JP5987534B2 - Linerless labels, laminated labels and tape labels - Google Patents

Description

  The present invention relates to a linerless label, a laminated label, and a tape-type label.

  In various fields such as the distribution field, labels are affixed to articles to be pasted, such as cardboard boxes and garbage bags, for the purpose of displaying precautions, warnings, and contents. As labels for such applications, a paper base material, a release layer provided on the surface of the paper base material, and a pressure-sensitive adhesive layer provided on the back surface of the paper base material and peelable from the release layer Linerless labels having the following are known.

  The linerless label is used in the form of a laminated label or a tape-type label from the viewpoint of reducing dust and reducing the environmental load as much as possible (for example, Patent Documents 1 to 3). Examples of the laminated label include those in which a plurality of congruent sheetless linerless labels are laminated on release paper. When using the laminated label, each linerless label is peeled off from the laminated label one by one and is attached to the article to be stuck. Further, examples of the tape type label include a belt-like linerless label that is adhered to the back surface and wound in a tape shape. When the tape-type label is used, the strip-shaped linerless label is rolled back from the outside of the tape-type label while being peeled off, cut for each part to be used, and attached to the article to be applied.

JP 2000-135750 A JP 2004-70272 A JP 2012-98638 A

  However, in conventional linerless labels such as Patent Documents 1 to 3, the release agent soaks into the paper substrate when the release layer is formed, and a release layer having a sufficient thickness cannot be formed. May become heavy. As a method for solving this problem, there is a method of forming a sealing layer on the surface side of the paper substrate. However, the manufacturing process is complicated and the cost is high, and the surface of the release layer is writable and imprintable. It is also difficult to give.

The present invention provides a linerless label, a laminated label, and a tape-type label that can be easily peeled off without providing a sealing layer on the surface of a paper substrate and that can impart writing properties to the surface.

The linerless label of the present invention includes a paper base material, a release layer provided so as to be in direct contact with the surface of the paper base material, and a pressure sensitive sensor provided on the back surface of the paper base material and capable of being peeled off from the release layer. An epoxy group-containing organopolysiloxane having a unit (A1) represented by the following formula (A1) and a unit (A2) represented by the following formula (A2): The total amount of the unit (A1) and the total amount of the unit (A2), which is a layer formed of the cationic curable silicone release agent (I) containing (A) and contained in the cationic curable silicone release agent (I) Is a linerless label in which the ratio P of the total amount of the unit (A1) to the total is 0.5 to 4 mol%.

However, in said formula, R < ¹ > -R < ³ > is a C1-C10 alkyl group each independently. X is an epoxy functional group.

In the laminated label of the present invention, a plurality of the linerless labels of the present invention are in close contact with the pressure-sensitive adhesive layer of each linerless label and the release layer of the adjacent linerless label. It is the lamination type label laminated | stacked so that.
In the laminated label of the present invention, it is preferable that a plurality of linerless labels of the sheet are laminated on the release paper with the pressure-sensitive adhesive layer side of the release paper.

  The tape-type label of the present invention is a tape-type label in which a belt-like linerless label of the present invention is self-back adhered and wound in a tape shape.

The linerless label of the present invention can be easily peeled off without providing a sealing layer on the surface of the paper substrate, and can also provide writing properties and sealability on the surface.
In the laminated label of the present invention, even if a sealing layer is not provided on the surface of the paper base material, the linerless label of each sheet can be peeled lightly and the surface can be provided with writability.
The tape-type label of the present invention is lightly peelable and easy to wrap and use, and can provide writability on the surface without providing a sealing layer on the surface of the paper substrate. It is.

It is sectional drawing which showed an example of the linerless label of this invention. It is the perspective view which showed an example of the laminated label of this invention. An example of the tape-type label of the present invention was shown.

  In this specification, “back” in the linerless label means the surface on the side of the article to be pasted when the peeled linerless label is stuck on the article to be pasted, and “front” means the surface on the side opposite to the article to be pasted. Means.

Hereinafter, an example of the linerless label of the present invention will be described with reference to FIG.
The linerless label 10 of the present embodiment is provided on the paper base 12, the release layer 14 provided on the front surface 12 a of the paper base 12, and the back surface 12 b of the paper base 12, and can be peeled from the release layer 14. Pressure-sensitive adhesive layer 16.

(Paper substrate)
Examples of the paper base 12 include wood pulp composed mainly of wood pulp and containing additives such as pigments and various auxiliary agents as necessary.
As wood pulp, either hardwood (L material) or softwood (N material) may be used, and various chemical pulps, semi-chemical pulps, mechanical pulps, regenerated pulps, and the like can be used.
Examples of chemical pulp include kraft pulp (KP), sulfite pulp (SP), and soda pulp (AP). Semi-chemical pulp includes semi-chemical pulp (SCP), chemi-ground wood pulp (CGP), and the like. Examples of the mechanical pulp include groundwood pulp (GP), thermomechanical pulp (TMP), bleached chemithermomechanical pulp (BCTMP), refiner groundwood pulp (RGP), and the like. Examples of recycled pulp include deinked pulp (DIP) made from waste paper.
Moreover, you may use the non-wood pulp which uses a raw material, such as a persimmon, three bases, hemp, and kenaf.

When the paper base 12 has a high whiteness, pulp bleached by combining various bleaching methods using chlorine, chlorine dioxide, oxygen, ozone, hydrogen peroxide, hypochlorous acid, or the like can be used. Among these, pulp produced by chlorine-free bleaching (ECF) or complete chlorine-free bleaching (TCF) produced in a process that does not use chlorine is preferably used because it hardly causes yellowing.
The pulp forming the paper base 12 may be one kind or two or more kinds.

80 to 650 mL is preferable and 200 to 600 mL is more preferable as the freeness after disaggregation based on Canadian Standard Freeness (freeness: CSF) defined by JIS P 8121 of pulp used for the paper base material 12. If the freeness is less than or equal to the upper limit value, the surface 12a of the paper base 12 is likely to be smooth, and the paper strength of the paper base 12 can be sufficiently obtained. If the freeness is equal to or greater than the lower limit, good papermaking properties such as good drainage and sufficient papermaking speed can be obtained, and the writing property on the surface of the release layer 14 can be easily obtained.
The pulp forming the paper substrate 12 preferably contains 50% by mass or more, more preferably 80% by mass or more of hardwood bleached kraft pulp (LBKP) having a freeness after disaggregation of 350 to 550 mL.

The paper base 12 may be blended with a pigment. By blending the pigment into the paper base material 12, it is possible to obtain effects such as imparting opacity to the paper base material 12 and imparting writing properties to the surface of the paper base material 12.
Examples of the pigment include light calcium carbonate, calcined kaolin, white carbon, talc, and titanium oxide. Of these, talc, light calcium carbonate, and white carbon are preferable, and talc and light calcium carbonate are particularly preferable because they are excellent in papermaking suitability (wire wear suitability) and easily stay during papermaking.
When a pigment is blended in the paper substrate 12, the content (ash content) of the pigment in the paper substrate 12 is preferably 0.1 to 30% by mass, and more preferably 10 to 20% by mass. If the pigment content is greater than or equal to the lower limit, the writing property will be good. If the pigment content is less than or equal to the upper limit, sufficient paper strength can be easily obtained.

An auxiliary agent may be blended in the paper base 12.
As auxiliary agents, for example, internal sizing agents (higher fatty acids, alkyl ketene dimers, etc.), fixing agents (sulfuric acid bands, cationic polymer electrolytes, etc.), paper strength enhancers (starch, polyacrylamide, polyvinyl alcohol, etc.) .), Cationizing agents, yield improvers, dyes, fluorescent whitening agents, antifungal agents and the like.

The paper base 12 uses a known paper machine such as a long paper machine, a circular paper machine, a Yankee paper machine, a twin wire former, an inclined wire former, and a dryer (Yankee dryer, multi-cylinder dryer, etc.). It can be obtained by paper making.
The paper base 12 may be subjected to a known process such as a calendar process.

The paper substrate 12 may be subjected to size processing by a size press or a gate roll for the purpose of adjusting surface strength, sizing properties, and the like.
Examples of the size treatment liquid used for the size treatment include a treatment liquid in which starches, polyvinyl alcohols, polyacrylamides, surface sizing agents, cationic resins, and the like are blended in a solvent. Examples of the surface sizing agent include styrene maleic acid copolymer, olefin copolymer, alkyl ketene dimer compound, alkenyl succinic anhydride compound, styrene-acrylic copolymer, higher fatty acid compound, and petroleum resin. Examples thereof include a sizing agent and a rosin sizing agent.

When performing size processing, the coating amount of the size processing liquid is preferably 0.3 to 5.0 g / m ² in terms of dry mass, and more preferably 0.5 to 3.0 g / m ² . If the coating amount is equal to or greater than the lower limit value, the effect of size treatment can be easily obtained. In addition, when the coating amount exceeds the upper limit value, the effect of the size treatment reaches a peak, and if the coating amount is equal to or less than the upper limit value, it is advantageous in terms of cost.
When the size treatment is performed on both sides, it is preferable that the coating amount of the size treatment liquid is within the above range in terms of the total of both sides.

The basis weight of the paper substrate 12 is preferably ^{40~210g / m 2, 60~120g / m} 2 is more preferable. If the basis weight is equal to or greater than the lower limit, sufficient paper strength can be easily obtained. If the basis weight is less than or equal to the upper limit value, it is easy to reduce the paper thickness.
The density of the paper base 12 is preferably 0.55 to 1.00 g / m ³ . If the density is equal to or higher than the lower limit, sufficient paper strength can be easily obtained. When the density is not more than the upper limit value, the writing property and the stamping property are good.

The paper base 12 is preferably uncoated paper or single-sided coated paper provided with a coating layer on one side. When the paper base 12 is a single-side coated paper, the paper base 12 may have a coating layer on the back surface 12b side, that is, the side where the release layer 14 is not provided, in that good writing properties can be obtained. preferable.
Examples of uncoated paper include high-quality paper, medium-quality paper, and glossy paper. Of these, high-quality paper is preferable in terms of printing ink peeling strength. Examples of the single-sided coated paper include a general printing paper, heat-sensitive recording paper, a sealing layer that suppresses permeation of a paper base material such as an adhesive, and a polyethylene laminate layer.
Examples of the method for providing the coating layer include a method using a blade coater, knife coater, bar coater, air knife coater, die coater, slot die coater, gravure coater and the like.

(Peeling layer)
The release layer 14 of the linerless label of the present invention comprises an epoxy group-containing organopolysiloxane (A1) having a unit (A1) represented by the following formula (A1) and a unit (A2) represented by the following formula (A2). ) (Hereinafter referred to as “organopolysiloxane (A)”) is a layer formed of a cationic curable silicone release agent (I) (hereinafter referred to as “release agent (I)”).

However, in said formula, R < ¹ > -R < ³ > is a C1-C10 alkyl group each independently. X is an epoxy functional group.
The number of carbon atoms in the alkyl group of ^{R 1} units (A1) is 1 to 5 is preferable, and more preferably 1.
The number of carbon atoms in the alkyl group of ^{R 2} units (A2) is 1 to 5 preferably, 1 is more preferred.
The carbon number of the alkyl group of ^{R 3} units (A2) is 1 to 5 is preferable, and more preferably 1.
It is particularly preferable that R ^{1 to} R ³ in the unit (A1) and the unit (A2) are all methyl groups.

  The epoxy functional group of X should just be what a ring-opening cationic polymerization advances by an onium salt photoinitiator. Preferably, γ-glycidyloxypropyl group, β- (3,4-epoxycyclohexyl) ethyl group, and β- (4-methyl-3,4 epoxycyclohexyl) propyl group can be exemplified.

  The degree of polymerization of the organopolysiloxane (A) is preferably 2 to 10,000, more preferably 5 to 5000, and still more preferably 10 to 500. If the degree of polymerization is not less than the lower limit, peeling can be sufficiently lightened. If the said polymerization degree is below an upper limit, it can be set as the viscosity which can fully apply the viscosity of release agent (I).

  The organopolysiloxane (A) is preferably an organopolysiloxane (A-1) having a structure represented by the following formula (A-1) from the viewpoint of easily forming a release layer 14 with light label peeling.

However, in said formula, R < ¹ > -R < ³ > is a C1-C10 alkyl group each independently. X is an epoxy functional group. n and m are each an integer of 1 or more, and n + m is an integer of 2 to 10,000.

The preferred embodiments of R ^{1 to} R ³ and X in the organopolysiloxane (A-1) are as described above.
All of R ^{1 to} R ³ in the organopolysiloxane (A-1) are preferably methyl groups.
n + m is preferably 2 to 10,000, more preferably 5 to 5000, and particularly preferably 10 to 500.

The organopolysiloxane (A) may be a random copolymer in which the unit (A1) and the unit (A2) are randomly incorporated in addition to the block copolymer such as the organopolysiloxane (A-1). Good. Moreover, it is good also as a molecular structure which has (A1) in both ends, and it is good also as a molecular structure which has (A2) in both ends.
The organopolysiloxane (A) that is a random copolymer is preferably an organopolysiloxane having the same structure as the organopolysiloxane (A-1) except that the units (A1) and (A2) are randomly incorporated. .

  The ratio P of the total amount of the unit (A1) to the total of the total amount of the unit (A1) and the total amount of the unit (A2) contained in the release agent (I) is 0.5 to 4 mol%, and 1 to 3 mol. % Is preferred. If the said ratio P is more than a lower limit, when forming the peeling layer 14, it can suppress that a peeling agent (I) permeates into the paper base material 12 even if it does not provide a sealing layer. If the said ratio P is below an upper limit, the peeling between peeling layer 14-pressure sensitive adhesive layer 16 will become light.

  The organopolysiloxane (A) contained in the release agent (I) may be only one type or two or more types. When two or more kinds of organopolysiloxane (A) are included, the ratio P is a unit (A1) relative to the sum of the total amount of units (A1) and the total amount of units (A2) in all organopolysiloxanes (A). Is the ratio of the total amount.

As an aspect which adjusts the said ratio P in peeling agent (I) to 0.5-4 mol%, the following aspect (i) and aspect (ii) are mentioned.
(I) A mode in which the ratio Q of the total amount of units (A1) to the total of the total amount of units (A1) and units (A2) in the molecule is adjusted only by the same organopolysiloxane (A).
(Ii) A mode in which two or more organopolysiloxanes (A) having different ratios Q are combined and adjusted.

The ratio Q of the organopolysiloxane (A) used in the embodiment (i) is 0.5 to 4 mol%, preferably 1 to 3 mol%.
In the embodiment (ii), at least one kind of organopolysiloxane (A ′) having a ratio Q of 0 to 2 mol%, more preferably 0.1 to 1.5 mol%, and a ratio Q of 4 mol% or more, More preferably, it is preferable to adjust the ratio P of the release agent (I) to 0.5 to 4 mol% by blending with 4.5 to 10 mol% of the organopolysiloxane (A ″). .

  In the embodiment (ii), it is preferable that at least one organopolysiloxane (A ′) is contained. From the viewpoint of light release of the laminated label and writing property, the ratio of the organopolysiloxane (A ′) to 100% by mass of all the organopolysiloxanes (A) used in the embodiment (ii) is 10% by mass or more. Is preferable, and 50 mass% or more is more preferable. When the compounding amount of the organopolysiloxane (A ′) is small, peeling may become too heavy or the writing property may be deteriorated. The ratio of the organopolysiloxane (A ″) to 100% by mass of all the organopolysiloxanes (A) used in the embodiment (ii) is preferably 90% by mass or less, more preferably 50% by mass or less, and particularly preferably The amount is 5% by mass or more and 50% by mass or less. If the amount of the organopolysiloxane (A ″) is too large, the film-forming property of the release layer becomes too high and the writing property tends to be lowered. When the amount of the organopolysiloxane (A ″) is too small, the release layer is hard to be cured and the release tends to be heavy.

The release agent (I) preferably contains an onium salt photoinitiator in addition to the organopolysiloxane (A).
Known onium salt photoinitiators can be used. Specific examples thereof include compounds represented by (R ¹ ) ₂ I ⁺ X ⁻ , ArN ₂ ⁺ X ⁻ , (R ¹ ) ₃ S ⁺ X ⁻ . R ¹ represents an alkyl group or an aryl group, and Ar represents an aryl group. X ⁻ includes [B (C ₆ H ₅ ) ₄ ] ⁻ , [B (C ₆ F ₅ ) ₄ ] ⁻ , [B (C ₆ H ₄ CF ₃ ) ₄ ] ⁻ , [(C ₆ F ₅ ) ₂ BF ₂ ] ⁻ , [C ₆ F ₅ BF ₃ ] ⁻ , [B (C ₆ H ₃ F ₂ ) ₄ ] ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , SbCl ₆ ⁻ , HSO ₄ ^- or ClO ₄ ^- and the like.

The amount of the onium salt photoinitiator used is not particularly limited, and the amount used can be appropriately adjusted. From the viewpoint of economy and production operability, 1 to 20 parts by mass is preferable with respect to 100 parts by mass of the organopolysiloxane (A).
The viscosity of the release agent (I) is preferably 5000 cps or less, and more preferably 1000 cps or less. If the viscosity is not more than the upper limit value, good writing property and sealability can be imparted to the surface of the release layer 14.

For the release agent (I), as necessary, other ultraviolet curable resins, electron beam curable resins, photopolymerization initiators, crosslinking agents, dyes, pigments, wetting agents, antifoaming agents, dispersing agents, Various auxiliaries such as an antistatic agent, a leveling agent, and a lubricant may be appropriately added as long as the desired effects are not impaired.
The amount of the auxiliary added is preferably 10% by mass or less with respect to the total mass of the release agent layer. With regard to the pigment, it is particularly preferable that no pigment is added (0% by mass). This is because when a pigment is blended in the release agent layer, the release may become heavy when a linerless label is formed.

Dry weight of the release layer 14 is preferably ^{0.2~2.0g / m 2, 0.5~1.5g / m} 2 is more preferable. If the dry mass of the said peeling layer 14 is more than a lower limit, peeling between the peeling layer 14-pressure sensitive adhesive layer 16 will become light. When the dry mass of the release layer 14 is not more than the upper limit value, the release layer 14 having good writing properties and sealability can be formed.

The smoothness of the surface of the release layer 14 is preferably 30 seconds to 200 seconds, and more preferably 50 seconds to 150 seconds. If the smoothness is equal to or higher than the lower limit value, peeling between the release layer 14 and the pressure-sensitive adhesive layer 16 becomes light. If the smoothness is less than or equal to the upper limit value, the release layer 14 having good writing properties and sealability can be formed.
Here, the smoothness is defined by “Oken type smoothness based on JAPAN TAPPI paper pulp test method No. 5-2”.

(Pressure sensitive adhesive)
Examples of the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer 16 include a solvent-type adhesive, an emulsion-type adhesive, and a hot-melt-type adhesive. Of these, a hot-melt adhesive is preferred because it is difficult for the adhesive to soak into the paper substrate 12 and the label peels lightly.
Examples of the hot melt adhesive include rubber-based hot melt adhesives, ethylene-vinyl acetate copolymers, ethylene-acrylic acid copolymers, and the like. Of these, rubber-based hot-melt pressure-sensitive adhesives are preferable from the viewpoints of stability of adhesive strength, bleeding, and cost.

  Examples of rubber-based hot melt adhesives include styrene-ethylene-butylene-styrene block copolymers (SEBS), styrene-butadiene-styrene block copolymers (SBS), and styrene-isoprene-styrene block copolymers. (SIS), and styrene copolymers such as styrene-ethylene-propylene-styrene block copolymer (SEPS). Of these, SIS is particularly preferable.

The pressure-sensitive adhesive forming the pressure-sensitive adhesive layer 16 includes a styrene copolymer (I) having a weight average molecular weight (Mw) of 1 × 10 ³ or more and less than 1 × 10 ^5, and a weight average molecular weight (Mw). It is preferable that 1 * 10 < ⁵ > -1 * 10 < ⁷ > styrene-type copolymer (II) is included. Thereby, the performance of a label becomes difficult to change according to temperature conditions, and the peelability of the label and the adhesiveness to the article to be stuck can be obtained more stably.
The mass ratio (I) / (II) of the styrene copolymer (I) and the styrene copolymer (II) is preferably 10/1 to 1/10, more preferably 5/1 to 1/5. 2/1 to 1/2 is particularly preferable.

  The pressure-sensitive adhesive layer 16 may contain a tackifier, a softener, a wax, or the like as necessary. The tackifier improves the tackiness of the pressure sensitive adhesive layer 16. The softener improves the device compatibility of the pressure sensitive adhesive layer 16. The wax lowers the instantaneous adhesiveness of the pressure-sensitive adhesive layer 16 and facilitates peeling without damaging the article to be applied immediately after application.

Examples of tackifiers include aliphatic (C5) petroleum resins, aromatic (C9) petroleum resins, copolymerized (C5 / C9) petroleum resins, dicyclopentadiene (DCPD) petroleum resins, and coumarone indene. Examples thereof include resins, acrylic resins, styrene resins, rosins, rosin ester resins, terpene resins, aromatic modified terpene resins, terpene phenol resins, and hydrogenated resins thereof.
Examples of the softener include various plasticizers, polybutene, liquid tackifier resin, polyisobutylene low polymer, polyvinyl isobutyl ether low polymer, lanolin, bulk polymerized rubber, process oil, naphthenic oil, paraffinic oil, additive And sulfur oil.
Preferred examples of the wax include plant waxes, animal waxes, mineral waxes, petroleum waxes, and synthetic waxes, as well as these processed / modified waxes. As the plant wax, carnauba wax and wood wax are more preferable. As the animal wax, beeswax is more preferable. As the mineral wax, montan wax and ozokerite are more preferable. As the petroleum wax, paraffin wax and microcrystalline wax are more preferable. As the synthetic wax, Fischer-Tropsch wax, polyethylene wax, polypropylene wax, oil-based (ester, ketones, amide) synthetic wax, and hydrogenated wax are more preferable. As the processed / modified wax, the above-described more preferable wax processed / modified wax is more preferable.
More preferable examples of the wax include paraffin waxes having various melting points of 42 to 73 ° C., microcrystalline waxes having melting points of 50 to 120 ° C., and polyolefin waxes such as polyethylene wax and polypropylene wax.
Polyolefin wax usually has a molecular weight of about 1,000 to 10,000, that is, generally known as a polyolefin wax. The polyolefin wax is usually obtained by a high pressure polymerization method, a low pressure polymerization method, or thermal decomposition of a high molecular weight polyolefin.
Specific examples of the processed / modified wax include, for example, those obtained by oxidizing the above-described wax and introducing a polar group such as a hydroxyl group, an ester group, a carboxyl group, an aldehyde group, or a peroxide group into the wax.

Examples of tackifiers include aliphatic (C5) petroleum resins, aromatic (C9) petroleum resins, copolymerized (C5 / C9) petroleum resins, dicyclopentadiene (DCPD) petroleum resins, and coumarone indene. Examples thereof include resins, acrylic resins, styrene resins, rosins, rosin ester resins, terpene resins, aromatic modified terpene resins, terpene phenol resins, and hydrogenated resins thereof.
When using a tackifier, 10-70 mass parts is preferable with respect to 100 mass parts of pressure sensitive adhesives, and, as for content of the tackifier in the pressure sensitive adhesive layer 16, 30-60 mass parts is more. Preferably, 30 to 50 parts by mass is particularly preferable. If the content of the tackifier is not less than the lower limit value, excellent adhesive force can be easily obtained, and it is possible to easily suppress that the label attached to the article to be applied is partially peeled off or completely dropped off. . If content of the said tackifier is below an upper limit, it will be easy to suppress that peeling of a label becomes heavy too much.

  The content of the softening agent in the pressure-sensitive adhesive layer 16 is preferably 1 to 50 parts by mass, more preferably 5 to 35 parts by mass, and particularly preferably 10 to 25 parts by mass with respect to 100 parts by mass of the pressure-sensitive adhesive. preferable. If content of the said softener is more than a lower limit, it will be easy to suppress that the viscosity of a pressure sensitive adhesive becomes high too much. If content of the said softening agent is below an upper limit, it will be easy to suppress that the viscosity of a pressure sensitive adhesive becomes low too much.

  The content of the wax in the pressure sensitive adhesive layer 16 is preferably 0.1 to 25 parts by mass, more preferably 0.5 to 15 parts by mass with respect to 100 parts by mass of the pressure sensitive adhesive. Part is particularly preferred. If the content of the wax is equal to or higher than the lower limit, the label can be easily peeled off without damaging the article to be stuck for a short time after sticking. If the content of the wax is not more than the upper limit value, sufficient adhesive strength can be obtained.

5-60 g / m < ² > is preferable and, as for the dry mass of the pressure sensitive adhesive layer 16, 10-30 g / m < ² > is more preferable. If the dry mass of the pressure sensitive adhesive layer 16 is more than a lower limit, sufficient adhesive performance will be obtained. If the dry mass of the pressure-sensitive adhesive layer 16 is less than or equal to the upper limit value, the ouse is good and economically excellent.

  3-20N / 10mm is preferable, as for the 180 degree peeling adhesive force measured based on JISZ0237 of the pressure sensitive adhesive layer 16, 4-16N / 10mm is more preferable, and 5-14N / 10mm is especially preferable. When the 180 ° peeling adhesive strength is equal to or higher than the lower limit, it is possible to prevent the label attached to the article to be applied from being partially peeled off or completely dropped off. If the 180 ° peeling adhesive strength is less than or equal to the upper limit value, label peeling becomes light.

The pressure-sensitive adhesive layer 16 is measured with an inclination angle of 30 ° measured according to JIS Z 0237 in that the label can be easily peeled off without damaging the article to be applied within a short time after the label is applied. The type ball tack is preferably 10 or less, and more preferably 5 or less. Further, the pressure-sensitive adhesive layer 16 preferably has one or more inclined ball tacks having an inclination angle of 30 °.
The inclined ball tack of the pressure-sensitive adhesive layer 16 having an inclination angle of 30 ° can be adjusted by using wax or the like. Specifically, by increasing the amount of wax used, the inclined ball tack of the pressure-sensitive adhesive layer 16 with an inclination angle of 30 ° can be reduced.

The storage elastic modulus of the pressure sensitive adhesive layer 16 measured in the range of 0 ° C. or more and 60 ° C. or less is preferably 5 × 10 ³ or more and 5 × 10 ⁶ or less. That is, the storage elastic modulus of the pressure-sensitive adhesive layer 16 is in the range of 5 × 10 ³ or more and 5 × 10 ⁶ or less when measured at any temperature condition in the range of 0 ° C. or more and 60 ° C. or less. Is preferred. When the storage elastic modulus is equal to or higher than the lower limit value, label peeling becomes light. If the storage elastic modulus is less than or equal to the upper limit value, sufficient adhesive strength can be obtained, and the label affixed to the article to be adhered is difficult to peel off. Further, since the storage elastic modulus is within the above-mentioned range over a wide temperature range of 0 ° C. or more and 60 ° C. or less, the influence of the temperature environment on the performance of the linerless label is small, the peelability of the label, and the attached adherend The stickiness of the label to the article can be obtained stably.
The storage elastic modulus of the pressure-sensitive adhesive layer 16 measured in the range of 0 ° C. or more and 60 ° C. or less is more preferably 5 × 10 ³ or more and 1 × 10 ⁶ or less, and preferably 1 × 10 ⁴ or more and 1 × 10 ⁵ or less. Particularly preferred.
The storage elastic modulus is measured by a dynamic viscoelasticity measuring device. The storage elastic modulus of the pressure-sensitive adhesive layer 16 of 0 ° C. or more and 60 ° C. or less is, for example, a specific ratio of the styrene copolymer (I) and the styrene copolymer (II), a tackifier, and a softener. It can be adjusted by using together.

(Production method)
The production method of the linerless label of the present invention is not particularly limited, and a conventionally known method can be adopted except that the release agent (I) is used.
For example, the release agent (I) is applied to the surface 12a of the paper substrate 12 and cured to form the release layer 14, and then the adhesive component including the pressure sensitive adhesive is applied to the back surface 12b of the paper substrate 12. Examples thereof include a method of forming the pressure-sensitive adhesive layer 16 by coating to obtain the linerless label 10. Further, the release layer 14 may be formed after the pressure-sensitive adhesive layer 16 is formed.

The amount of the release agent (I) applied is preferably such that the dry mass of the release layer 14 is within the above range.
The coating method of release agent (I) is not specifically limited, For example, the method of using a bar coater, a multistage roll coater, an air knife coater, a gravure coater, an offset gravure coater etc. is mentioned. Of these, flexographic printing is preferred.
Examples of the device for curing the release agent (I) include a hot air dryer, a far-infrared dryer, an ultraviolet irradiation device, and an electron beam irradiation device.

The coating amount of the pressure-sensitive adhesive component is preferably such that the dry mass of the pressure-sensitive pressure-sensitive adhesive layer 16 is within the above range.
The method for applying the pressure-sensitive adhesive component is not particularly limited, and when a hot-melt type pressure-sensitive adhesive is used as the pressure-sensitive pressure-sensitive adhesive, examples thereof include a relief printing method and a method using a hot-melt die coater. Moreover, when using a solvent-type adhesive and an emulsion-type adhesive, the method of using a roll coater, a reverse roll coater, a knife coater, a bar coater, an air knife coater, a die coater, a slot die coater, a gear in die coater etc. is mentioned, for example.

  In the linerless label of the present invention described above, since the release layer is formed of the release agent (I), the release agent (I) can be used as a paper base material without providing a sealing layer on the surface of the paper base material. Infiltration into the inside is suppressed, and peeling between the release layer and the pressure-sensitive adhesive layer is light. Further, since the linerless label of the present invention does not require a sealing layer on the surface of the paper substrate, it can be easily produced at a low cost, and it is easy to impart writability to the surface of the release layer. is there.

  In addition, the linerless label of this invention is not limited to the form which provides a peeling layer and a pressure sensitive adhesive layer in the whole surface of a paper base material. For example, a mode in which a release layer is provided in a strip shape on the side portion of the front surface of the paper base material to make that portion a non-adhesive portion, and a pressure-sensitive adhesive layer is provided on the back surface of the paper base material corresponding to the non-adhesive portion It is good. This aspect is preferable in that the adhesive strength of the label can be controlled widely from strong to weak adhesion by adjusting the type of pressure-sensitive adhesive and the position and shape of the non-adhesive portion. In this case, the form of the non-adhesive part and the pressure-sensitive adhesive layer corresponding thereto may be any form as long as they are provided on at least one side of the paper base material, from the point of preventing peeling of the label attached to the article to be applied. The form provided in the four sides of a paper base material over the perimeter of this paper base material is preferable.

In the linerless label of the present invention, it is preferable to print a pattern, a letter, an eye mark or the like on the front surface or the back surface of the paper base as necessary. As a method for printing a pattern, a character, an eye mark, etc., letterpress printing, offset printing, and flexographic printing are preferable. The ink to be used is preferably an ultraviolet curable ink, more preferably an ultraviolet curable ink with a small amount of amines, or an amineless ultraviolet curable ink containing no amines.
Further, if necessary, the medium ink can be printed on the entire surface of the paper base on the side where the release layer is formed. The printing method of the medium ink is preferably letterpress printing, offset printing or flexographic printing. The ink to be used is preferably an ultraviolet curable ink, more preferably an ultraviolet curable ink with a small amount of amines, or an amineless ultraviolet curable ink containing no amines.

(Laminated label)
The laminated label of the present invention is obtained by laminating a plurality of linerless labels in a single sheet. As an example of the embodiment of the laminated label of the present invention, for example, the laminated label 1 illustrated in FIG.
The laminated label 1 is a laminated body in which a plurality of rectangular linerless labels 10 are laminated on a rectangular release paper 20. In the laminated label 1, the pressure-sensitive adhesive layer 16 on the back surface of each linerless label 10 is in close contact with the release layer 14 on the surface of the linerless label 10 located thereunder so as to be peelable.

  In addition, in the laminated label of the present invention, a pressure-sensitive adhesive layer is provided on at least one side or corner as a turning margin because it is possible to easily peel off each laminated linerless label. It is preferable that there is no part. Specifically, at least one side of each linerless label of the laminated label has a turning margin not provided with a pressure-sensitive adhesive layer, or at least one of each linerless label of the laminated label It is preferable that a turning margin not formed with a pressure-sensitive adhesive layer is formed at the corner.

Further, the turning margin as described above may be formed by providing a pressure-sensitive adhesive layer on the entire back surface of the paper substrate and providing a paste-killing layer on the portion to be turned over.
As a method for forming the paste-killing layer, offset printing, flexographic printing, and lator press printing (letter printing) are preferable. From the viewpoint of quick drying, ultraviolet curing offset printing, ultraviolet curing flexographic printing, ultraviolet curing printing Rator press printing (letterpress printing) is more preferable, and from the viewpoint that the thickness of the paste-killing layer can be increased, ultraviolet curing flexographic printing is particularly preferable. Any adhesive can be used as long as it can prevent the pressure-sensitive adhesive layer from sticking, and it is used for printing for offset printing, flexographic printing, and lator press printing (letter printing). Ink, medium ink, and paste-killing ink can be preferably mentioned, and UV curable ink is particularly preferable.
The coating amount of the paste-killing agent when forming the paste-killing layer is preferably 0.01 to 20 g / m ² , more preferably 0.1 to 10 g / m ² in terms of dry mass. When the coating amount is less than the lower limit value, it may be impossible to prevent the pressure-sensitive adhesive layer from sticking. If the coating amount is larger than the upper limit value, only the portion to which the paste-killing layer is applied is too thick, so that when the laminated label is formed, only the portion swells and the appearance may not be good.

The use of the laminated label of the present invention is not particularly limited. For example, it is attached to an article to be pasted, such as a logistics label such as a tag label or a label for alerting a broken object, a process management use such as a management label, etc. Can be used.
Moreover, you may use a laminated label for uses other than the use used by sticking to a to-be-adhered article. For example, the laminated label of the present invention may be dust / dust removal or the like. The dust / dust removal and the like made of the laminated label of the present invention can easily maintain the cleanliness of the surface by peeling one by one from the top when the surface becomes dirty due to use. It can also be used as memo paper.
Note that the laminated label of the present invention may not have release paper.

(Tape type label)
The tape-like label is obtained by adhering the belt-like linerless label of the present invention to the back surface and winding it in a tape shape. As an example of embodiment of the tape-type label of this invention, the tape-type label 2 illustrated in FIG. 3 is mentioned, for example.
The tape-type label 2 is obtained by adhering a belt-like linerless label 10 on its back and winding it in a tape shape. In the self-back-bonded tape-type label 2, the pressure-sensitive adhesive layer 16 on the back surface of the linerless label 10 is in close contact with the release layer 14 on the surface of the linerless label 10 located on the inner periphery thereof. . When the tape-type label 2 is used, it can be used by winding the wound linerless label 10 and cutting it appropriately for each part to be used.

  The use of the tape-type label of the present invention is not particularly limited. For example, it is applied to an article to be pasted, such as a logistics label such as a tag label or a label for calling attention such as a broken object, or a process management use such as a management label. Can be used.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by the following description. In the examples, “%” represents mass% unless otherwise specified. “Part” means part by mass.
[Example 1]
(Manufacture of paper substrate)
Hardwood bleached kraft pulp (LBKP) was beaten to a freeness of 430 mL (CSF) to prepare a pulp slurry having a concentration of 0.5%. In this pulp slurry, cationized starch 2.0%, alkyl ketene dimer 0.4%, anionized polyacrylamide resin 0.1%, polyamide polyamine epichlorohydrin resin 0.7%, and pigment, based on the absolute dry mass of the pulp Talc was added and dispersed with sufficient stirring. The amount of talc added was 2% with respect to the finished paper substrate. Next, water was added to oxidized starch (trade name “ACE A”, manufactured by Oji Cornstarch Co., Ltd.) and dissolved by heating, and the concentration was adjusted to 5% to obtain a size press solution. The pulp slurry was made with a paper machine to obtain a base paper, and then a size treatment was performed on both sides of the base paper with the size press liquid with a size press attached to the paper machine to obtain a paper base material. The amount of the size press liquid absorbed into the paper substrate was 50 mL / m ² in total on both sides. Finally, a calendar process was performed with a machine calendar at the end of the paper machine to obtain a paper substrate having a basis weight of 100 g / m ² , a density of 0.85 g / cm ³ , and a steecht size of 35 seconds. Moreover, it was 350 mL when the freeness after disaggregation based on the Canadian standard freeness (freeness; CSF) prescribed | regulated by JISP8121 was measured about the obtained paper base material.

(Manufacture of laminated labels)
On one side of the obtained paper base material, a picture and a character pattern are printed using amine-less UV ink (trade name: NVR) manufactured by TOKA, and further on the whole surface of the paper base material using a flexographic printing machine. Release agent (I-1) obtained by mixing 5 parts of an onium salt photoinitiator (trade name “Silicolyse CATA211”, manufactured by Rhodia) with 100 parts of organopolysiloxane (A) having a Q of 1 mol% ( Ratio P: 1.0 mol%) was applied, and cured with a high-pressure mercury ultraviolet irradiation device under the condition of an ultraviolet irradiation amount of 140 mJ / cm ² to provide a release layer. The coating amount of the release agent (I-1) was 1.2 g / m ² . It was 0.8 g / m < ² > when the dry mass of the formed peeling layer was measured with the fluorescent X ray apparatus.
Next, with a hot melt die coater, a hot melt pressure-sensitive adhesive (trade name “TN-530Z”, manufactured by Moresco) is applied to the back surface of the paper substrate (the surface opposite to the release layer) at a coating amount of 20 g / as will be m ^2, although only one side upon the stacked labels, by coating by providing a portion having no width 1cm hot melt type adhesive, provided pressure-sensitive adhesive layer label original sheet Was made.
Next, the label raw material was cut into a rectangle of 8 cm in length and 12 cm in width to obtain 50 rectangular labels. Thereafter, these 50 labels were laminated so that each pressure-sensitive adhesive layer and the release layer were in contact with each other to obtain a laminated label.

[Example 2]
A single-side coated paper (trade name: OK top coat +, basis weight 84.9 g / m ² base paper) is used as the paper base, and amine-less UV ink (trade name: NVR) manufactured by TOKA is used. A picture and a character pattern are printed on the coated surface, and further, the following release agent (I-2) is coated on the entire surface of the paper substrate with a flexographic printing machine, and the ultraviolet irradiation amount is applied with a high-pressure mercury ultraviolet irradiation device. It hardened | cured on 140 mJ / cm < ² > conditions, and provided the peeling layer. The coating amount of the release agent (I-2) was 1.2 g / m ² . It was 0.9 g / m < ² > when the dry mass of the formed peeling layer was measured with the fluorescent X ray apparatus.
(Release agent (I-2))
50 parts of a product name “Silicolys POLY201” manufactured by Rhodia as an organopolysiloxane (A) having a ratio Q of 1 mol% and an organopolysiloxane (A) having a ratio Q of 4.6 mol%, 5 parts of an onium salt photoinitiator (trade name “Silicolys CATA211”, manufactured by Rhodia) were mixed to obtain a release agent (I-2) (ratio P: 2.8 mol%).
Next, with a hot melt die coater, a hot melt pressure-sensitive adhesive (trade name “TN-530Z”, manufactured by Moresco) is applied to the entire back surface of the paper substrate (the surface opposite to the release layer). Coating was performed at 20 g / m ^2, and a pressure-sensitive adhesive layer was provided to prepare a label original.
The obtained linerless label original fabric was finished into a 50 mm width roll by a slitter to obtain a tape-type label.

[Comparative Example 1]
Release agent (I-3) in which 5 parts of an onium salt photoinitiator (trade name “Silicolys CATA211”, manufactured by Rhodia) are mixed with 100 parts of organopolysiloxane (A) having a ratio Q of 0.2 mol%. A laminated label was obtained in the same manner as in Example 1 except that (ratio P: 0.2 mol%) was used. The coating amount of the release agent (I-3) was 1.2 g / m ² . When the dry mass of the formed release layer was measured with a fluorescent X-ray apparatus, it was 0.3 g / m ² despite the same operation as in Example 1. Since the fluorescent X-ray apparatus measures the coating amount of the release layer formed on the surface of the paper substrate, the reason for the difference from Example 1 is that the release agent soaked into the paper substrate.

[Comparative Example 2]
An onium salt-based photoinitiator (trade name “Silicolyse CATA211”, manufactured by Rhodia) is added to 100 parts of the trade name “Silicolys POLY201” manufactured by Rhodia as an organopolysiloxane (A) having a ratio Q of 4.6 mol%. A tape-type label was obtained in the same manner as in Example 2 except that 5 parts were mixed and the release agent (I-4) (ratio P: 4.6 mol%) was used. The coating amount of the release agent (I-4) was 1.2 g / m ² . It was 1.0 g / m < ² > when the dry mass of the formed peeling layer was measured with the fluorescent X ray apparatus.

(Writing evaluation)
“A” on the blank paper part on which no label picture / character pattern is printed by using an oil-based pen (trade name: for magic ink fine writing-black) and an oil-based ballpoint pen (trade name: UNIi Lakknock: fine-character -0.7 black) Was written and rubbed with a fingertip 10 seconds after writing. The results are shown in Table 1.
○: Characters can be written neatly and can be read after friction.
Δ: Characters can be written neatly, but after rubbing, the ink flow or discoloration makes it impossible to read the characters.
X: The character could not be written neatly.

(Turnability evaluation)
In the case of a laminated label: One rectangular linerless label was peeled off from the obtained laminated label by hand, and the ease of peeling was evaluated. The results are shown in Table 1.
In the case of a tape-type label: The obtained tape-type label was peeled by hand while rewinding, and the ease of peeling was evaluated. The results are shown in Table 1.
○: Lightly peelable and easy to peel off.
X: Heavy peeling and difficult to peel or not peeled off.

As shown in Table 1, Example 1 and Example 2 in which the release layer was formed using the release agent (I) having a ratio P of 0.5 to 4 mol% had good turnability, and the release layer- Peeling between pressure-sensitive adhesive layers was light and writing property was good. This is because the release agent (I) is prevented from penetrating into the paper substrate without forming a sealing layer on the paper substrate surface.
On the other hand, in Comparative Example 1 using a release agent having a ratio P of less than 0.5 mol%, it was not possible to prevent the release agent from permeating into the paper substrate during the formation of the release layer, and the release layer-pressure sensitive adhesive. The peeling between the agent layers was heavy. In Comparative Example 2 using a release agent having a ratio P of more than 4 mol%, sufficient writing property was not obtained.

  DESCRIPTION OF SYMBOLS 1 ... Laminated type label, 2 ... Tape type label, 10 ... Linerless label, 12 ... Paper base material, 14 ... Release layer, 16 ... Pressure-sensitive adhesive layer.

Claims (4)

A paper base, a release layer provided so as to be in direct contact with the surface of the paper base, and a pressure-sensitive adhesive layer provided on the back surface of the paper base and capable of being peeled off from the release layer. ,
The cation curable silicone in which the release layer includes an epoxy group-containing organopolysiloxane (A) having a unit (A1) represented by the following formula (A1) and a unit (A2) represented by the following formula (A2) It is a layer formed by the system release agent (I),
The ratio P of the total amount of the unit (A1) to the total of the total amount of the unit (A1) and the total amount of the unit (A2) contained in the cationic curable silicone release agent (I) is 0.5 to 4 mol%. Linerless label.

(However, in said formula, R < ¹ > -R < ³ > is a C1-C10 alkyl group each independently. X is an epoxy functional group.)   The linerless label according to claim 1 is laminated so that the pressure-sensitive adhesive layer of each linerless label and the release layer of the adjacent linerless label are in close contact with each other. Laminated label.   The laminated label according to claim 2, wherein a plurality of the linerless labels of the sheet are laminated on the release paper with the pressure-sensitive adhesive layer facing the release paper.   A tape-type label in which the linerless label according to claim 1 is bonded to its back surface and wound into a tape shape.

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