerization that does not contain a surfactant can be used.

Among those mentioned above, a 35/65 to 65/35 (mono ratio) copolymer of methyl methacrylate and ethyl or butyl acrylate is used as the backbone polymer, -COOH, CH20
Water-dispersible acrylics each containing 0.1 to 10% by weight of H are particularly suitable in terms of easy adhesion and transparency of the laminated film.

The composition of the adhesive layer in the present invention is not particularly limited as long as it has adhesive properties, but a typical example is a polymer-based adhesive layer with a softener or tackifier added thereto as necessary. Depending on the situation, fillers and anti-aging agents may be added. Examples of the polymer used here include recycled rubber, various rubbers such as styrene-butadiene rubber, polyisoprene rubber, butyl rubber, polyvinyl ether, and polyacrylate ester. Tackifiers include polyterpene resins, gum rosin, rosin esters and rosin derivatives, oil-soluble phenol resins, coumaron-indene resins, and petroleum-based hydrocarbon resins, while softeners include mineral oil, liquid polybutene, Liquid polyacrylates and lanolin may be mentioned.

Fillers to be added as necessary include zinc white, hydrated aluminum, titanium oxide, calcium carbonate, clay, pigments, etc., and anti-aging agents include anti-aging agents for rubber, di-
Examples include thiocarbamates and metal chelating agents.

In addition, the center line roughness (Ra) of the surface of the resin layer C is 0.2 to 0.8.
It is more preferable that the glossiness is 60% or less because the adhesiveness of the resin layer C is further improved. In this case, the label also has a unique matte appearance, which may be very desirable depending on the application.

The method of imparting such properties to the resin layer C is not particularly limited, but a typical method is to add inorganic particles to the resin layer C or polyester film. However, among these methods, it is more preferable to use a method of physically roughening the surface of the resin layer C (specifically, a method known as hairline processing or sandblasting) because the adhesiveness is significantly improved.

between the adhesive layer and the polyester film, if necessary.
Post-processing such as vapor deposition, matte processing, hairline processing, etc. may be performed.

Next, the manufacturing method of the present invention will be explained. First, polyester pellets polymerized by a conventional method are sufficiently dried, then co-fed into a known extruder, and then processed into a sheet through a slit-shaped die at a temperature above the melting temperature of the pellets and below the temperature at which the polymer decomposes. An unstretched sheet is produced by melt extrusion, cooling and solidification. At this time, it is desirable that the intrinsic viscosity of the unstretched sheet is 0.5 or more from the viewpoint of film properties. Next, the unstretched sheet or the unstretched sheet is heated to 70 to 14
A coating material prepared in a predetermined amount is applied onto a film stretched 2.0 to 8.0 times at 0°C, and while drying the film, the film is stretched 2.0 to 8.0 times.
When using an unstretched film at 60°C, 2
．． The film is stretched by 0 to 8.0 times and 2.0 to 8.0 times in the transverse direction, or by 2.0 to 8.0 times in the case of using an axially stretched film. Further, the biaxially oriented film thus obtained is further heated at 100 to 180°C by 1°1 to 1° in one or more directions.
It may be stretched 3.0 times. Furthermore, the biaxially oriented film is heat treated at 150 to 240° C. for 1 to 60 seconds while giving 0 to 10% relaxation, if necessary.

The coating method is not particularly limited and may be an extrusion lamination method or a melt coating method, but the gravure coating method using a water-soluble or water-dispersed coating material because it is possible to coat a thin film at high speed; It is preferable to apply known methods such as a reverse coat method, a kiss coat method, a die coat method, and a metal ring bar code method. In this case, if necessary, the film is subjected to a known surface treatment such as corona discharge treatment in the air or various other atmospheres before coating, which not only improves the coating properties but also improves the quality of the modified layer. can be formed more firmly on the film surface. Although the coating material concentration and coating drying conditions are not particularly limited, it is desirable that the coating film drying conditions be within a range that does not adversely affect the properties of the laminated polyester film.

After performing necessary processing such as hairline processing and vapor deposition on the opposite side of the resin layer C of the film thus obtained, an adhesive layer is provided. At this time, a female pattern paper and a release film may be provided on the adhesive surface if necessary.

On the other hand, after performing post-processing such as sand matting and hairline processing as necessary on the resin layer C, oxidative polymerization type or U
Labels are made by printing with hardening ink or by providing a heat-sensitive coloring layer.

The characteristic values of the present invention are based on the following measurement method and evaluation criteria.

(1) Grafting rate (%) The grafted polymer was subjected to CNMR method, IHNMR method,
It was calculated from the following formula based on the analysis results of various analysis methods such as the INEPT method and the INEPT method.

Grafting rate (%) = (2) Center line average roughness Ra shown in DIN 4768 is to be measured.

(3) Glossiness Measured based on ASTM D2457.

(4) On the easily adhesive resin layer C, the following three types of ink were applied and cured to a thickness of 2 μm after drying, a cross cut was made on the coating film, and the cross cut surface was coated with 450 cellophane. Apply Chiban's registered trademark "Cello Tape"CT-24> to the adhesive tape, apply a load of approximately 5 ka using a hand roller,
Press the modified layer back and forth 10 times, then peel off the cellophane adhesive tape by hand to determine the degree of difficulty in peeling off the modified layer: 0: Good (Peeling area: 2)
(Less than 0%), X: Poor (Peeling area 20% or more).

■Kuboi Ink II UV Ace Sumi ■Toka Shiki■ Toka 161 Sumi ■Jujo Kako II 9000 Sumi However, for ■ and ■, use a 3QW/Cm UV lamp at a height of 10CrIl
Then, it was irradiated with 3S80 and cured.

For method (2), it was left to dry in a hot air oven at 140°C for 2 minutes, and then left in a hot air oven at 60°C for one day to cure.

(5) When a sample obtained in the same manner as in (5) is scratched with a nail, those that are easily scratched are judged as scratch resistant rXJ, and those that are slightly scratched are judged as rOJ. did.

[Examples] The present invention will be explained using the following Examples and Comparative Examples, but the present invention is not limited thereto.

Example 1 (1) Graft copolymer resin C: 100 parts of dimethyl terephthalate, 100 parts of dimethyl isophthalate, 7 parts of dimethyl 5-sodium sulfoisophthalate, 95 parts of ethylene glycol, 95 parts of neopentyl glycol, manganese acetate Mix 0.106 parts of tetrahydrate and 0.07 parts of calcium acetate dihydrate, and heat for 140 minutes under nitrogen stream.
After distilling methanol out at ~220°C and performing a transesterification reaction, 0.09 part of trimethyl phosphate and 0.06 part of antimony dioxide are added, and the temperature is raised from 240°C to 280°C over 1 hour and 30 minutes. At the same time, the pressure was gradually lowered from normal pressure to 0.5 ff 1 mH (l), the generated ethylene glycol was removed from the system, and this state was further maintained for 40 minutes to carry out the polycondensation reaction. η] = 0.58 polyester copolymer (a)
I got it. Next, a mixture of 250 parts of this polyester copolymer and 110 parts of butyl cellosolve was stirred at 150° C. for 4 hours to obtain a uniform solution. 480 parts of water was gradually added dropwise to the resulting solution under high-speed stirring to obtain a uniform, milky white, opaque dispersion with a solid content concentration of 25%.

Polyester resin dispersion 700 thus obtained
100 parts of water were added to the mixture, and further a dispersion of a polymerization initiator consisting of 30 parts of water, 1.5 parts of benzoyl peroxide, 12 parts of methyl methacrylate, and 2.5 parts of polyoxyethylene alkyl ether phosphate was added. The mixture was bubbled with nitrogen gas for 1 hour under stirring and then warmed to 75°C.

Next, a total of 280 parts of methyl methacrylate, butyl acrylate, and glycidyl methacrylate were mixed as a graft compound in a ratio of 2:1:1 and added dropwise to the stirring mixture at 85° C. over 60 minutes, and polymerization was carried out under a nitrogen stream. The reaction was carried out while varying the temperature and time to obtain a water-dispersed graft copolymer COW with a solid content concentration of 25%. Incidentally, the grafting rate of the graft compound was 40%.

(2) In a laminated polyester film, 1 homopolymer chip of polyethylene terephthalate (intrinsic viscosity = 0.62, melting point = 259°C) manufactured by a conventional method
It was dried under reduced pressure (3 mm HO) at 80° C. for 2 hours. This chip was co-fed to an extruder at 280°C, melted and extruded from a T-type nozzle, and wound around a cooling drum with a surface temperature of 20°C using an electrostatic application method to cool and solidify it to form an unstretched film.
The obtained film was stretched 3.3 times in the machine direction by roll stretching at 90°C. Next, water was added to dilute the above polymer, and a melamine crosslinking agent "Nikaratsuku" MW-121F (manufactured by 11 Sanwa Chemical Co., Ltd.) was added as a crosslinking agent per 100 parts by weight of resin solid content. 5 parts by weight of silica sol with an average particle size of 0.10 μm was added as a lubricant.
Cataroid'' (manufactured by Catalysts Kasei Kogyo II) with a resin solid content of 1
A coating material containing 0.5 parts by weight per 00 parts by weight and a final adjusted concentration of 5.0 parts by weight was applied onto one side of the above-mentioned axially stretched film using a metaling bar, and the applied layer was dried. The resin layer C0,1 was stretched by 3.6 times in the transverse direction at 100°C, and then heat-treated at 210°C while relaxing by 2% in the transverse direction.
A laminated film having a thickness of 50 μm and having a thickness of 2 μm was obtained.

An adhesive made of ethylene-vinyl acetate copolymer resin is applied to the uncoated surface of the film thus obtained, and after drying, paper laminated with polyethylene coated with thermosetting silicone is used as a release layer and dried. Laminate. The labels prepared in this manner were evaluated for easy adhesion and claw resistance. The results are shown in Table 1.

Example 2 The grafting compound to be dropped was 700 parts, and the grafting rate was 4.
The same procedure as in Example 1 was carried out except that 100% was used instead of 0%, and the results are shown in Table 1.

Example 3 The same procedure as in Example 1 was carried out, except that 1400 parts of the graft compound was added and the graft ratio was changed from 40% to 200%, and the results are shown in Table 1.

Example 4 The same procedure as in Example 1 was carried out, except that 2800 parts of the graft compound was added and the graft ratio was changed from 40% to 400%, and the results are shown in Table 1.

Comparative Example 1 The same procedure as Example 1 was carried out except that after polymerizing only the graft compound, the polyester resin (a) was mixed and the graft ratio was set to 0%. The results are shown in Table 1.

Comparative Example 2 The same procedure as in Example 1 was carried out, except that 7000 parts of the graft compound was added and the graft ratio was changed from 40% to 1000%, and the results are shown in Table 1.

Comparative Example 3 The same procedure as in Example 1 was carried out except that the amount of crosslinking agent added was changed from 5 parts by weight to 0 parts by weight, and the results are shown in Table 1.

Example 5 Except that the amount of crosslinking agent added was changed from 5 parts by weight to 10 parts by weight,
The test was carried out in the same manner as in Example 1, and the results are shown in Table 1.

Example 6 The same procedure as in Example 1 was carried out except that 15 parts by weight of a 1:1 copolymer of methyl methacrylate and butyl acrylate was further added to 100 parts by weight of the graft compound, and the results are shown in Table 1. Shown below.

Example 7 The same procedure as in Example 1 was carried out, except that 30 parts by weight of a 1:1 copolymer of methyl methacrylate and butyl acrylate was further added to 1 part by weight of 100 parts of the graft compound.
The results are shown in Table 1.

Example 8 A sand matting process (processing in which sand is applied at high speed to roughen the surface) was performed on the resin layer C, and the center line average roughness was 0.4 μm.
The same procedure as in Example 1 was carried out except that the gloss level was 35%, and the results are shown in Table 1.

Example 9 The same procedure as in Example 1 was carried out, except that hairline processing (scratching with metal claws) was performed on the resin layer C, the center line average roughness was set to 0.3 μm, and the gloss level was set to 42%. The results are shown in Table 1.

As shown in the table, only the cases within the range of the present invention exhibit excellent properties. Further, within the range of the present invention, winding was possible without blocking property. In particular, when an acrylic resin is further added, the claw resistance is further improved.

[Effects of the Invention] The present invention provides a copolymer (c) in which a hydrophilic group-containing polyester resin (a) is grafted with a compound (b) having an unsaturated bond, and a crosslinking agent as the main components. Since a resin layer having a combined grafting ratio of 0.5 to 600% was provided, the label was excellent in (1) printability, (2) processability, and (2) patternability.

Claims (2)

[Claims] (1) The main components are adhesive layer A, polyester film B, a copolymer (c) obtained by grafting a compound (b) having an unsaturated bond to a hydrophilic group-containing polyester resin (a), and a crosslinking agent. The grafting rate of the copolymer is 0.5~
600% resin layer C is laminated in this order. (2) The label according to claim 1, wherein the resin layer C has a center line roughness of 0.2 to 0.8 μm and a glossiness of 60% or less.