TW202031972A - Release paper, and pressure-sensitive adhesive sheet, label base paper, and label all including same - Google Patents

Abstract

The purpose of the present invention is to provide: release paper which includes a sealing layer comprising a biomass-derived resin and/or a biodegradable resin and which, despite this, is equal in releasability to conventional release papers including a layer of a fossil-fuel-derived polyolefin; and a pressure-sensitive adhesive sheet, a label base paper, and a label all including the release paper. The present invention provides release paper 10 which comprises: a paper base 11; one or two sealing layers 12 disposed on one or both surfaces of the paper base 11 and each comprising a biomass-derived resin and/or a biodegradable resin; and a release layer 13 disposed on at least one of the sealing layers 12.

Description

Release paper, adhesive sheet using this, label base paper and label

The present invention relates to a release paper, adhesive sheet, label base paper and label using the release paper.

In recent years, in order to reduce the burden on the environment, it has been reviewed to replace some of the raw materials derived from fossil fuels with bio-derived raw materials and biodegradable resins that are generated from animals and plants and renewable organic resources. .

However, in the release paper with a release agent layer on the surface of the paper substrate, in order to prevent the release agent from penetrating into the paper substrate as much as possible, so as to exert the limit of the release property, it is generally between the paper substrate and the release agent layer. The barrier layer is formed of a polyolefin layer (refer to Patent Document 1). The purpose of the formation of the barrier layer is to prevent the release agent from penetrating into the paper substrate during coating, so as to form a uniform release agent layer on the surface. Moreover, for the above reasons, it is also desired that the polyolefin forming the polyolefin layer preferably contains a biodegradable resin and a biodegradable resin. Patent literature

[Patent Document 1] Japanese Patent Laid-Open No. 02-191796

Problems to be solved by the invention

In terms of bio-derived resins, various researches and developments have been carried out, such as: polylactic acid; cellulose resins; polytrimethyl terephthalate using 1,3-propanediol derived from biomass, and using bio-derived resins Bio-polyester of ethylene glycol; Bio-polyamide such as nylon 11 and nylon 4 using fatty acid derived from biomass; Bio-polyurethane using glycol derived from biomass; Bio-based ethylene using biomass Polyolefins such as polyethylene, bio-polypropylene, etc. using bio-derived propylene.

However, although it is expected that the release paper can be developed to reduce the environmental load, the bio-derived resin and biodegradable resin have not been used as a barrier on the release paper from the viewpoint of manufacturing cost and popular use. Floor.

Therefore, the object of the present invention is to provide a barrier layer that contains bio-derived resin and/or biodegradable resin, but has the same release properties as the polyolefin layer derived from fossil fuels, and is not inferior to previous types of separators. Type paper, as well as the adhesive sheet, label base paper and label using it. Means to solve the problem

In view of the above situation, the inventors of this case have deliberately studied. As a result, it was found that the barrier layer containing bio-derived resin and/or biodegradable resin has the same release properties as the polyolefin layer derived from petrochemical fuels, and is not inferior to the previous types of release paper, and the use of this adhesive Base paper and labels for sheets and labels. Specifically, the present invention provides the following items.

(1) The first aspect of the present invention is a release paper, which is characterized by comprising: a paper base material; one or both sides of the paper base material contains resin derived from biomass and/or biodegradable resin Barrier layer; and a release agent layer on at least one of the barrier layers.

(2) The second aspect of the present invention is the release paper as described in item (1), wherein the above-mentioned bio-derived resin contains bio-derived monomer polymerization of bio-polyolefin.

(3) The third aspect of the present invention is the release paper as described in (2), wherein the above-mentioned biomass-derived monomer is biomass-derived ethylene.

(4) The fourth aspect of the present invention is the release paper as described in (2), wherein the biomass polyolefin has a density of 0.910 g/cm ³ or more and less than 0.965 g/cm ³ .

(5) The fifth aspect of the present invention is the release paper as described in any one of (1) to (4), wherein the bio-derived resin contained in the barrier layer is relative to the barrier The total barrier layer is 1% by weight or more.

(6) The sixth aspect of the present invention is the release paper as described in (1), wherein the biodegradable resin is selected from aliphatic polyesters and their derivatives.

(7) The seventh aspect of the present invention is the release paper as described in (1), wherein the biodegradable resin contained in the barrier layer is 50% by weight or more relative to the entire barrier layer.

(8) The eighth aspect of the present invention is the release paper as described in any one of (1) to (7), wherein the barrier layer further contains polyolefin derived from fossil fuels.

(9) The ninth aspect of the present invention is the release paper as described in any one of (2) to (5), wherein the main resin forming the barrier layer is polyethylene.

(10) The tenth aspect of the present invention is the release paper as described in any one of (1) to (9), wherein the release agent layer contains a silicone-based release agent.

(11) The eleventh aspect of the present invention is the release paper as described in (10), wherein the silicone-based release agent is an emulsion type or a solvent-free silicone-based release agent.

(12) The twelfth aspect of the present invention is an adhesive sheet characterized by containing the release paper as described in any one of items (1) to (11), an adhesive layer, and a substrate for an adhesive sheet .

(13) The 13th aspect of the present invention is the adhesive sheet as described in (12), wherein the adhesive layer contains a bio-based adhesive.

(14) The fourteenth aspect of the present invention is the adhesive sheet as described in (13), wherein the bio-binder contains a tackifier, and the tackifier contains a resin selected from the group consisting of rosin resin and terpene One or more resins, and the biomass ratio of the adhesive layer is 1.0% or more.

(15) The 15th aspect of the present invention is the adhesive sheet as described in any one of (12) to (14), wherein the substrate for the adhesive sheet is paper or a bio-resin film.

(16) The 16th aspect of the present invention is a base paper for labels, which is characterized by containing the release paper as described in any one of (1) to (11), an adhesive layer, and a label substrate .

(17) The 17th aspect of the present invention is the base paper for labels as described in (16), wherein the adhesive layer contains a bio-based adhesive.

(18) The 18th aspect of the present invention is the base paper for labels as described in (17), wherein the above-mentioned bio-adhesive contains a tackifier, and the above-mentioned tackifier contains a rosin resin and terpene One or more olefin resins, and the biomass ratio of the adhesive layer is 1.0% or more.

(19) The 19th aspect of the present invention is the label base paper as described in any one of (16) to (18), wherein the label substrate is paper or a bio-resin film.

(20) The twentieth aspect of the present invention is a label characterized by using the label base paper described in any one of (16) to (19). Effect of invention

In the present invention, even if the barrier layer contains biodegradable resin and/or biodegradable resin, it has the same release properties as the polyolefin layer derived from fossil fuels, and is not inferior to the conventional release paper , And the adhesive sheet, base paper and label used for the label.

Implementation of the invention

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

(Release paper) Fig. 1 is a schematic cross-sectional view of an embodiment of the release paper 10 in the present invention. The release paper 10 in this embodiment includes: a paper substrate 11; a barrier layer 12 containing bio-derived resin and/or biodegradable resin on one or both sides of the paper substrate 11; and A release agent layer 13 on at least one of the barrier layers 12. In addition, the release paper 10 can also form a barrier layer 12 and a release agent layer 13 on both sides of the paper substrate 11 to become a double-sided release paper (not shown). In addition, in the release paper 10 of this embodiment, the paper substrate 11 may further form a warpage suppression layer on the surface of the opposite side where the barrier layer 12 and the release agent layer 13 are formed. The warpage suppression layer is not particularly limited, and may be, for example, a barrier layer 12 and a polyolefin layer 14 derived from petrochemical fuels described later.

(Paper substrate) The paper substrate 11 used for the release paper 10 in this embodiment is not particularly limited. Examples include: cellophane, semi-cellophane, forest paper, kraft paper, clay-coated paper, molded paper, alkaline paper, Coated paper, paperboard, white paperboard, or dust-free paper as generally known as low dust generation disclosed in Japanese Patent Publication No. 6-11959. In addition, the paper substrate 11 may be subjected to various surface treatments such as heating or corona discharge treatment in advance in order to improve adhesion to the barrier layer 12.

The paper substrate 11 preferably has a thickness of 40 μm or more and 300 μm or less. When the thickness of the paper substrate 11 is less than 40μm, the release paper 10, the label base paper 20, and the adhesive sheet will increase the occurrence of wrinkles; when the label base paper 20 is manufactured, it will be cut during label processing. Poor processing suitability. On the other hand, when the thickness of the paper base 11 exceeds 300 μm, the rigidity becomes too high, and therefore the workability is deteriorated. In addition, the thickness of the paper substrate 11 is measured in accordance with JIS P8118:2014.

The square meter weight of the paper substrate 11 is preferably 40g/m² or more and 200g/m² or less, and more preferably 50g/m² or more and 160g/m² or less. When the square meter weight of the paper substrate 11 is less than 40g/m², the paper strength may be poor and the processing suitability may be poor. On the other hand, when the square meter weight of the paper substrate 11 exceeds 200 g/m², the workability may be poor.

(Barrier layer) The barrier layer 12 in this embodiment contains bio-derived resin and/or biodegradable resin, but may also contain polyolefin derived from fossil fuel. In the present invention, when the barrier layer 12 contains bio-derived resin, the amount of polyolefin derived from fossil fuels can be reduced compared to the previous one, and therefore the environmental load can be reduced. In addition, when the barrier layer 12 contains a biodegradable resin, the release paper 10 will be partially biodegradable, so that the load on the environment can be reduced.

Bio-derived resins refer to resins made with biomass as raw materials. At the same time, the resin derived from biomass can also be regarded as having the function of biological decomposition. In the present invention, the bio-resin having a biodegradation function is defined as bio-resin. In this case, the barrier layer 12 may contain two or more kinds of resins derived from biomass with different biomass ratios. The biomass-derived monomers used to make the biomass-derived resin can be exemplified by biomass-derived olefins such as biomass-derived ethylene and biomass-derived propylene. Among them, the biomass-derived ethylene is preferred. These biomass-derived monomers can be used alone or in combination of two or more. In the present invention, it is preferable that the resin derived from biomass contains biopolyolefin derived from the polymerization of monomers derived from biomass; the biopolyolefin is polyethylene derived from biopolymers derived from ethylene. Better. In addition, in the present invention, "bio-derived resin" and "bio-derived polyolefin" refer to the use of bio-derived raw materials for at least a part of the raw materials and all of the raw materials using bio-derived materials.

The above-mentioned bio-derived ethylene can be produced from the following bio-derived raw materials as follows. First of all, biomass ethanol is produced from biomass. The biomass that becomes the raw material of biomass ethanol, for example: sucrose, corn, sugar beet, cassava, sugar beet, wood, algae, etc. Among these types of biomass, in terms of production efficiency, it is better to contain a lot of sugar or starch, sucrose, corn and sugar beet.

Then, using biomass ethanol as the starting material, it is converted into ethylene through a dehydration reaction, and the resulting biomass-derived ethylene is separated from the produced water. The separated biomass-derived ethylene is then refined by the adsorption method. Ethylene, which is derived from refined biomass, can be used as a raw material for polyethylene using conventionally known chemical engineering techniques.

The above-mentioned biomass-derived polyethylene is not particularly limited. Examples include high-density polyethylene (HDPE), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), linear low-density polyethylene ( LLDPE) and so on. Among them, the polyethylene derived from biomass is preferably linear low-density polyethylene (LLDPE) from the viewpoints of popular use and easy availability.

In addition, the biomass-derived propylene can be produced by metathesis by using the above-mentioned biomass-derived ethylene as the starting material. At the same time, other manufacturing methods can also change the fermentation conditions of the above-mentioned biomass-derived raw materials to produce 1,3-propanediol. The substance can be dehydrated to produce biomass-derived propylene.

In the barrier layer 12, the bio-derived resin formed by the polymerization of the above-mentioned bio-derived monomers is preferably 1% by weight or more relative to the entire barrier layer 12, more preferably 5% by weight or more, and 8 It is more preferable that it is more than weight %. When the content of the biomass-derived resin in the barrier layer 12 is more than 1% by weight, the amount of fossil fuel used can be reduced compared with the previous one. In addition, the barrier layer 12 does not necessarily contain 100% by weight of resin derived from biomass. Moreover, the barrier layer 12 may contain polyolefins derived from fossil fuels in addition to biodegradable resins and/or resins derived from biomass. On the other hand, when bio-polyolefin is used in the barrier layer 12, as the blending ratio of the bio-derived resin increases, the tackiness on the surface of the barrier layer 12 tends to increase, and When the barrier layer 12 is laminated on the paper substrate 11, processing suitability such as winding properties may deteriorate. Therefore, when biomass polyolefin is used, the barrier layer 12 should preferably contain polyolefin derived from fossil fuels in addition to biodegradable resin and/or resin derived from biomass. , Bio-derived resin is preferably 100% by weight or less, more preferably 50% by weight or less, and more preferably 30% by weight or less.

In bio-polyolefin, in theory, when all the raw materials of polyolefin are olefins such as bio-derived ethylene, the concentration of bio-derived carbon is 100%, so the biomass ratio of bio-polyolefin is 100%. At the same time, the concentration of biomass-derived carbon in polyolefins derived from fossil fuels that are made only with raw materials derived from fossil fuels is 0%, so the biomass ratio of polyolefins derived from fossil fuels is 0%. In the barrier layer 12, at least part of the raw materials used are raw materials derived from biomass, and the biomass ratio is not necessarily 100%. The biomass ratio in the barrier layer 12 is preferably 1% or more, more preferably 3% or more, and even more preferably 5% or more. When the biomass ratio in the barrier layer 12 is 1% or more, the load on the environment can be reduced compared to the previous one.

Here, the biomass ratio refers to an index indicating the mixing ratio of raw materials derived from fossil fuels and raw materials derived from biomass, and is determined by measuring the concentration of radiocarbon (C ¹⁴ ), and then expressed by the following formula. Biomass ratio (%) = C ¹⁴ concentration (pMC) × 0.935

Among them, C ^{14 has} a certain concentration in biomass, but it hardly exists in fossil fuels. Therefore, the concentration of C ¹⁴ measured by accelerator mass spectrometry can be used as an indicator of the biomass ratio contained.

The polymerization method of the biomass polyolefin in this embodiment is not particularly limited, and it can be carried out by a conventionally known method. The polymerization temperature and polymerization pressure are preferably adjusted appropriately depending on the polymerization method and polymerization device. In addition, the polymerization device is not particularly limited, and conventionally known devices can be used.

Bio-polyolefin has a density above 0.910g/cm ³ and less than 0.965g/cm ³ . When the density is less than 0.910g/cm ³ , there is a tendency to show a decrease in heat resistance. On the other hand, when the density is 0.965 g/cm ³ or more, the release force will increase. The density of the biomass polyolefin can be measured in accordance with the method specified in Method A in JIS K7112-1980 after the annealing (annealing) described in JIS K6760-1995.

The biodegradable resin has biodegradability and good film forming properties. When the barrier layer 12 is formed, it only needs to satisfy the mechanical properties and durability of the release paper 10, and it is not particularly limited. It can be a material derived from biology. It can also be a material derived from petroleum. Examples of such biodegradable resins include: aliphatic polyesters and their derivatives, polyesters produced by microorganisms, aromatic-aliphatic polyesters, aliphatic polyester carbonates, aliphatic polyester amides, fatty acids Polyester ether, polyamino acid, polyvinyl alcohol, starch, cellulose and cellulose acetate, hydroxyethyl cellulose, hydroxypropyl cellulose and other cellulose derivatives, chitin, chitosan, mannose Among polysaccharides such as polysaccharides, aliphatic polyesters and their derivatives are preferably used.

The aliphatic polyester and its derivatives may, for example, be polylactic acid (PLA), polybutylene succinate-based resin, polyester whose monomer unit contains 3-hydroxyalkyl acid, and the like.

The above-mentioned polylactic acid (PLA) is made from lactic acid obtained from the fermentation of corn and other plants as raw materials. Because of its interlocking nature that can be broken down into water and carbon dioxide by microorganisms, and then used for the development of plants, it is a type of biological reuse. It is better to use in the present invention.

Specific examples of the above-mentioned polybutylene succinate resin include: polybutylene succinate (PBS), polybutylene succinate-adipate (PBSA), polybutylene succinate-lactide Wait. Usable polybutylene succinate resin products (commodities), for example, polybutylene succinate resin "BioPBS" (registered trademark) manufactured by Mitsubishi Chemical Corporation (polybutylene succinate, polysuccinate) Acid-butylene adipate, etc.), the polybutylene succinate resin "Bionore" (registered trademark) manufactured by Showa Denko Corporation, the polybutylene succinate resin manufactured by Shandong Fuwin New Material, and BASF Polyadipate-butylene terephthalate resin "Ecoflex" (registered trademark), etc. The above-mentioned polybutylene succinate resin may be a material derived from biology or a material derived from petroleum.

Specific examples of the polyester whose monomer unit contains 3-hydroxyalkanoic acid include: PHB (poly(3-hydroxybutyric acid), or poly-3-hydroxybutyric acid], PHBH (poly(3-hydroxybutyric acid) -co-3-hydroxyhexanoic acid), or poly(3-hydroxybutyric acid-co-3-hydroxyhexanoic acid)), PHBV (poly(3-hydroxybutyric acid-co-3-hydroxyvaleric acid), or poly( 3-hydroxybutyric acid-co-3-hydroxybutyric acid)], P3HB4HB (poly(3-hydroxybutyric acid-co-4-hydroxybutyric acid), or poly(3-hydroxybutyric acid-co-4-hydroxybutyric acid)] , Poly(3-hydroxybutyric acid-co-3-hydroxyoctanoic acid), or poly(3-hydroxybutyric acid-co-3-hydroxyoctadecanoic acid), etc.

Commercial products of the above-mentioned aliphatic polyesters and their derivatives, for example, in terms of aliphatic polyesters obtained by polycondensation of diols (diols) and polycarboxylic acids, 1,4-butanediol and amber Acid-derived PBS (for example: Bionore 1000 series products (registered trademark): Showa Denko Corporation, BioPBS FZ series products (registered trademark): Mitsubishi Chemical Corporation); PBSA copolymerized with adipic acid in PBS (for example: Bionore 3000 series products (registered trademark): manufactured by Showa Denko Corporation, BioPBS FD series products (registered trademark): manufactured by Mitsubishi Chemical Corporation); polyethylene glycol and succinic acid derived from polyethylene succinate (PES), hydroxyalkyl acid Poly(3-hydroxyalkanoate) of aliphatic polyester copolymer obtained with polycarboxylic acid (including, for example: poly(3-hydroxybutyric acid-co-3-hydroxyhexanoic acid) (PHBH) ( For example: AONILEX (registered trademark): manufactured by Kaneka Corporation); PBAT (copolymer of 1,4-butanediol, adipic acid and terephthalic acid) which is a copolymer of aliphatic polyester and terephthalate ( For example: Ecoflex (registered trademark): manufactured by BASF Corporation); 1,4-butanediol, succinic acid and terephthalic acid copolymer of polybutylene terephthalate (PBTS) (for example: Biomax (Registered trademark): manufactured by DuPont); PLA (for example: REVODE (registered trademark): manufactured by Hisun Biomaterials, Ingeo (registered trademark): manufactured by NatureWorks); Polycaprolactone (PCL) (for example: CAPA6800 ( Registered trademark): manufactured by Perstorp Corporation) etc.

In the barrier layer 12, the above-mentioned biodegradable resin is preferably 50% by weight or more relative to the entire barrier layer 12, more preferably 60% by weight or more, and more preferably 70% by weight or more. When the barrier layer 12 contains more than 50% by weight of the biodegradable resin, the release paper 10 has partial biodegradability, and therefore can reduce the load on the environment compared to the previous one.

The barrier layer 12 may also contain polyolefins derived from fossil fuels which are formed by polymerization of monomers derived from fossil fuels. Monomers derived from fossil fuels are not particularly limited. Examples include ethylene, propylene, 1-butene, 2-methyl-1-butene, 2-methyl-1-pentene, and 1-hexene. Ene, 2,2-dimethyl-1-butene, 2-methyl-1-hexene, 4-methyl-1-pentene, 1-heptene, 3-methyl-1-hexene, 2,2-Dimethyl-1-pentene, 3,3-dimethyl-1-pentene, 2,3-dimethyl-1-pentene, 3-ethyl-1-pentene, 2 , 2,3-trimethyl-1-butene, 1-octene, 2,2,4-trimethyl-1-octene and other α-olefins. These fossil fuel-derived monomers can be used alone or in combination of two or more. In addition, the main resin forming the barrier layer 12 is preferably polyethylene.

The barrier layer 12 preferably has a thickness of 0.5 μm or more and 50 μm or less, and more preferably has a thickness of 5 μm or more and 50 μm or less. When the thickness of the barrier layer 12 is less than 0.5 μm, it is difficult to prevent the release agent from penetrating into the paper substrate 11. On the other hand, when the thickness of the barrier layer 12 exceeds 50 μm, there will be an extra thickness, which is not suitable for application.

In the barrier layer 12, various additives, fillers, etc. may be added as needed within the range where the effects of the present invention are not hindered. The fillers are clay, silica, calcium carbonate, titanium oxide, zinc oxide, and the like.

The method of forming the barrier layer 12 on one or both sides of the paper substrate 11 is not particularly limited. It can be a conventionally known method, for example, the paper substrate 11 is made of biodegradable resin and biomass. The resin coating solution is applied and then dried to form the barrier layer 12 and the paper substrate 11 and the barrier layer 12 are laminated with an adhesive; the paper substrate 11 and the barrier layer are simultaneously laminated by the melt extrusion method The barrier layer 12 is extruded and formed. In this embodiment, it is preferable to form by a melt extrusion method or a method of laminating with an adhesive.

In the case of the method of laminating the paper substrate 11 and the barrier layer 12 with an adhesive, the adhesive used is not particularly limited, and examples include pressure-sensitive adhesives, heat-sensitive adhesives, and laminate adhesives. Moreover, as for the polymer composed of an adhesive, for example, acrylic adhesive, polyisocyanate adhesive, epoxy adhesive, rubber adhesive, etc. can be used. Among them, acrylic adhesives are particularly suitable for use because they are composed of a single component and have good transparency and durability. Acrylic adhesives, such as: n-butyl acrylate, 2-ethylhexyl acrylate, etc. as main components; components that impart cohesion to the main components, such as methyl acrylate, ethyl acrylate, methyl methacrylate Esters, styrene, acrylonitrile, vinyl acetate, etc.; functional monomers as crosslinking points, such as acrylic acid, methacrylic acid, acrylamide derivatives, hydroxyethyl acrylate, glycidyl methacrylate, etc. , The polymer obtained by copolymerization is mixed with appropriate cross-linking agent to use as adhesive.

The release paper 10 in the present invention may also contain a resin layer derived from fossil fuels. Specifically, it may contain a polyolefin layer 14 derived from fossil fuels. The polyolefin layer 14 containing petrochemical fuels can improve barrier properties and pore resistance. The polyolefin layer 14 derived from fossil fuels is a resin layer made of resin materials containing monomers derived from fossil fuels. The biomass ratio of the polyolefin layer 14 derived from fossil fuels is 0%. Figure 2 is a schematic cross-sectional view of another embodiment of the release paper 10 of the present invention. Release paper 10 includes a paper substrate 11, a barrier layer 12 containing biodegradable resin and bio-derived resin on one or both sides of the above-mentioned paper substrate 11, and a petrochemical fuel-derived made from raw materials derived only from fossil fuels The polyolefin layer 14 and the release agent layer 13. In addition, the release paper 10 can also be formed by the barrier layer 12 and/or the polyolefin layer 14 derived from fossil fuels and the release agent layer 13 on both sides of the paper substrate 11 to become a double-sided release paper (not shown). At the same time, the release paper 10 in this embodiment can also be formed on the paper substrate 11 with the barrier layer 12, the polyolefin layer 14 derived from petrochemical fuel, and the release agent layer 13 on the opposite end surface, forming a warp Curve suppression layer. The warpage suppression layer is not particularly limited. For example, it may be the barrier layer 12 or the polyolefin layer 14 derived from petrochemical fuel.

The polyolefin layer 14 derived from petrochemical fuel contains polyolefin formed by polymerizing monomers derived from the above-mentioned petrochemical fuel. Monomers derived from fossil fuels can be used alone or in combination of two or more. Polyolefin derived from petrochemical fuels is preferably polyethylene formed by polymerization of ethylene-containing monomers.

The method for polymerizing polyolefins derived from fossil fuels is not particularly limited, and it can be operated by conventionally known methods. The polymerization temperature and polymerization pressure are preferably adjusted appropriately depending on the polymerization method and polymerization device. In addition, the polymerization device is not particularly limited, and conventionally known devices can be used.

The polyolefin layer 14 derived from fossil fuels preferably has a thickness of 0.1 μm or more and 30 μm or less. In addition, the polyolefin layer 14 derived from petrochemical fuel may contain more than two layers, each of which may have the same composition or different compositions.

In the polyolefin layer 14 derived from petrochemical fuels, various additives, fillers, etc. may be added as needed within the scope of the effects of the present invention. The above-mentioned fillers are clay, silica, calcium carbonate, titanium oxide, and oxide. Zinc etc.

The method of forming the polyolefin layer 14 derived from petrochemical fuel on the barrier layer 12 is not particularly limited. It can be a conventionally known method, for example: coating the barrier layer 12 with polyolefin derived from petrochemical fuel Liquid coating and drying to form the polyolefin layer 14 derived from fossil fuels and the method of simultaneously extruding the paper base material 11, the barrier layer 12 and the polyolefin layer 14 derived from fossil fuels by the melt extrusion method . In this embodiment, it is preferable to form by a melt extrusion method. In the release paper 10 of this embodiment, the barrier layer 12 can prevent the release agent in the release agent layer 13 from penetrating into the paper base material 11, that is, it performs the function of a so-called barrier layer. Therefore, when the release paper 10 of the present embodiment includes the barrier layer 12, the release agent in the release agent layer 13 can be prevented from penetrating into the paper substrate 11.

(Release agent layer) The release agent used on the release agent layer 13 in this embodiment is not particularly limited. For example, silicone-based, fluorine-based, alkyd resin, long-chain alkane-based resin, various waxes, etc. can be used. Type agent. Among them, from the viewpoint of release characteristics, the release agent is preferably a silicone-containing release agent. In addition, as the biodegradable release agent, it is preferable to use the release agent disclosed in Japanese Patent Laid-Open No. 2002-212428.

Silicone-based release agent resins, such as: trimethylchlorosilane, dimethyldichlorosilane, methyltrichlorosilane, diphenyldichlorosilane, phenyltrichlorosilane, methyl vinyl Homopolymer or copolymer of dichlorosilane, etc. These can be used alone or as a mixture of any two or more. In addition, the silicone-based release agent can be used in any form of solvent, solventless, or emulsion, but from the environmental point of view, the emulsion or solventless type is preferred.

The release agent layer 13 preferably has a thickness of 0.01 μm or more and 10 μm or less, and more preferably 0.1 μm or more and 5 μm or less.

The method of coating the release agent on the barrier layer 12 is not particularly limited. For example, it can be appropriately selected: blade coater, air knife coater, bar coater ( Various coating devices such as rod blade coater, bar blade coater, gravure coater, bar coater, and multi-stage roll coater are used.

The use of the release paper 10 in this embodiment is not particularly limited. For example, the protection of the adhesive layer of the adhesive sheet, adhesive tape, label, etc. (protection of the adhesive surface of the adhesive product).

(Adhesive sheet) The release paper 10 of this embodiment can be used as an adhesive sheet formed by adhering an adhesive layer on the surface of the release agent layer 13 to a base material for an adhesive sheet. The adhesive sheet can be coated on the surface of the release agent layer 13 of the release paper 10 of the present invention by a generally known method, dried to form an adhesive layer, and then pasted on the adhesive layer for the adhesive sheet The base material can be easily manufactured by winding.

The base material for the adhesive sheet in this embodiment is not particularly limited, and it may be composed of a paper-based material or a resin-based film with a resin-based material as a main component. Examples of resin-based films include resin films made from raw materials derived from fossil fuels, recycled resin films made from recycled resins, and bio-resin films made from resins derived from biomass. Adhesive sheet substrates, among them, from the viewpoint of reducing the load on the environment, paper, recycled resin films made from recycled resins, or bio-based resin films made from bio-derived resins are preferable, paper or bio-based Resin film is better. The base material for the adhesive sheet of the paper series can be, for example, coated paper such as forest paper, art paper, coated paper, foil paper, colored paper/fancy paper, impregnated paper, cellophane, dust-free paper, etc. The resin used in the resin film can be, for example, polyester, polyethylene terephthalate, polyethylene, polylactic acid, polyurethane-urea, vinyl chloride, polystyrene, polytetrafluoroethylene, Polyimide, ABS, polyester-based synthetic paper, etc. The base material for the adhesive sheet can be appropriately selected depending on the application and environment of the adhesive sheet.

The adhesive used in the adhesive layer in this embodiment is not particularly limited, and examples include rubber, acrylic, silicone, epoxy, polyester, urethane, and poly From the viewpoint of reducing the environmental load of olefin-based, vinyl ether-based, or bio-derived bio-based adhesives, among them, bio-based adhesives are preferred. At the same time, it can also be solvent-free adhesives such as solvent-based adhesives, emulsion-based adhesives, hot-melt adhesives, etc., and can be cured by irradiating energy rays into a releasable energy-ray-curable adhesive. In addition, the adhesive used in the adhesive layer in this embodiment may be blended with coloring agents such as tackifiers, softeners, anti-aging agents, fillers, dyes, or pigments, if necessary. Examples of tackifiers include rosin resins, terpene phenol resins, terpene resins, aromatic hydrocarbon-modified terpene resins, petroleum resins, coumarone-indene resins, and styrene resins. Resin, phenolic resin, xylene resin, etc. The adhesive layer in this embodiment preferably contains a tackifier. The tackifier is preferably one or more selected from rosin resin and terpene resin selected from plant-derived resins. When the tackifier contains one or more selected from the rosin resin and terpene resin of plant-derived resin, it can increase the biomass ratio of the adhesive layer. The biomass ratio of the adhesive layer in this embodiment is preferably 1.0% or more. The upper limit of the biomass ratio of the adhesive layer, the higher the better, and the application is preferably below 90%.

The biomass binder is preferably formed from an emulsion-type binder composition containing an emulsion-type binder and an emulsion-type tackifier. In addition, the tackifier of the emulsion-type tackifier preferably contains one or more selected from rosin resin and terpene resin, and the biomass ratio of the adhesive layer is 2.9% or more and less than 24.8%.

The adhesive sheet of this embodiment can be formed into a suitable form such as a sheet, tape, and label shape, and used for bonding of an adhesive body and other applications suitable for the previous adhesive sheet. Hereinafter, another specific example of the adhesive sheet suitable for use in this embodiment will be given.

(Base paper and label for label) The release paper 10 of this embodiment can be used as the base paper 20 for labels. Fig. 3 is a schematic cross-sectional view of one embodiment of the base paper 20 for labels using the release paper 10 of the present invention. The base paper 20 for labels includes a release paper 10, an adhesive layer 21, and a base material 22 for labels. In addition, not shown in the figure, the surface of the label substrate 22 may contain a conventionally known laminated film in order to protect the label substrate 22 and prevent fading.

In addition, the label base paper 20 of the present embodiment may also include a release paper 10, an adhesive layer 21, a label base material 22, an adhesive layer 21, and a release paper 10 (not shown). As mentioned above, the surface of the label substrate 22 may contain a conventionally known laminated film (not shown) in order to protect the label substrate 22 and prevent fading.

The adhesive used in the adhesive layer 21 in this embodiment is not particularly limited. The same adhesive used in the above-mentioned adhesive sheet can be used, but from the viewpoint of reducing the load on the environment, the biomass The binder is better. The bio-binder is preferably formed by an emulsion-type binder composition containing an emulsion-type binder and an emulsion-type tackifier. In addition, the adhesive layer 21 preferably contains a tackifier. In terms of the tackifier, one or more selected from the group consisting of rosin resin and terpene resin, and the biomass ratio of the adhesive layer 21 is preferably 1.0% or more.

The adhesive layer 21 preferably has a dry thickness of 5 μm or more and 200 μm or less, and more preferably 10 μm or more and 100 μm or less. When the dried thickness is less than 5 μm, the adhesive force may be insufficient and the thickness of the adhesive layer 21 may be difficult to be uniform. On the other hand, when the dried thickness exceeds 200 μm, the drying time after the adhesive is applied may be time-consuming, and the adhesive may easily overflow from the label base paper 20, which may reduce production efficiency.

The label substrate 22 in this embodiment is not particularly limited, and the same substrate as the substrate used in the above-mentioned adhesive sheet substrate can be used, but from the viewpoint of reducing the load on the environment, among them, Paper, recycled resin film made of recycled resin, or bio-resin film made of bio-derived resin is preferable, and paper or bio-resin film is more preferable. The label base material 22 can be appropriately selected depending on the purpose and environment in which the label base paper 20 is used. The label substrate 22 is preferably used as a printing substrate capable of printing patterns and information or printing in various printing methods.

In addition, from the viewpoint of making the toner, ink, etc. stable, it is better to have a printing layer on the surface of the back end of the adhesive layer 21 of the label substrate 22 (not shown). The printing layer can be formed by coating various coating agents for printing. The coating agent for printing is preferably acrylic resin or polyester resin, or a coating agent for printing used in combination with these. From the viewpoint of reducing the load on the environment, the coating agent for printing is preferably a coating agent composed of a resin derived from biomass.

At the same time, the label base paper 20 is used to protect the toner and printing ink, etc., and a coating agent may be further coated on the label base 22 or the printing layer. The coating agent used is not particularly limited. From the viewpoint of reducing the load on the environment, it is preferable to use a polyurethane resin and a polylactic acid resin derived from biomass.

In addition, by using the label base paper 20 of this embodiment, printing of the label base material 22, and half cut and cutting of the label base paper 20 as necessary can obtain the label of this embodiment. Plastic bottles, labels with product designs, logo packaging, bottle cap sealing films, combined packaging, etc., in terms of environmental awareness and resource conservation, require the use of materials with a high proportion of bio-resin. Therefore, the label base paper 20 of this embodiment using the release paper 10 of this embodiment is particularly suitable for this purpose. Example

Hereinafter, examples and comparative examples are used to further illustrate the present invention in detail, but the present invention is not limited in any way. In addition,% and parts, unless specifically limited, mean% by weight and parts by weight.

(Example 1) First, on one surface of the cellophane with a square meter weight of 83g/m², use the biomass polyolefin as LLDPE (manufactured by Braskem Company, trade name: SLL118, density 0.916g/cm ³ , MFR=1.0 g/10 minutes, the biomass ratio of 87%) 10% by weight, fossil fuel derived LDPE (biomass ratio of 0%) 45% by weight, and fossil fuel derived HDPE (biomass ratio of 0%) 45% by weight mixture, A bio-polyolefin layer with a thickness of 20μm was formed by the melt extrusion method (mass ratio 8.7%). On the bio-polyolefin layer, a release agent layer with a thickness of 0.5 μm is formed with a silicone-based release agent to obtain a release paper. After that, an acrylic adhesive (manufactured by LINTEC Corporation, trade name: PAT1) was applied on the release agent layer to a dry thickness of 20 μm by a casting method. Then, it was pasted on polypropylene synthetic paper (manufactured by YUPO, trade name: SGS-80) to make an adhesive sheet.

(Example 2) First, on both sides of road forest paper with a square meter weight of 78g/m², the biomass polyolefin is used as LLDPE (manufactured by Braskem Company, trade name: SLL118, density 0.916g/cm ³ , MFR). =1.0g/10 minutes, biomass ratio 87%) 10% by weight, LDPE derived from fossil fuels (biomass ratio 0%) 45% by weight, and HDPE derived from fossil fuels (biomass ratio 0%) 45% by weight The mixture is melted and extruded to form a 20μm-thick bio-polyolefin layer (biomass ratio 8.7%). On the bio-polyolefin layer, a release agent layer with a thickness of 0.5 μm is formed with a silicone-based release agent to obtain a release paper. After that, an acrylic adhesive (manufactured by LINTEC Corporation, trade name: PAT1) was applied on the release agent layer to a dry thickness of 20 μm by a casting method. Then, it was pasted on polypropylene synthetic paper (manufactured by YUPO, trade name: SGS-80) to make an adhesive sheet.

(Example 3) First, on one surface of cellophane with a square meter weight of 83g/m², PBS (polybutyl succinate) (bio-derived PBS (manufactured by Mitsubishi Chemical Co.) , Trade name: BioPBS FZ91, density 1.26g/cm ³ , MFR=5.0g/10 minutes, biomass ratio 50%) 100% by weight, and a 17μm-thick biomass PBS layer is formed by the melt extrusion method. On the base PBS layer, a release agent layer with a thickness of 0.5μm is formed with a silicone-based release agent. Then, an acrylic adhesive (manufactured by LINTEC, trade name: PAT1) is applied to the release agent layer by the spreading method It was coated to a dry thickness of 20μm. Then, it was pasted on polypropylene synthetic paper (manufactured by Yupo, trade name: SGS-80) to make an adhesive sheet.

(Example 4) First, on one surface of cellophane with a square meter weight of 83g/m², the biomass resin is PBSA (polysuccinate-dibutyl adipate) (bio-derived PBS ( Manufactured by Mitsubishi Chemical Corporation, trade name: BioPBS FD92, density 1.24g/cm ³ , MFR=4.0g/10 minutes, biomass ratio 35%) 100% by weight, and a 32μm-thick BioPBS layer is formed by melt extrusion. On the biogenic PBS layer, a release agent layer with a thickness of 0.5 μm was formed with a silicone-based release agent. Then, an adhesive (manufactured by LINTEC, trade name: PAT1) was applied on the release agent layer to extend The flow method is applied to a dry thickness of 20μm. Then, it is pasted on polypropylene synthetic paper (manufactured by YUPO, trade name: SGS-80) to make an adhesive sheet.

(Example 5) Except that the polypropylene synthetic paper (manufactured by YUPO Corporation, trade name: SGS-80) of Example 1 was changed to a polylactic acid-based film with a thickness of 50μm (manufactured by Mitsubishi Plastics Corporation, trade name: ECOLOJU SA, 50μm thick, aliphatic Except that the polyester content is 95% by weight or more), an adhesive sheet was produced in the same manner as in Example 1.

(Example 6) Except that the polypropylene-based synthetic paper (manufactured by YUPO Corporation, trade name: SGS-80) of Example 1 was changed to a paper base material (Dawlin paper with a thickness of 80μm and a square meter weight of 100g/m²), the same applies to Example 1. The same method is used to make an adhesive sheet.

(Example 7) Except that the polypropylene synthetic paper (manufactured by YUPO Company, trade name: SGS-80) of Example 1 was changed to mechanical recycled polyester resin film (thickness 50μm, mechanical recycled polyester resin content: 80% by weight) , Non-renewable resin content: 20% by weight), the same method as in Example 1 was used to make an adhesive sheet.

(Example 8) Except that the adhesive of Example 1 (manufactured by LINTEC, trade name: PAT1) was changed to the following emulsion type adhesive, the same method as in Example 1 was used to produce an adhesive sheet.

(Manufacturing of emulsion type adhesive) The emulsion type adhesive is manufactured using a reactor including a mixer, a thermometer, a circulating cooler, and a dropping funnel. In the reactor, 55% by weight of ion-exchanged water was heated to 80°C under stirring. Then, when the temperature of the ion-exchange water reached 80°C, 0.1% by weight of ammonium persulfate as a polymerization initiator was added to prepare an aqueous ammonium persulfate solution. In addition to the aqueous solution of ammonium persulfate, 60% by weight of 2-ethylhexyl acrylate, 38% by weight of butyl acrylate, and 2% by weight of acrylic acid are used with an anionic reactive emulsifier (product name "NEW FRONTIER A-229E", manufactured by Daiichi Industrial Pharmaceutical Co., Ltd.) 1% by weight, an appropriate amount of 25% ammonia water for neutralization, and 0.4% by weight of ammonium persulfate, added to 43% by weight of ion exchange water and stirred by a mixer to Obtain a pre-emulsion.

Secondly, keeping the temperature in the reactor at 80°C, while dripping the aqueous solution of ammonium persulfate into the pre-emulsion in 2 hours. Then, 1% by weight of persulfuric acid was added after 1 hour and 2 hours after the dripping into the pre-emulsion to terminate the polymerization reaction, and the acrylic emulsion adhesive was manufactured. Next, 100% by weight of the acrylic emulsion type adhesive (converted to solid content) is mixed with emulsion type adhesive 1 (product name "HARIESTER", product number "SK-218NS", manufactured by Harima Chemical Group), Tackifying resin: Rosin resin, Tackifying resin softening temperature: 100°C) 10% by weight (converted to solid content), Emulsion type tackifier 2 (product name "SUPER ESTER", product number "E-730-55" , Manufactured by Arakawa Chemical Industry Co., Ltd., tackifier resin: rosin resin, tackifier resin softening temperature: 125°C) 0.5% by weight (converted to solid content), and emulsion type tackifier 3 (product name "SUPER ESTER", product No. "E-788", manufactured by Arakawa Chemical Industry Co., Ltd. Tackifying resin: rosin resin, Tackifying resin softening temperature: 160°C) 2.5% by weight (converted to solid content), formulated as an emulsion-type adhesive composition.

(Comparative example 1) First, a mixture of 50% by weight of LDPE derived from fossil fuels and 50% by weight of HDPE derived from fossil fuels is formed on one surface of a cellophane with a weight of 83g/m² by melt extrusion to form a polyolefin layer with a thickness of 20μm. On the polyolefin layer, a release agent layer with a thickness of 0.5 μm is formed with a silicone-based release agent. After that, the adhesive (manufactured by LINTEC Corporation, trade name: PAT1) was applied on the release agent layer to a dry thickness of 20 μm by a casting method. Then, it was pasted on polypropylene synthetic paper (manufactured by Yupo, trade name: SGS-80) to make a sample. The biomass ratio of the polyolefin layer of the release paper is 0%.

>Release evaluation> The laminate layer of the base material for the adhesive sheet and the adhesive layer is peeled from each adhesive sheet. When the release paper can be peeled off without breaking, it is ○, and when the release paper is broken, it is x. The results obtained in Examples 1 to 8 and Comparative Example 1 are shown in Table 1.

[Table 1] Evaluation of Release Adhesive sheet Release paper Adhesive layer Base material for adhesive sheet Paper substrate Barrier layer Example 1 ○ Cellophane square meter weight 83g/m² Biomass polyolefin (20μm, biomass ratio 8.7%) Acrylic adhesive Polypropylene Synthetic Paper Example 2 ○ Dowling Paper Example 3 ○ cellophane Aliphatic polyester resin trade name: BioPBS FZ91 Acrylic adhesive Polypropylene Synthetic Paper Example 4 ○ cellophane Aliphatic polyester resin PBS: BioPBS FD92 Acrylic adhesive Polypropylene Synthetic Paper Example 5 ○ cellophane Biomass polyolefin (20μm, biomass ratio 8.7%) Acrylic adhesive Polylactic acid film Example 6 ○ cellophane Acrylic adhesive Daolin paper (weight per square meter 100g/m²) Example 7 ○ cellophane Acrylic adhesive Mechanically recycled polyester resin film Example 8 ○ cellophane Biomass emulsion type adhesive Polypropylene Synthetic Paper Comparative example 1 ○ cellophane Polyolefin derived from fossil fuels (20μm, biomass ratio 0%) Acrylic adhesive Polypropylene Synthetic Paper

It can be seen from Table 1 that Example 1, using biodegradable polyolefin instead of cellophane paper, Example 2, using biodegradable resin instead of cellophane, Example 3 and Example 4, substituted polypropylene Examples 5 to 7 in which paper uses polylactic acid film, paper, and mechanically recycled polyester resin film, and Example 8 in which bio-based adhesives are used instead of acrylic adhesives, show the origin of all and the use of fossil fuels Comparative Example 1 of polyolefin has the same excellent release properties. Therefore, the release paper of the present invention can provide a release paper that is not inferior to the conventional release paper, as well as the adhesive sheet, label base paper and label used therewith.

Above, the present invention has been described with embodiments and examples. It is not necessary to further explain that the technical scope of the present invention is not limited to the above-mentioned embodiments and examples. Those in the industry can also understand that the above-mentioned embodiments and examples can be used as Various changes or improvements. At the same time, the description of the scope of the patent application can also clarify the technical scope that the present invention can include.

10: Release paper 11: Paper substrate 12: Barrier layer 13: Release agent layer 14: Polyolefin layer derived from fossil fuels 20: Base paper for label 21: Adhesive layer 22: Substrate for label

[Figure 1] Shows a schematic cross-sectional view of one embodiment of the release paper of the present invention. [Figure 2] Shows a schematic cross-sectional view of another embodiment of the release paper of the present invention. [Figure 3] Shows a schematic cross-sectional view of one embodiment of the base paper for labels using the release paper of the present invention.

10: Release paper

11: Paper substrate

12: Barrier layer

13: Release agent layer

20: Base paper for label

21: Adhesive layer

22: Substrate for label

Claims (20)

A release paper, characterized by comprising: a paper substrate; a barrier layer containing bio-derived resin and/or biodegradable resin on one or both sides of the aforementioned paper substrate; and at least a barrier layer of the aforementioned barrier layer Release agent layer on one side. The release paper described in item 1 of the scope of patent application, wherein the aforementioned bio-derived resin contains bio-derived polyolefin polymerized by monomers. The release paper as described in item 2 of the scope of patent application, wherein the aforementioned biomass-derived monomer is biomass-derived ethylene. The release paper as described in item 2 of the scope of patent application, wherein the aforementioned biomass polyolefin has a density of 0.910 g/cm ³ or more and less than 0.965 g/cm ³ . The release paper described in any one of items 1 to 4 of the scope of the patent application, wherein the resin derived from the biomass contained in the barrier layer is 1% by weight or more relative to the entire barrier layer. The release paper described in item 1 of the scope of patent application, wherein the aforementioned biodegradable resin is selected from aliphatic polyesters and their derivatives. The release paper described in the first item of the scope of patent application, wherein the biodegradable resin contained in the barrier layer is 50% by weight or more relative to the entire barrier layer. The release paper described in any one of items 1 to 7 of the scope of patent application, wherein the aforementioned barrier layer contains polyolefin derived from fossil fuel. As for the release paper described in any one of items 2 to 5 in the scope of the patent application, the main resin forming the aforementioned barrier layer is polyethylene. The release paper described in any one of items 1 to 9 in the scope of the patent application, wherein the release agent layer contains a silicone-based release agent. The release paper described in item 10 of the scope of patent application, wherein the aforementioned silicone release agent is an emulsion type or solvent-free silicone release agent. An adhesive sheet, which is characterized by containing the release paper, an adhesive layer, and a base material for the adhesive sheet as described in any one of items 1 to 11 in the scope of the patent application. The adhesive sheet described in item 12 of the scope of patent application, wherein the adhesive layer contains a biomass adhesive. The adhesive sheet according to item 13 of the scope of patent application, wherein the bio-based adhesive contains a tackifier, and the tackifier contains one or more selected from the group consisting of rosin resin and terpene resin, and the aforementioned adhesive The biomass ratio of the layer is more than 1.0%. The adhesive sheet described in any one of items 12 to 14 in the scope of the patent application, wherein the substrate for the adhesive sheet is paper or a bio-resin film. A base paper for labels, which is characterized by containing the release paper, adhesive layer and label substrate as described in any one of items 1 to 11 in the scope of the patent application. The label base paper described in the 16th item of the scope of patent application, wherein the aforementioned adhesive layer contains a bio-based adhesive. The label base paper described in item 17 of the scope of patent application, wherein the aforementioned bio-adhesive agent contains a tackifier, and the aforementioned tackifier contains one or more selected from the group consisting of rosin resin and terpene resin, and the aforementioned adhesive The biomass ratio of the agent layer is 1.0% or more. The base paper for labels described in any one of items 16 to 18 of the scope of the patent application, wherein the aforementioned base material for labels is paper or a bio-resin film. A label characterized by using the label base paper described in any one of items 16 to 19 of the scope of patent application.

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