JP2013035975A - Laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a pressure-sensitive adhesive which is excellent in pasting fitness onto the skin, is fixed firmly when being pasted onto the skin, and forms a pressure-sensitive adhesive layer that can be peeled off easily without leaving the pressure-sensitive adhesive on the skin when being peeled, and also to provide a laminate using the pressure-sensitive adhesive.SOLUTION: The laminate is produced by allowing a lipophilic pressure-sensitive adhesive containing a styrene-based block copolymer, a softener and a tackifier resin, and a hydrophilic pressure-sensitive adhesive containing water and at least one selected from polyvinyl alcohol, a cellulose derivative, gelatin, proteinous polymer, a polyacrylic acid resin, a polyacrylate polymer and an N-alkyl acrylamide-based copolymer to form each an adhesive layer on an identical surface of a sheet-like substrate.

Description

  The present invention relates to a laminate using a lipophilic pressure-sensitive adhesive and a hydrophilic pressure-sensitive adhesive. In detail, this invention relates to the laminated body used suitably for sticking to skin.

Adhesive sheets are used in various forms in the medical field, such as adhesive bandages, surgical tapes, and electrode fixing sheets for electrocardiogram measurement. Many of the pressure-sensitive adhesives used in conventional medical pressure-sensitive adhesive sheets are made of an acrylic polymer. In general, the acrylic polymer is applied to, for example, a support substrate or release paper after adjusting the viscosity using an organic solvent or the like. The organic solvent used for viscosity adjustment is volatilized and removed after coating.
At this time, the organic solvent and the unreacted acrylic monomer are not sufficiently removed by volatilization (insufficient drying), and the organic solvent and the acrylic monomer may remain in the pressure-sensitive adhesive. In an adhesive sheet in which an adhesive such as an adhesive bandage is in direct contact with the human body, if the drying is insufficient, the organic solvent remaining in the adhesive may be absorbed from the skin into the body and cause inflammation such as a rash. In addition, the organic solvent that has been volatilized and removed in the drying process causes environmental pollution, and there is a concern that the health and safety of workers may be threatened.

  On the other hand, conventional methods for producing a pressure-sensitive adhesive tape that does not use a solvent include a hot-melt method in which a hot-melt pressure-sensitive adhesive is heated and melted and applied onto the substrate, and an emulsion-type pressure-sensitive adhesive is applied to the substrate and dried. Emulsion method, extrusion polymerization method in which heat-polymerizable monomer liquid is extruded and coated on a substrate while heating, kneading, and polymerizing in a heated barrel, and photoirradiating monomer liquid is applied to the substrate and then irradiated in an inert atmosphere. A photopolymerization method for polymerization is known. These are not yet sufficient from the viewpoint of workability (introduction of light irradiation device, reaction time) and adhesive properties such as adhesiveness to skin, irritation and adhesive residue, and are not suitable for medical use such as bandages. None of the pressure-sensitive adhesive sheets were suitably used.

  As an example of a pressure-sensitive adhesive not using a solvent, a pressure-sensitive adhesive using urethane crosslinking, which is a pressure-sensitive adhesive using an oxyalkylene polymer, is known (see Patent Documents 1 and 2).

  Also known is a multilayer ionic conductive adhesive obtained by crosslinking or curing an ionic conductive adhesive precursor containing a urethane acrylate oligomer, a humectant and an electrolyte (see Patent Document 3).

  Moreover, the adhesive composition for medical adhesive tape containing the pressure-sensitive-adhesive polymer obtained by UV-curing a urethane acrylate oligomer is known (refer patent document 4).

  In addition, it is for skin patch which is obtained by curing a pressure-sensitive adhesive composition containing a polyether polymer having at least one alkenyl group at the terminal, a compound having 1 to 10 hydrosilyl groups in the molecule, and the like. Is known (see Patent Document 5).

  It also has (meth) acrylate ester monomers having an alkyl chain with 4 to 20 carbon atoms, copolymers containing acidic comonomers, hydrophilic plasticizers, water, water-soluble salts, surfactants, and amine functionality. A conductive pressure-sensitive adhesive containing a polymer is known (see Patent Document 6).

  The pressure-sensitive adhesives described in Patent Documents 1 and 2 have been reported to have excellent properties such as adhesion to skin, moisture permeability, water absorption, etc., but because of the use of urethane cross-linking, the curing speed is adjusted. Is difficult, and the toxicity of unreacted isocyanate groups is feared.

  The multilayer ion conductive adhesive described in Patent Document 3 has been reported to have excellent adhesion, but unreacted carboxyl groups and unreacted isocyanate groups remain in the adhesive layer. Toxicity is a concern.

  In the pressure-sensitive adhesive composition described in Patent Document 4, the isocyaninate group remains in the pressure-sensitive adhesive layer. In addition, oligomers that have not been UV cured remain and cause skin irritation when applied to the skin.

  The pressure-sensitive adhesive composition described in Patent Document 5 has been reported to have little skin irritation when applied to the skin, but has low adhesive strength, and when applied to the skin for a long time, the adhesive sheet peels off from the skin. May end up.

  In the conductive pressure-sensitive adhesive described in Patent Document 6, the acrylic monomer remains in the adhesive layer, and there is skin irritation when it is applied to the skin.

JP 7-310066 A JP 2002-60456 A JP 2004-107378 A JP 2005-58288 A JP 2005-110875 A Special table 2003-501545 gazette

  The object of the present invention is excellent in the applicability to the skin, firmly fixed when applied to the skin, and can be easily removed without leaving a pressure-sensitive adhesive on the skin. The object is to provide a laminate using a pressure-sensitive adhesive capable of forming a pressure-sensitive adhesive layer.

The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems.
That is, the present invention provides a lipophilic pressure-sensitive adhesive comprising a styrenic block copolymer, a softener and a tackifying resin, and
At least one selected from polyvinyl alcohol, cellulose derivatives, gelatin, protein polymers, polyacrylic acid resins, polyacrylate polymers, and N-alkylacrylamide copolymers and water. The present invention relates to a laminate characterized in that the hydrophilic pressure-sensitive adhesive contained therein is formed by forming an adhesive layer on the same surface of a sheet-like substrate.

In addition, the present invention is a lipophilic pressure sensitive adhesive,
Styrene block copolymer (A) having a styrene ratio of 10 to 40% by weight and having a triblock type structure,
The present invention relates to the above laminate comprising a mineral oil softener (B) having a weight average molecular weight of 700 to 10,000 and a tackifying resin (C) having a softening point of 80 to 160 ° C.

In the present invention, the hydrophilic pressure-sensitive adhesive is
It is related with the said laminated body characterized by using both the UV curable adhesive and the adhesive which is not UV curable.

  Moreover, this invention relates to the said laminated body characterized by the viscosity in 170 degreeC of a lipophilic pressure sensitive adhesive (1) being 500-50000 mPa * s by a B-type viscosity meter.

The present invention also relates to the above laminate, wherein the total coating amount of the lipophilic pressure-sensitive adhesive and the hydrophilic pressure-sensitive adhesive is 1 to 2000 g / m ² .

  The present invention also relates to the above laminate, wherein at least one adhesive layer is laminated in a foamed state.

  The present invention also relates to the above laminate, wherein at least one adhesive layer is laminated in a bead state.

  The present invention also relates to the above laminate, wherein at least one adhesive layer is laminated in a spiral state.

  The present invention also relates to the above laminate, wherein at least one adhesive layer is laminated in a curtain state.

  The present invention also relates to the above laminate, wherein at least one adhesive layer is laminated in a dot state.

  Moreover, this invention relates to the said laminated body characterized by the two or more types of adhesive bond layers being alternately laminated | stacked on the stripe.

  Moreover, this invention relates to the said laminated body characterized by the two or more types of adhesive bond layers being laminated | stacked alternately by mesh shape.

The present invention further relates to the above laminate, which further comprises a transdermal drug.

  According to the present invention, the pressure-sensitive adhesive has excellent aptitude for application to the skin, is firmly fixed when applied to the skin, and can be easily removed without leaving a pressure-sensitive adhesive on the skin. It has become possible to provide a laminate using a pressure-sensitive adhesive capable of forming an agent layer. Furthermore, the laminate in which the pressure-sensitive adhesive layer is laminated on one side or both sides can be stored without the pressure-sensitive adhesive layer protruding from the end portion over time.

The conceptual diagram of the laminated body laminated | stacked on the bead state. The conceptual diagram of the laminated body laminated | stacked in the spiral state. The conceptual diagram of the laminated body laminated | stacked in the curtain state. The conceptual diagram of the laminated body laminated | stacked in the dot state. The conceptual diagram of the laminated body laminated | stacked by stripe alternately. Conceptual diagram of a laminate that is alternately layered in a mesh

The lipophilic pressure-sensitive adhesive of the present invention will be described.
The lipophilic pressure-sensitive adhesive of the present invention contains a styrene block copolymer (A), a mineral oil softener (B), a tackifier resin (C), and other additives as required. It becomes a lipophilic pressure-sensitive adhesive composition.

The styrene block copolymer (A) constituting the lipophilic pressure-sensitive adhesive used in the present invention is a styrene-butadiene-styrene block copolymer (hereinafter also abbreviated as “SBS”), styrene-butadiene-styrene. Hydrogenated block copolymer (hereinafter also abbreviated as “SEBS”), styrene-isoprene-styrene block copolymer (hereinafter also abbreviated as “SIS”), hydrogen of styrene-isoprene-styrene block copolymer Additives (hereinafter abbreviated as “SEPS”), styrene-butadiene-isoprene-styrene block copolymer (hereinafter also abbreviated as “SBIS”), hydrogenated styrene-butadiene-isoprene-styrene block copolymer (Hereinafter abbreviated as “SEEPS”) at least one selected from the group consisting of It is.
Further, the copolymer may be carboxyl-modified, and further, the styrene block in the copolymer is a mixture of styrene and other aromatic vinyl compounds such as α-methylstyrene. A copolymer may be included.
Further, the styrene-based block copolymer (A) has a styrene ratio of 10 to 40% by weight of the entire copolymer (A) and has a triblock type structure part. However, the present invention is not limited to the structure having only the structure part, and may have a part of diblock structure. The diblock type content is preferably 60% by weight or less, and more preferably 50% by weight or less. If it exceeds 60% by weight, the cohesive force is lowered. These are preferable because they are excellent in heat resistance during melting. The styrenic block copolymer (A) may be used alone or in combination of two or more.

  When the total of the styrenic block copolymer (A), mineral oil softening agent (B), and tackifying resin (C) constituting the lipophilic pressure-sensitive adhesive of the present invention is 100 parts by weight, the lipophilic feeling The compounding quantity of the styrenic block copolymer (A) used for a pressure type adhesive is 5-65 weight part. Preferably it is 10-60 weight part. When the blending amount of the styrenic block copolymer (A) is less than 5 parts by weight, the cohesive force of the resulting pressure-sensitive adhesive tends to decrease. When the blending amount of the styrenic block copolymer (A) exceeds 65 parts by weight, production by kneading may be difficult.

  The mineral oil softening agent (B) constituting the lipophilic pressure-sensitive adhesive used in the present invention is a mixture of hydrocarbons containing aromatics, hydrocarbons containing naphthenic rings, paraffin chains, and the number of paraffin chain carbons. Paraffin-based mineral oil softeners that account for 50% or more of the total number of carbon atoms are preferred. In general, paraffinic mineral oil softeners whose paraffin chain carbon number occupies 50% or more of the total carbon number, naphthenic mineral oil softener whose naphthenic ring carbon number occupies 30 to 40% by weight of the total carbon number, Those having an aromatic carbon number of 30% by weight or more of the total carbon number are called aromatic mineral oil softeners and are distinguished.

  The polystyrene-reduced weight average molecular weight of the mineral oil softener (B) constituting the lipophilic pressure-sensitive adhesive used in the present invention by a gel permeation chromatography method (hereinafter also abbreviated as “GPC”) is 700 to 10,000. . Preferably it is 800-9500. If the mineral oil softening agent (B) has a weight average molecular weight of less than 700, bleeding out tends to occur. If the weight average molecular weight of the mineral oil softening agent (B) exceeds 10,000, the fluidity at the time of melting tends to decrease.

  When the total of the styrenic block copolymer (A), mineral oil softening agent (B) and tackifying resin (C) constituting the lipophilic pressure-sensitive adhesive of the present invention is 100 parts by weight, the pressure-sensitive adhesive The blending amount of the mineral oil softener (B) used in is 10 to 94 parts by weight. Preferably it is 15-90 weight part. If the blending amount of the mineral oil softening agent (B) is less than 10 parts by weight, the processability is deteriorated. When the blending amount of the mineral oil softener (B) exceeds 94 parts by weight, it becomes difficult to maintain the cohesive strength.

As the tackifier (C) constituting the lipophilic pressure-sensitive adhesive used in the present invention, phenol resin, modified phenol resin, terpene phenol resin, xylene phenol resin, cyclopentadiene-phenol resin, xylene resin, aliphatic system , Alicyclic and aromatic petroleum resins, hydrogenated aliphatic, alicyclic and aromatic petroleum resins, phenol-modified petroleum resins, rosin ester resins, hydrogenated rosins Examples thereof include ester resins, low molecular weight polystyrene resins, terpene resins, and hydrogenated terpene resins.
A tackifier (C) may be used independently, or 2 or more types may be used together.

The softening point of the tackifier resin (C) is preferably 80 to 160 ° C. When the softening point of the tackifier resin (C) is less than 80 ° C., the cohesive force is lowered, and the cohesive failure may occur at the time of peeling. When the softening point of the tackifying resin (C) exceeds 160 ° C., tack may disappear in a low temperature range.
In addition, the softening point in this invention is the temperature calculated | required by the method prescribed | regulated to JISK6863. That is, after leaving the specified ring filled with the lipophilic pressure-sensitive adhesive for 12 hours or more, put it in the heat medium and place the specified ball on the specified ring filled with the pressure-sensitive adhesive. When the temperature of the heat medium is increased at a rate of λ, the temperature when the sphere sinks due to softening of the lipophilic pressure-sensitive adhesive and touches the bottom plate of the ring platform.

  When the total of the styrenic block copolymer (A), mineral oil softening agent (B) and tackifying resin (C) constituting the lipophilic pressure-sensitive adhesive of the present invention is 100 parts by weight, the pressure-sensitive adhesive The compounding amount of the tackifier resin (C) used in is 1 to 60 parts by weight. Preferably it is 3-58 weight part. If the compounding amount of the tackifier resin (C) is less than 1 part by weight, the processability is deteriorated. When the amount of the tackifier resin (C) exceeds 60 parts by weight, tack may disappear in a low temperature range.

Examples of the hydrophilic pressure-sensitive adhesive of the present invention include UV curable adhesives and non-UV curable adhesives. Only one or both can be used. Moreover, you may form an adhesive bond layer by mixing 2 or more types or using separately.
The hydrophilic pressure-sensitive adhesive of the present invention is preferably composed of, for example, polyvinyl alcohol, cellulose derivative, gelatin, protein polymer, and water.

Water contained in the hydrophilic pressure-sensitive adhesive is an important component for hydrating the skin portion to which the skin adhesive sheet of the present invention has been applied in a wet state. Water is preferably contained in the hydrophilic pressure-sensitive adhesive within the range of 10 to 90% by weight, more preferably within the range of 30 to 70% by weight of the entire hydrophilic pressure-sensitive adhesive. If the water content is less than 10% by weight, tack may disappear, and if it exceeds 90% by weight, a hydrophilic pressure-sensitive adhesive layer is formed when a hydrophilic pressure-sensitive adhesive layer is formed on the support. The mechanical strength of the layer may be insufficient.

Examples of the UV curable hydrophilic pressure-sensitive adhesive of the present invention include polyacrylate polymers and N-alkylacrylamide copolymers. Specifically, poly (meth) acrylic acid alkali metal salt, sodium (meth) acrylate-vinyl alcohol copolymer ((meth) methyl acrylate-vinyl acetate copolymer saponified product), poly (meth) acrylonitrile series Saponified polymer, poly (meth) acrylic acid derivative such as hydroxyethyl methacrylate polymer or poly (meth) acrylamide, polyacrylamide and alginic acid derivative of sodium alginate or propylene glycol alginate, N-alkylacrylamide copolymer, PVA -Acrylate copolymer, vinyl alcohol-acrylate (carboxyl group-containing) copolymer crosslinked product, self-crosslinked polyacrylic acid neutralized product, acrylate copolymer crosslinked product, Polyacrylic acid partial neutralized cross-linked product, poly Cross-linked crylate, acrylate-vinyl acetate copolymer and saponified product thereof, acrylate-acrylate copolymer cross-linked, acrylate-acrylamide copolymer cross-linked, acrylamide Copolymer hydrolyzate cross-linked product, 2-acrylamido-2-methylpropane sulfonic acid-acrylic acid cross-linked product, polyacrylonitrile cross-linked hydrolyzate, acrylonitrile copolymer hydrolyzed Cross-linked product, polyethylene oxide cross-linked with acrylic acid, copolymer cross-linked product of methoxypolyethylene glycol and acrylic acid, polyacrylate cross-linked product, hydrolyzate of acrylic ester-vinyl acetate copolymer, acrylic acid A salt-acrylamide copolymer cross-linked product is a preferred example.

Although it does not specifically limit as a drug for percutaneous absorption added to the lipophilic pressure sensitive adhesive of the present invention, hydrophilic pressure sensitive adhesive, and UV curable hydrophilic pressure sensitive adhesive, vitamin A, vitamin E and oil solubility are not particularly limited. Vitamin C derivatives, ceramide, licorice extract, rosehip oil, coenzyme Q10 and the like can also be used. These are also effective as decorative sheets. In addition, anti-inflammatory / analgesic ingredients such as indomethacin, horse chestnut extract, arnica tincture, ferbinac, ketoprofen flurbiprifen, camphor, menthol and other refreshing agents; Nitroglycerin and isosorbide nitrate are used for heart disease, and tubuterol is used to widen the airway to ease breathing, fentanyl is used as a painkiller for cancer, and hormones such as steroids An agent can be used.
Any can be used as long as transdermal absorption can be applied, and in particular, estrogen, luteinizing hormone and the like can be mentioned. Examples of the estrogen include 17β-estradiol or an ester thereof, ethinyl estradiol or an ester thereof, estriol or an ester thereof, or conjugated estrogens. Examples of progesterone include progesterone, chlormadinone acetate, hydroxyprogesterone acetate, dihydrogesterone, allylestrenol, norethisterone, hydroxyprogesterone, and esters thereof.

  The lipophilic pressure-sensitive adhesive and the hydrophilic pressure-sensitive adhesive of the present invention include an antioxidant, an ultraviolet absorber, a light stabilizer, an adhesion progress preventive agent, a silane coupling agent, and an antibacterial agent as long as the object of the invention is not impaired. , Deodorant, fragrance, moisturizer, water absorbing agent, electrolyte salt, refreshing agent, bactericidal agent, whitening agent, wrinkle / dullness inhibitor, oil, steroidal anti-inflammatory agent, non-steroidal anti-inflammatory agent, local anesthetic An analgesic, hemostatic agent, wound healing promoter, antipruritic agent, moisturizer, reactive monomer, additive, photopolymerization initiator, and the like may be added.

  Examples of the antioxidant include pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4- Hydroxyphenyl) propionate, diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate, 4,6-bis (octylthiomethyl) -o-cresol, ethylenebis (oxy Ethylene) bis [3- (5-t-butyl-4-hydroxy-m-tolyl] propionate, tris (2,4-di-t-butylphenyl) phosphite, bis (2,4-di-t-butyl) Phenyl) pentaerythritol diphosphite, etc. These antioxidants may be used alone or in two kinds. Above may be used in combination.

  The above-mentioned phenolic antioxidant is stabilized by donating hydrogen to ROO (peroxy radical) generated in the chain growth process of auto-oxidation, and becomes a stable phenoxy radical protected by an ortho-position substituent. It functions as a radical trapping agent that stops the chain reaction, thereby effectively suppressing thermal degradation of the resin composition. In particular, a combination of a phenol-based antioxidant and a lactone-based antioxidant, a vitamin E-based antioxidant, or the like, which has a faster radical trapping reaction than the phenol-based antioxidant, can be further improved. In addition, the above phosphorus antioxidants have the function of non-radically decomposing peroxides and ROOH and stopping the chain reaction in the auto-oxidation process, thereby effectively preventing the thermal deterioration of the resin composition. To suppress.

  The ultraviolet absorber is not particularly limited, and examples thereof include commonly used ones such as salicylic acid series, benzophenone series, and benzotriazole series. These ultraviolet absorbers may be used alone or in combination of two or more.

  Examples of the light stabilizer include those usually used as hindered amines.

  Examples of the above-mentioned adhesive progress preventive agent include fatty acid amides, polyethyleneimine long-chain alkyl grafts, soybean oil-modified alkyd resins (for example, trade name “Arachid 251” manufactured by Arakawa Chemical Industries, Ltd.), tall oil-modified alkyd resins ( For example, Arakawa Chemical Industries, Ltd., trade name “Arachid 6300” and the like. These adhesive progress inhibitors may be used alone or in combination of two or more.

  Examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycidoxy. Propyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3 -Aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxy Run, 3-mercaptopropyl trimethoxysilane, 3-mercaptopropyl triethoxy silane, mercaptopropyl butyl trimethoxy silane, 3-mercaptopropyl methyl dimethoxy silane, and the like. These silane coupling agents may be used alone or in combination of two or more.

  Examples of the antibacterial agents include benzylamine antibacterial agents such as butenafine and salts thereof, bifonazole, neticoconazole, ketoconazole, lanoconazole, clotrimazole, miconazole, oxyconazole, thioconazole, croconazole, omoconazole, sulconazole and salts thereof Imidazole antibacterial agents, allylamine antibacterial agents such as terbinafine and its salts, morpholine antibacterial agents such as amorolfine and its salts, thiocarbamic acid antibacterial agents such as rilanaphthate, tolnaftate and tosiclate, nystatin, tricomycin, variocin, siccanin, And antibacterial agents such as antibiotics such as pyrrolnitrin. In addition, Kumagusu extract, tea catechin and the like can be mentioned. These antibacterial agents may be used alone or in combination of two or more.

  The deodorant is not particularly limited as long as it has a deodorizing effect, but lauryl methacrylate, geranyl chlorinate, citronellyl senecionate, terpene aldehydes, pyruvate esters, zinc 2-ethylhexanoate And zinc ricinoleate. These deodorizers may be used independently and 2 or more types may be used together.

  Examples of the above fragrances include hydrocarbon fragrances such as pinene and limonene, alcoholic fragrances such as linalool, geraniol, citronellol, menthol, borneol, benzyl alcohol, anis alcohol and β-phenethyl alcohol, and phenolic fragrances such as anethole and eugenol. , N-butyraldehyde, isobutyraldehyde, hexyl aldehyde, citral, citronellal, benzaldehyde, aldehyde fragrance such as cinnamaldehyde, ketone fragrance such as carvone, menthone, camphor, acetophenone, ionone, γ-butyl lactone, coumarin, cineol Lactone fragrances such as octyl acetate, benzyl acetate, cinnamyl acetate, butyl propionate, methyl benzoate and the like. These fragrance | flavors may be used independently and 2 or more types may be used together.

  Examples of the humectant include NMF such as 1,3-butylene glycol, ethylene glycol, propylene glycol, dipropylene glycol, glycerin, maltitol, sorbitol, and trehalose, pyrrolidone carboxylic acid, lactic acid, urea, and amino acid. Ingredients, heparin, hyaluronic acid, chondroitin sulfate, chitin, chitosan, sodium alginate, aloe, pectin and other polysaccharides, collagen, elastin, keratin, gelatin, casein, silk, wheat protein, petrolatum, soybean protein, DNA and other pebutides And hydrolysates thereof, sodium chloride, seawater and other minerals, ceramide, cholesterol ester and the like. These humectants may be used alone or in combination of two or more.

  Examples of the water-absorbing agent include starch, crosslinked carboxylmethylated cellulose, a polymer or copolymer of acrylic acid or an alkali metal acrylate, crosslinked polyacrylic acid and a salt thereof, and a polyacrylate graft polymer. These water absorbing agents may be used alone or in combination of two or more.

  Examples of the electrolyte salt include alkali metal halides such as sodium halide, potassium halide, magnesium halide, and calcium halide, alkaline earth metal halides and other metal halides, and hypochlorous acid of various metals. Salts, chlorites, chlorates, perchlorates, sulfates, nitrates, phosphates, ammonium salts, inorganic salts such as various complex salts, and monovalent organic carboxylic acids such as acetic acid, benzoic acid, lactic acid, tartaric acid Acid salts, monovalent or divalent salts of polyvalent carboxylic acids such as fumaric acid, succinic acid, adivic acid, citric acid, metal salts and organic ammonium salts of organic acids such as sulfonic acids and amino acids, Polymer electrolysis such as (meth) acrylic acid, polyvinyl sulfonic acid, polytertiary butylacrylamide sulfonic acid, polyallylamine, polyethyleneimine Such as salt, and the like. These electrolyte salts may be used independently and 2 or more types may be used together.

It does not specifically limit as said refreshing agent, Eucalyptus oil, 1-menthol, dl-camphor, etc. are mentioned. These refreshing agents may be used alone or in combination of two or more.

The above bactericide is not particularly limited, and examples thereof include chlorhexidine hydrochloride and fradiomycin sulfate. These bactericides may be used independently and 2 or more types may be used together.

The whitening agent is not particularly limited, and examples thereof include ascorbic acid and derivatives thereof, hydroquinone derivatives, kojic acid and derivatives thereof, animal placenta extracts, plant extracts, and the like.

The wrinkle / dullness inhibitor is not particularly limited, and various synthetic vitamins, natural vitamins and derivatives thereof, amino acids and derivatives thereof can be used. These wrinkle / dullness preventing agents may be used alone or in combination of two or more.

The oil component is not particularly limited as long as it is an oil component used as a raw material for cosmetics and cosmetics. Avocado oil, camellia oil, turtle oil, macadamia nut oil, corn oil, mink oil, olive oil, rapeseed oil, egg yolk oil , Sesame oil, persic oil, wheat germ oil, sasanqua oil, castor oil, flaxseed oil, safflower oil, cottonseed oil, eno oil, soybean oil, peanut oil, tea seed oil, kaya oil, rice bran oil, cinnagiri oil, Japanese kiri oil , Jojoba oil, germ oil, glyceryl trioctanoate, glyceryl triisopalmitate, cetyl isooctanoate, isopropyl myristate, squalane, isoparaffin, methylsilicone, methylphenylsilicone, and di- (phytosteryl 2-L-glutamate) Liquid oils such as octyldodecyl), cacao butter, coconut oil, Fat, horse oil, hydrogenated coconut oil, palm oil, beef tallow, sheep fat, hydrogenated beef tallow, palm kernel oil, pork tallow, beef bone oil, owl kernel oil, hydrogenated oil, cow leg fat, owl, hydrogenated castor oil, beeswax, Candelilla wax, cotton wax, carnauba wax, bayberry wax, bota wax, whale wax, montan wax, nuka wax, lanolin, capok wax, lanolin acetate, liquid lanolin, sugar cane wax, lanolin fatty acid isopropyl, lauric acid hexyl, reduced lanolin, jojoballow, hard lanolin, shellac wax, Examples include ozokerite, microcrystalline wax, ceramide, cholesterol, phytosterol, macadamia nut oil fatty acid phytosteryl, N-lauroyl-L-glutamate di (phytosteryl, behenyl, 2-octyldodecyl). These oil components may be used independently and 2 or more types may be used together.

  The steroidal anti-inflammatory agent is not particularly limited, and examples thereof include prednisolone acetate, hydrocortisone acetate, and dexamethasone. These steroidal anti-inflammatory agents may be used alone or in combination of two or more.

  The non-steroidal anti-inflammatory agent is not particularly limited, and examples thereof include indomethacin, diclofenac sodium, piroxicam, ibuprofen, lysozyme chloride, glycyrrhetinic acid and the like. These non-steroidal anti-inflammatory agents may be used alone or in combination of two or more.

  The local anesthetic is not particularly limited, and examples thereof include lidocaine and ethyl aminobenzoate. These local anesthetics may be used alone or in combination of two or more.

  The analgesic is not particularly limited, and examples thereof include morphine and pentazocine. These analgesics may be used independently and 2 or more types may be used together.

  The hemostatic agent is not particularly limited, and examples thereof include zinc oxide, methyl ephedrine hydrochloride, and tannic acid. These hemostatic agents may be used alone or in combination of two or more.

  It does not specifically limit as said wound healing promoter, Allantoin, aluminum dihydroxy allantoin etc. are mentioned. These wound healing promoters may be used alone or in combination of two or more.

  The above antipruritic agent is not particularly limited, and examples thereof include diphenhydramine hydrochloride.

Examples of the reactive monomer include methoxypolyethylene glycol acrylate, ethoxydiethylene glycol acrylate, polyethylene glycol diacrylate, and polypropylene glycol diacrylate. These reactive monomers may be used independently and 2 or more types may be used together.

The above additives include potassium carbonate (anhydrous), sodium carbonate, calcium carbonate, sodium bicarbonate, tetrapotassium pyrophosphate, tetrasodium pyrophosphate, sodium polyphosphate, disodium dihydrogen pyrophosphate, sodium metaphosphate, polyphosphoric acid Examples include potassium, dipotassium hydrogen phosphate, disodium hydrogen phosphate, potassium metaphosphate, tripotassium phosphate, trisodium phosphate, potassium dihydrogen phosphate, disodium dihydrogen phosphate, and the like. These additives may be used independently and 2 or more types may be used together.

The photopolymerization initiator is not particularly limited as long as it generates radicals by cleavage with ultraviolet rays or visible rays. For example, α-hydroxyketone, α-aminoketone, benzylmethyl ketal, bisacylphosphine oxide, metallocene, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methylpropan-1-one, 2-methyl-1-[(methylthio) phenyl] -2-morpholinopropane-1- ON, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, and the like. These photoinitiators may be used independently and 2 or more types may be used together.

  UV absorbers, light stabilizers, adhesion promoters, silane coupling agents, antibacterial agents, deodorants, fragrances, moisturizers, water absorbing agents, electrolyte salts, cooling agents that can be added within the range not impairing the object of the present invention , Disinfectant, whitening agent, anti-wrinkle agent, oil, steroidal anti-inflammatory agent, non-steroidal anti-inflammatory agent, local anesthetic agent, analgesic agent, hemostatic agent, wound healing promoter, antipruritic agent, moisturizer, reaction The addition amount of additives such as a photopolymerizable monomer, an additive, and a photopolymerization initiator is preferably 20% by weight or less, more preferably 18% by weight or less in 100% by weight of the pressure-sensitive adhesive. If it exceeds 10% by weight, bleeding may occur.

  The method for producing the oleophilic pressure-sensitive adhesive of the present invention is not particularly limited, and the mixture is heated and mixed using a roll, a Banbury mixer, a kneader, a melting kettle equipped with a stirrer, a uniaxial or biaxial extruder, and the like. Any method such as a hot melt method or a solvent method dissolving in an appropriate solvent can be used, but the hot melt method is preferable because it has a small influence on the environment.

The lipophilic pressure-sensitive adhesive of the present invention can be applied at 150 to 180 ° C. to prevent deterioration caused by applying excessive heat, and when it is melted or rolls that require low-viscosity coating. It can also be used with a melting pot equipped with an agitator. From such a viewpoint, the pressure-sensitive adhesive of the present invention preferably has a viscosity at 170 ° C. of 500 to 50000 mPa · s.
When the viscosity at 170 ° C. is less than 500 mPa · s, there is a possibility that a pressure-sensitive adhesive may sag when the coating amount is increased.
The viscosity of the pressure-sensitive adhesive is a value measured using a B-type viscometer (measurement conditions are 170 ° C., rotor No. 3, 12 rpm, 30 seconds).

In the lipophilic pressure-sensitive adhesive and the hydrophilic pressure-sensitive adhesive of the present invention, an adhesive layer is formed on the same surface of a sheet-like substrate by coating or the like. An adhesive layer may be formed on each of both surfaces. Each of these adhesives is heated and melted, its solution, etc., using a coating machine or hot melt coating machine usually used for sheet-like substrates such as paper, resin, nonwoven fabric, and the like in a mirror surface state and a foamed state. It can be applied in various patterns such as bead state, spiral state, curtain state, dot state, etc., and pressure sensitive adhesive layer can be formed by heating, cooling and UV irradiation as necessary. Various laminates in which the agent layers are laminated can be obtained. Lipophilic pressure-sensitive adhesives and hydrophilic pressure-sensitive adhesives can be applied in layers. Lipophilic pressure-sensitive adhesives and hydrophilic pressure-sensitive adhesives are applied in parallel, diagonally, and meshed on the same sheet-like substrate. It can also be divided.
The formation of the adhesive layer is only in one of a mirror surface state, a foamed state, a bead state, a spiral state, a curtain state, and a dot state, and the other may be in other forms (for example, FIG. 1 to FIG. 1). 4). Note that the spiral state of FIG. 2 is a ring state. FIG. 5 is a conceptual diagram in which two types of adhesives are alternately formed with an adhesive layer in a bead state, and the adhesive layers are close to each other and formed as a stripe as a whole. FIG. 6 is a conceptual diagram in which alternate adhesive layers are formed in a bead state, and the mutual adhesive layers are formed with a distance and formed in a net shape as a whole.
In addition, a bead state is formed when a coating port is apply | coated with the coating head of one shape, and the weight per one adhesive formed is 0.5-3 g / m. The curtain state is formed by coating with a coating head having a plurality of coating ports, and the weight per one pressure-sensitive adhesive formed is 0.01 to 0.5 g / m.

  Moreover, after providing a pressure sensitive adhesive layer on the releasable sheet mentioned later, the laminated body of this invention can be obtained also by bonding the said pressure sensitive adhesive layer and a sheet-like base material.

  The lipophilic pressure-sensitive adhesive of the present invention is excellent in heat resistance and can be suitably used as a pressure-sensitive adhesive because the change in melt viscosity with time is small even at a high melting temperature. In forming the pressure-sensitive adhesive layer, it is preferable that the lipophilic pressure-sensitive adhesive is heated and melted and applied onto the substrate.

Next, the laminate of the present invention will be described.
The basic structure of the laminate of the present invention is a single-area layered body such as “sheet-like substrate / pressure-sensitive adhesive layer / release sheet”, or “release sheet / pressure-sensitive adhesive layer / sheet form”. It is a double-sided laminate such as “base material / pressure-sensitive adhesive layer / release sheet”. At the time of use, the release sheet is peeled off, and the pressure-sensitive adhesive layer is stuck on the adherend.

  There is no restriction | limiting in particular as a raw material of a sheet-like base material, It can use. As resin sheets, polyester resins, polycarbonate resins, polyarylate resins, acrylic resins, polyphenylene sulfide resins, polystyrene resins, vinyl resins, vinyl chloride resins, polyimide resins, epoxy resins, polyethylene, polypropylene In addition, there are single layers or laminates of polyolefin resins such as Poorinorbornene. A resin sheet in a foamed state can also be used. Other examples include breathable films, non-woven fabrics, woven fabrics, fabrics, paper, glass, metal foils, metal meshes, and composites containing these. Further, if necessary, the surface of the sheet may be subjected to easy adhesion treatment such as corona discharge treatment, plasma treatment, blast treatment, chemical etching treatment, antistatic treatment, coloring treatment and the like.

  Although there is no restriction | limiting in particular in the thickness of these sheet-like base materials, 1-1000 micrometers is preferable from workability | operativity.

The application amount of the pressure-sensitive adhesive layer is preferably 1 to 2000 g / m ² , more preferably 5 to 1980 g / m ² . If the application amount of the pressure-sensitive adhesive layer is less than 1 g / m ² , it is difficult to develop adhesive force. Even when the coating amount of the pressure-sensitive adhesive layer exceeds 2000 g / m ² , in particular, improvement in required characteristics cannot be expected in many cases.

  The pressure-sensitive adhesive layer can be used by being bonded to a release sheet or the like as necessary. The release sheet is not particularly limited as long as the surface is subjected to a release treatment, such as polyester resin such as polyethylene terephthalate, polyolefin resin such as polyethylene, polypropylene and polynorbornene, polyphenylene sulfide resin, and triacetyl cellulose. The thing which uses as a base material the sheet | seat which consists of resin, acrylic resin, etc. is mentioned.

  The laminate of the present invention has either a configuration in which the pressure-sensitive adhesive layer is sandwiched between the sheet-like base material and the release sheet, or between the sheet-like base material and the sheet-like base material. However, it is preferably sandwiched between the sheet-like substrate and the release sheet.

EXAMPLES Hereinafter, the present invention will be described specifically and in detail with reference to examples. However, these examples are only one aspect of the present invention, and the present invention is not limited to these examples.
In the examples, “part” means “part by weight” and “%” means “% by weight”.
The weight average molecular weight by GPC in the present invention refers to a polystyrene conversion obtained by flowing a dilute resin solution through a column packed with gel-like particles and measuring different times until it flows out depending on the molecular size. The weight average molecular weight.
Specific measurement conditions are as follows.
Equipment: Prominence manufactured by Shimadzu Corporation
Column: TOSgel TSKgel GMH × 2 connected detector: RID-10A
Solvent: THF (tetrahydrofuran)
Column temperature: 40 ° C
Flow rate: 1 mL / min

(Production Examples 1-17)
Styrene block copolymer (A), tackifier resin (B), tackifier resin (C), and (A), (B) as necessary, in a kneader equipped with a stirrer in the number of parts shown in Table 1. , (C) and other components were added and stirred at 160 ° C. for 3 hours to obtain a pressure-sensitive adhesive.

The abbreviations of the styrenic block copolymer (A) shown in Table 1 are shown below.
SBS1: SBS, styrene ratio 29% by weight, triblock content 83%, diblock content 17%
SBS2: SBS, styrene ratio 43% by weight, triblock content 100%
SEBS1: SEBS, styrene ratio 34% by weight, triblock content 100%
SEBS2: SEBS, styrene ratio 31% by weight, triblock content 100%
SEBS3: SEBS, styrene ratio 60% by weight, triblock content 100%
SEBS4: SEBS, styrene ratio 32% by weight, triblock content 100%
SEBS5: SEBS, styrene ratio 33% by weight, triblock content 100%
SEBS6: SEBS, styrene ratio 30% by weight, triblock content 88%, diblock content 12%
SEPS1: SEPS, styrene ratio 18% by weight, triblock content 100%
SEPS2: SEPS, styrene ratio 13% by weight, triblock content 100%
SEEPS1: SEEPS, styrene ratio 32% by weight, triblock content 100%
SEEPS 2: SEEPS, styrene ratio 30% by weight, triblock content 100%
SIBS: SIBS, styrene ratio 19% by weight, triblock content 74%, diblock content 26%
SIS: SIS, styrene ratio 16% by weight, triblock content 44%, diblock content 56%

The abbreviations of the mineral oil softener (B) listed in Table 1 are shown below.
Mineral oil 1: Paraffinic mineral oil softener, paraffin chain carbon number in total carbon number: 72.1%, naphthene ring carbon number in total carbon number: 21.5%, aromatic carbon number in total carbon number : 6.4%, weight average molecular weight 1100
Mineral oil 2: Paraffinic mineral oil softener, paraffin chain carbon number in total carbon number: 71%, naphthene ring carbon number in total carbon number: 29%, weight average molecular weight 1000
Mineral oil 3: Paraffinic mineral oil softener, paraffin chain carbon number in total carbon number: 73%, naphthene ring carbon number in total carbon number: 27%, weight average molecular weight 1200
Mineral oil 4: naphthenic mineral oil softener, paraffin chain carbon number in total carbon number: 40.7%, naphthene ring carbon number in total carbon number: 47.2%, aromatic ring carbon in total carbon number Number: 12.1%, weight average molecular weight 1800
Mineral oil 5: Paraffinic mineral oil softener, paraffin chain carbon number in total carbon number: 67.1%, naphthene ring carbon number in total carbon number: 32.8%, aromatic carbon number in total carbon number : 0.1%, weight average molecular weight 750
Mineral oil 6: Paraffinic mineral oil softener, paraffin chain carbon number in total carbon number: 100%, weight average molecular weight 500

Abbreviations for tackifying resins (C) listed in Table 1 are shown below.
Tackifying resin 1: terpene-based tackifying resin, softening point 115 ° C
Tackifying resin 2: Hydrogenated petroleum-based tackifying resin, softening point 100 ° C.
Tackifier resin 3: hydrogenated terpene tackifier resin, softening point 115 ° C.
Tackifying resin 4: terpene-based tackifying resin, softening point 125 ° C
Tackifying resin 5: Hydrogenated petroleum-based tackifying resin, softening point 125 ° C.
Tackifying resin 6: partially hydrogenated petroleum-based tackifying resin, softening point 115 ° C.
Tackifying resin 7: Hydrogenated terpene tackifying resin, softening point 125 ° C.
Tackifying resin 8: Copolymer of α-methylstyrene and styrene, softening point 120 ° C.
Tackifying resin 9: Terpenic tackifying resin partially hydrogenated, softening point 115 ° C.
Tackifying resin 10: Hydrogenated petroleum-based tackifying resin, softening point 115 ° C.
Tackifying resin 11: Rosin-based tackifying resin, softening point 150 ° C.
Tackifying resin 12: Copolymer of α-methylstyrene and styrene, softening point 100 ° C.
Tackifying resin 13: Hydrogenated petroleum-based tackifying resin, softening point 70 ° C

Abbreviations of other components listed in Table 1 are shown below.
Antioxidant: Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]
Humectant 1: Vaseline humectant 2: Glycerin humectant 3: Propylene glycol UV absorber: 2- [5-Chloro (2H) -benzotriazol-2-yl] -4-methyl-6- (tert-butyl) phenol Silane coupling agent: 3-methacryloxypropylmethyldimethoxysilane water-absorbing agent: cross-linked carboxylmethylated cellulose antibacterial agent: benzylamine antibacterial agent fragrance: limonene deodorant: 2-ethylhexanoic acid zinc electrolyte salt 1: sodium chloride electrolyte salt 2: Potassium chloride acrylic monomer: Acrylic acid additive: Calcium carbonate photopolymerization initiator: 2-hydroxy-2-methyl-1-phenyl-propan-1-one Reactive monomer: Polyethylene glycol diacrylate transdermal drug: Fentanyl

Applicator with forming device, applicator with beating coating, applicator with spiral coating, applicator with spray coating, applicator with curtain coating, dot By combining an applicator that can be coated, a foamed pressure-sensitive adhesive layer is formed on a PET (polyethylene terephthalate) sheet as a base material by coating at a coating amount of 500 g / m ² and heating to 170 ° C. Further, a release sheet was further bonded to obtain the following various laminates having a configuration of “release sheet / foamed pressure-sensitive adhesive layer / PET sheet”. The foaming density was set to 0.2 g / cm ³ .
Laminate (1): “Releasable sheet / PET sheet in which pressure-sensitive adhesive layers of Production Example 1 and Production Example 16 are alternately applied in parallel at a width of 10 mm”
Laminate (2): “Releasable sheet / Layer / PET sheet in which the pressure-sensitive adhesives of Production Example 5 and Production Example 15 in the foamed state are alternately applied in parallel in a 10 mm width”
Laminate (3): “Releasable sheet / layer in which pressure-sensitive adhesive layers of Production Example 6 and Production Example 17 in foamed state are alternately applied in parallel with a width of 10 mm / Hydrophilic pressure-sensitive adhesive layer (half surface) / PET sheet "
Laminate (4): “Releasable sheet / layer in which pressure-sensitive adhesive layers of Production Example 4 and Production Example 16 in a foamed state were alternately applied in parallel with a width of 10 mm / hydrophilic pressure-sensitive adhesive layer of Production Example 17 (Half side) / PET sheet "
Laminate (5): “Releasable sheet / Layer / PET sheet coated with pressure-sensitive adhesives of Production Example 7 and Production Example 16 alternately in parallel in a bead state”
Laminate (6): “Releasable sheet / Layer / PET sheet coated with pressure-sensitive adhesives of Production Example 2 and Production Example 15 alternately in parallel in a bead state”
Laminate (7): “Releasable sheet / Layer / PET sheet in which pressure-sensitive adhesives of Production Example 4 and Production Example 17 were applied alternately in parallel in a bead state”
Laminate (8): “Releasable sheet / Layer / PET sheet in which pressure-sensitive adhesives of Production Example 8 and Production Example 18 are alternately applied in parallel in a spiral state”
Laminate (9): “Releasable sheet / Layer / PET sheet in which pressure-sensitive adhesives of Production Example 8 and Production Example 15 were applied in a curtain state alternately in parallel with a width of 20 mm”
Laminate (10): “Releasable sheet / Layer / PET sheet in which the pressure-sensitive adhesives of Production Example 2 and Production Example 15 were applied in a curtain state alternately in parallel with a width of 20 mm”
Laminate (11): “Releasable sheet / Layer / PET sheet in which the pressure-sensitive adhesives of Production Example 3 and Production Example 15 are alternately applied in parallel in a dot state”
Laminate (12): “Releasable sheet / layer / PET sheet in which the pressure-sensitive adhesives of Production Example 1 and Production Example 15 were alternately applied in parallel in a dot state”
Laminate (13): “Releasable sheet / layer in which pressure-sensitive adhesives of Production Example 8, Production Example 16 and Production Example 18 were alternately applied in parallel in a dot state / PET sheet”
Laminate (14): “Releasable sheet / Layer / PET sheet in which pressure-sensitive adhesives of Production Example 6, Production Example 15 and Production Example 17 were alternately applied in parallel in a spiral state”
Laminate (15): “Release sheet / foamed production example 7: layer / PET sheet coated with the pressure-sensitive adhesive of production example 18 alternately in parallel in a bead state”
Laminated body (16): “Releasable sheet / foamed production example 5 Layer / PET sheet coated with pressure-sensitive adhesive of production example 18 alternately in parallel in a bead state”

Laminate (17): “Releasable sheet / Plate sheet coated with pressure-sensitive adhesive of Production Example 9 over the entire surface”
Laminate (18): “Releasable sheet / layer in which pressure-sensitive adhesive of production example 10 in foamed state is applied / PET sheet”
Laminate (19): “Releasable sheet / layer on which the pressure-sensitive adhesive of Production Example 11 in foamed state was applied over the entire surface / PET sheet”
Laminate (20): “Releasable sheet / layer in which pressure-sensitive adhesive of Production Example 12 is applied in a bead state at intervals of 10 mm / PET sheet”
Laminate (21): “Releasable sheet / layer in which pressure-sensitive adhesive of Production Example 13 is applied in a spiral state / PET sheet”
Laminate (22): “Releasable sheet / layer in which the pressure-sensitive adhesive of Production Example 14 was applied to the entire surface in a curtain state / PET sheet”

[Coating suitability]
The pressure-sensitive adhesive was heated and melted, and the viscosity was measured at 170 ° C. using a B-type viscometer. Moreover, it left still in 170 degreeC atmosphere for 3 hours, and the change of the hue was confirmed.
[Criteria]
A: The viscosity was 5000 mPa · s or more and less than 15000 mPa · s. As a result of visual confirmation, there was almost no change in hue.
○: The viscosity was more than 15000 mPa · s and less than 50000 mPa · s. As a result of visual confirmation, there was almost no change in hue.
X: As a result of visual confirmation with a viscosity exceeding 50000 mPa · s, the hue changed to brown.
◎ and ○ are judged to be usable.

[Peel strength]
A laminate (1) cut to a length of 10 cm and a width of 2.5 cm was prepared, the release sheet was peeled off, and then applied to the backs of five volunteers. . After the elapse of 8 hours, the laminate was peeled off, and the peeling force at that time was measured. The measurement was performed using a tensile tester “Autograph AGS-100D” manufactured by Shimadzu Corporation under the conditions of a temperature of 23 ° C., a relative humidity of 65%, a tensile speed of 300 mm / min, and a peeling angle of 180 degrees (N / 25 mm). ). The peel strength is shown as an average value of 5 volunteers. It was visually confirmed whether the peeled state of the pressure-sensitive adhesive layer after peeling was cohesive failure or interfacial peeling.
[Criteria]
A: The peel strength was 5.0 N / 25 mm or more, and the pressure-sensitive adhesive did not remain at the time of peeling and could be easily peeled off. The peeled state was interfacial peeling.
○: The peel strength was 3.0 N / 25 mm or more and less than 5.0 N / 25 mm, and the pressure-sensitive adhesive could be easily peeled off at the time of peeling, and the peeled state was interfacial peeling.
X: The peel strength was less than 3.0 N / 25 mm, the pressure-sensitive adhesive remained at the time of peeling, and could not be easily peeled off, and the peeled state was cohesive failure.
was.
◎ and ○ are judged to be usable.

[Re-adhesion]
Prepare a laminate (1) cut to a length of 10 cm and a width of 2.5 cm, peel off the release sheet, immerse in 23 ° C. water for 30 minutes, and dry the laminate in a 37 ° C. atmosphere for 5 hours. It was. A pressure sensitive adhesive layer is pressure-bonded to a stainless steel plate by reciprocating a 2 kg rubber roller, and after standing for 8 hours, it is peeled off at a speed of 300 mm / min in the direction of 180 degrees and the peel strength is measured. did. The peel strength was compared with the peel strength measured in the same manner except that the immersion in the water at 23 ° C. and the drying step were not performed, and the determination was made according to the following criteria.
[Criteria]
(Double-circle): Compared with the peeling strength when there was no immersion in 23 degreeC water and a drying process, peeling strength was 90% or more.
A: The peel strength was 75 to less than 90% compared to the peel strength when there was no immersion in 23 ° C. water and no drying step.
X: The peel strength was less than 75% as compared to the peel strength when there was no immersion in water at 23 ° C. and no drying step.
◎ and ○ are judged to be usable.

The pressure-sensitive adhesive of the present invention is excellent in applicability to skin, and can produce a laminate that can be firmly fixed when applied to the skin and easily peeled when peeled. The characteristics include coating suitability, peel strength, and re-adhesiveness. Considering environmental efforts in recent years, the required characteristics are expected to become increasingly severe. Therefore, the pressure-sensitive adhesive of the present invention is considered to be more useful because it can exhibit the above characteristics.
The pressure-sensitive adhesive of the present invention is also very useful for adhesive bandages, surgical tapes, electrocardiographic electrode fixing sheets, poultice fixing adhesive sheets, adhesive bandages, injection needle fixing sheets, magnetic particle fixing sheets, etc. Can be used for

1. 1. Lipophilic pressure sensitive adhesive Hydrophilic pressure sensitive adhesive

Claims (13)

A lipophilic pressure-sensitive adhesive comprising a styrenic block copolymer, a softener and a tackifying resin, and
At least one selected from polyvinyl alcohol, cellulose derivatives, gelatin, protein polymers, polyacrylic acid resins, polyacrylate polymers, and N-alkylacrylamide copolymers and water. The laminated body characterized by the adhesive pressure layer forming being formed in the same surface of a sheet-like base material, respectively. Lipophilic pressure sensitive adhesive
Styrene block copolymer (A) having a styrene ratio of 10 to 40% by weight and having a triblock type structure,
The laminate according to claim 1, comprising a mineral oil softener (B) having a weight average molecular weight of 700 to 10,000 and a tackifying resin (C) having a softening point of 80 to 160 ° C. Hydrophilic pressure sensitive adhesive
The laminate according to claim 1 or 2, wherein both a UV curable adhesive and a non-UV curable adhesive are used. The laminate according to any one of claims 1 to 3, wherein the lipophilic pressure-sensitive adhesive (1) has a viscosity at 170 ° C of 500 to 50,000 mPa · s as measured by a B-type viscometer. Lipophilic pressure sensitive adhesive, and the coating amount of the total hydrophilic pressure sensitive adhesive, the laminate of claims 1 to 4, wherein any one, which is a 2000 g / m ^2. The laminate according to any one of claims 1 to 5, wherein at least one adhesive layer is laminated in a foamed state. The laminate according to any one of claims 1 to 6, wherein at least one adhesive layer is laminated in a bead state. The laminate according to any one of claims 1 to 7, wherein at least one adhesive layer is laminated in a spiral state. The laminate according to any one of claims 1 to 8, wherein at least one adhesive layer is laminated in a curtain state. The laminated body according to claim 1, wherein at least one adhesive layer is laminated in a dot state. The laminate according to any one of claims 7 to 10, wherein two or more types of adhesive layers are alternately laminated in a stripe. The laminate according to any one of claims 7 to 10, wherein two or more kinds of adhesive layers are alternately laminated in a mesh shape. Furthermore, the chemical | medical agent for transdermal absorption is included, The laminated body in any one of Claims 1-12 characterized by the above-mentioned.

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