Resin composition and laminate using the resin composition

Abstract

To provide a resin composition that can be applied at low temperatures and is less prone to decrease in adhesion even when wet with water.SOLUTION: A resin composition contains a styrenic block copolymer (A), a tackifier resin (B), mineral oil (C) and wax (D). In the total of these components of 100 mass%, the styrenic block copolymer (A) is 3 to 15 mass%, the tackifier resin (B) is 50 to 80 mass%, the mineral oil (C) is 3 to 20 mass%, and the wax (D) is 3 to 20 mass%. In the styrenic block copolymer (A), a styrene block content is 10 to 40 mass% and a diblock content is 0 to 50 mass%.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a resin composition and a laminate using the resin composition.

Background Art

[0002] Conventionally, a heat-melted adhesive has been used for bonding disposable products typified by disposable diapers and napkins, and it is required to be easy to apply and strongly adhere. The heat-melted adhesive can be applied to various constituent members by various methods. However, regardless of the method used, the heat-melted adhesive is heated and melted so as to have an appropriate viscosity, and is applied to various constituent members in a planar shape, a spiral shape, a dot shape, a linear shape, a streak shape, etc.

[0003] Conventionally, various proposals have been made for hot-melt adhesives for disposable products and disposable water-absorbing articles, as shown in Patent Documents 1 to 2 below.

[0004] The hot-melt adhesive disclosed in Patent Document 1 has a high peel strength, and good results for peel strength, loop tack, etc. However, since the viscosity is high and it must be applied at a high temperature, fumes are likely to be generated during application, and heat deterioration and odor when used for a long time are problems.

[0005] The hot-melt adhesive disclosed in Patent Document 2 is excellent in heat stability and low-temperature coatability at 130°C. However, at a lower temperature of 120°C, the viscosity is high and it is not suitable for coating methods such as spiral coating. In addition, the peel strength when wet is low, and the stickiness of the adhesive after coating is strong, which is a problem.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0007] An object of the present invention is to provide a resin composition that can be applied at low temperature and whose adhesive strength does not decrease even when wetted with water.

Means for Solving the Problems

[0008] In a total of 100% by mass of a styrenic block copolymer (A), a tackifier resin (B), a mineral oil (C), and a wax (D), the styrenic block copolymer (A) is 3 to 15% by mass, the tackifier resin (B) is 50 to 80% by mass, the mineral oil (C) is 3 to 20% by mass, and the wax (D) is 3 to 20% by mass, and relates to a resin composition characterized in that in the styrenic block copolymer (A), the styrene block content is 10 to 40% by mass and the diblock content is 0 to 50% by mass.

[0009] Relates to a resin composition characterized in that the wax (D) contains a wax (D1) having a melting point of 50°C or higher and less than 70°C and a wax (D2) having a melting point of 70°C or higher and 130°C or lower.

[0010] Relates to a resin composition characterized in that the tackifier resin (B) contains at least one of a rosin-based tackifier resin and a terpene-based tackifier resin.

[0011] Relates to a laminate having a resin layer formed from any of the above resin compositions on at least one side of a substrate.

Effects of the Invention

[0012] According to the present invention, it is possible to provide a resin composition that can be applied at low temperature and whose adhesive strength does not decrease even when wetted with water. Furthermore, by applying at low temperature, there is less fume during application, it is possible to suppress heat deterioration and odor when used for a long time, and it is possible to provide a resin composition that is not sticky even when wetted with water.

Embodiments for Carrying Out the Invention

[0013] In this specification, unless otherwise specified, the numerical range specified using "~" shall include the numerical values described before and after "~" as the range of the lower limit value and the upper limit value.

[0014] The resin composition of the present invention will be described. The resin composition of the present invention is It is important that it contains a styrene-based block copolymer (A) having a styrene block content of 10 to 40% by mass and a diblock content of 0 to 50% by mass, a tackifier resin (B), a mineral oil (C), and a wax (D), and other additives may be blended as necessary.

[0015] The styrene-based block copolymer (A) constituting the resin composition used in the present invention preferably has a triblock structure part. Specifically, Styrene-butadiene-styrene block copolymer (hereinafter also abbreviated as "SBS"), Hydrogenated product of styrene-butadiene-styrene block copolymer (hereinafter also abbreviated as "SEBS"), Styrene-isoprene-styrene block copolymer (hereinafter also abbreviated as "SIS"), Hydrogenated product of styrene-isoprene-styrene block copolymer (hereinafter also abbreviated as "SEPS"), Styrene-butadiene-isoprene-styrene block copolymer (hereinafter also abbreviated as "SBIS"), It is preferable to contain at least one selected from the group consisting of hydrogenated products of styrene-butadiene-isoprene-styrene block copolymers (hereinafter also abbreviated as "SEEPS"). From the viewpoint of improving the adhesive strength, styrene-butadiene-styrene block copolymers are preferable. Further, the copolymer may be carboxyl-modified. Furthermore, the styrene block in the copolymer may contain a copolymer of styrene and other aromatic vinyl compounds such as α-methylstyrene.

[0016] The styrene block content of the styrenic block copolymer (A) of the present invention is 10 to 40% by mass, preferably 13 to 37% by mass. By having a styrene block content of 10 to 40% by mass, the cohesive force of the resin composition can be maintained.

[0017] In the present invention, the "styrene block content" refers to the ratio of the styrene block in the styrenic block copolymer (A).

[0018] Furthermore, it is preferable to use the styrenic block copolymer (A) having a triblock structural part, but it is not limited to those having only a triblock type structural part, and those having a diblock structural part in part may also be used. The styrenic block copolymer (A) may or may not contain a diblock, but the diblock content is 0 to 50% by mass, preferably 0 to 45% by mass. When the diblock content is 0 to 50% by mass, it has excellent heat resistance during melting. When the diblock content exceeds 50% by mass, the cohesive force decreases, and it becomes difficult to maintain the shape of the resin layer when peeling after coating. The styrenic block copolymer (A) may be used alone or in combination of two or more.

[0019] In the present invention, the "diblock content" refers to the content of styrene-butadiene block copolymer (hereinafter also abbreviated as "SB"), Hydrogenated styrene-butadiene block copolymer (hereinafter also abbreviated as "SEB"), Styrene-isoprene block copolymer (hereinafter also abbreviated as "SI"), Hydrogenated styrene-isoprene block copolymer (hereinafter also abbreviated as "SEP"), Styrene-butadiene-isoprene block copolymer (hereinafter also abbreviated as "SBI"), or Refers to the content of hydrogenated styrene-butadiene-isoprene block copolymer (hereinafter also abbreviated as "SEEP").

[0020] When the total of the styrenic block copolymer (A), tackifier resin (B), mineral oil (C), and wax (D) constituting the resin composition of the present invention is 100% by mass, the blending amount of the styrenic block copolymer (A) is 3 to 15% by mass. Preferably it is 5 to 13% by mass. When the blending amount of the styrenic block copolymer (A) is less than 3% by mass, the cohesive force of the resulting resin composition tends to decrease. When the blending amount of the styrenic block copolymer (A) exceeds 15% by mass, the viscosity becomes high, and there is a risk that low-temperature coating becomes difficult.

[0021] Examples of the tackifier resin (B) constituting the resin composition of the present invention include phenol resin, modified phenol resin, terpene phenol resin, xylene phenol resin, xylene resin, cyclopentadiene-phenol resin, petroleum resins such as aliphatic, alicyclic, and aromatic, hydrogenated petroleum resins such as aliphatic, alicyclic, and aromatic, phenol-modified petroleum resins, rosin ester resins, hydrogenated rosin ester resins, low molecular weight polystyrene resins, terpene resins, hydrogenated terpene resins, and the like. The tackifier resin (B) may be used alone or in combination of two or more. From the viewpoint of improving the adhesive strength, rosin-based tackifier resins and terpene-based tackifier resins are preferred.

[0022] The softening point of the tackifying resin (B) is preferably 85 to 130 °C. When the softening point of the tackifying resin is 85 °C or higher, the cohesive force can be maintained, making it difficult for cohesive failure to occur during peeling. Also, if the softening point of the tackifying resin (B) is 130 °C or lower, it is preferable as it becomes easier to maintain the adhesive strength in the low-temperature range. In the present invention, the softening point is the temperature determined by the method specified in JIS K 6863. Details are described in the Examples section.

[0023] When the total of the styrenic block copolymer (A), tackifying resin (B), mineral oil (C), and wax (D) constituting the resin composition of the present invention is 100% by mass, the blending amount of the tackifying resin (B) is 50 to 80% by mass, more preferably 53 to 77% by mass. When the blending amount of the tackifying resin (B) is less than 50% by mass, the processability deteriorates. When the blending amount of the tackifying resin (B) exceeds 80% by mass, the adhesiveness may not be maintained.

[0024] Examples of the mineral oil (C) constituting the resin composition used in the present invention include paraffinic mineral oil, naphthenic mineral oil, and aromatic mineral oil. Paraffinic mineral oil is preferable from the viewpoint of hue. Generally, those in which the number of carbon atoms in the paraffin chain accounts for 50% or more of the total number of carbon atoms are called paraffinic mineral oil, those in which the number of carbon atoms in the naphthene ring accounts for 35 to 45% of the total number of carbon atoms are called naphthenic mineral oil, and those in which the number of aromatic carbon atoms accounts for 30% or more of the total number of carbon atoms are called aromatic mineral oil, and they are distinguished.

[0025] When the total of the styrenic block copolymer (A), tackifying resin (B), mineral oil (C), and wax (D) constituting the resin composition of the present invention is 100% by mass, the blending amount of the mineral oil (C) is 3 to 20% by mass. Preferably it is 5 to 18% by mass. When the blending amount of the mineral oil (C) is less than 3% by mass, the processability deteriorates. Also, when the blending amount of the mineral oil (C) exceeds 20% by mass, it becomes difficult to maintain the cohesive force.

[0026] As the wax (D) constituting the resin composition used in the present invention, it is preferable to use in combination a wax (D1) having a melting point of 50°C to less than 70°C and a wax (D2) having a melting point of 70°C to 130°C or lower. By using the wax (D1) and the wax (D2) in combination, it becomes easier to achieve both a solidification rate and adhesiveness. In the present invention, the melting point is the temperature at the peak top when the temperature is raised at 10°C / min by differential scanning calorimetry measurement. Details are described in the Examples section.

[0027] Examples of the wax (D) include paraffin wax, microcrystalline wax, montan wax, Fischer-Tropsch wax, polyethylene wax, polypropylene wax, polyethylene-polypropylene wax, carnauba wax, low molecular weight polyethylene, low molecular weight polypropylene, low molecular weight ethylene-propylene copolymer, oxide of low molecular weight ethylene-propylene copolymer, low molecular weight ethylene-butene copolymer, low molecular weight propylene-butene-ethylene copolymer, styrene graft of low molecular weight ethylene-propylene copolymer, maleic anhydride oxide of ethylene-propylene copolymer, maleic anhydride oxide of propylene-butene-ethylene copolymer, and other modified waxes. Among these, paraffin wax is preferable in terms of fast solidification and high adhesive strength.

[0028] The penetration of the wax (D) is preferably 0.2 to 30 at 25°C, more preferably 0.5 to 25. When the penetration is within the above range, it becomes easier to increase the adhesive strength. The penetration in the present invention is a value obtained by the method defined in JIS K 2235. Details are described in the Examples section.

[0029] When the total of the styrenic block copolymer (A), tackifier resin (B), mineral oil (C), and wax (D) constituting the resin composition of the present invention is 100% by mass, the blending amount of the wax (D) is 3 to 20% by mass. More preferably, it is 5 to 18% by mass. When the blending amount of the wax (D) is less than 3% by mass, the coatability deteriorates. When the blending amount of the wax (D) exceeds 20% by mass, it becomes difficult to maintain the adhesiveness.

[0030] In 100% by mass in total of the styrenic block copolymer (A), tackifier resin (B), mineral oil (C), and wax (D) constituting the resin composition of the present invention, when the blending amount of the wax (D) is 3 to 20% by mass, the blending amount of the wax (D1) is preferably 2 to 19% by mass, and the blending amount of the wax (D2) is preferably 1 to 18% by mass. Further, in 100% by mass in total of the styrenic block copolymer (A), tackifier resin (B), mineral oil (C), and wax (D) constituting the resin composition of the present invention, when the blending amount of the wax (D) is 5 to 18% by mass, the blending amount of the wax (D1) is preferably 3 to 18% by mass, and the blending amount of the wax (D2) is preferably 2 to 17% by mass. When the blending amount of the wax (D1) is 2% by mass or more, it becomes less sticky, and when it is 19% by mass or less, it is preferable because it is easy to maintain the adhesiveness. Also, when the blending amount of the wax (D2) is 1% by mass or more, the solidification becomes faster, and when it is 18% by mass or less, it is preferable because it is easy to maintain the adhesiveness.

[0031] Additives such as antioxidants, ultraviolet absorbers, antibacterial agents, deodorants, insect repellents, silane coupling agents, colorants, adhesion promotion inhibitors, light stabilizers, fillers, and fragrances may be added to the resin composition of the present invention as long as the object of the invention is not impaired.

[0032] Examples of the antioxidant include phenolic antioxidants such as 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, and ethylene bis(oxyethylene) bis[3-(5-t-butyl-4-hydroxy-m-tolyl]propionate, and phosphorus antioxidants such as tris(2,4-di-t-butylphenyl) phosphite and bis(2,4-di-t-butylphenyl) pentaerythritol diphosphite. These antioxidants may be used alone or in combination of two or more.

[0033] The above phenolic antioxidants function as radical trap agents that donate hydrogen to ROO· (peroxyl radical) generated in the chain growth process of autoxidation to stabilize it, and themselves become stable phenoxy radicals protected by ortho substituents to stop the chain reaction, thereby effectively suppressing the thermal degradation of the resin composition. In particular, by combining the phenolic antioxidant with a lactone antioxidant (e.g., 5,7-di-tert-butyl-3-(3,4-dimethylphenyl)-3H-benzofuran-2-one) or a vitamin E antioxidant (3,4-dihydro-2,5,7,8-tetramethyl-2-(4,8,12-trimethyltridecyl)-2H-benzopyran-6-ol) that has a faster radical trap reaction than the phenolic antioxidant, it becomes more excellent. In addition, the above phosphorus antioxidants have a function of non-radically decomposing peroxides and ROOH and stopping the chain reaction in the autoxidation process, thereby effectively suppressing the thermal degradation of the resin composition.

[0034] The ultraviolet absorber is not particularly limited, and examples include those commonly used such as salicylic acid-based, benzophenone-based, and benzotriazole-based ones. These ultraviolet absorbers may be used alone or in combination of two or more.

[0035] Examples of the antibacterial agent include benzylamine antibacterial agents such as butenafine and its salts, imidazole antibacterial agents such as bifonazole, neticonazole, ketoconazole, lanoconazole, clotrimazole, miconazole, oxiconazole, tioconazole, croconazole, omoconazole, sulconazole and their salts, allylamine antibacterial agents such as terbinafine and its salts, morpholine antibacterial agents such as amorolfine and its salts, thiocarbamate antibacterial agents such as rilanaftate, tolnaftate and tolciclate, and antibiotics such as nystatin, trichomycin, validamycin, sikannin, and pyrrolnitrin. These antibacterial agents may be used alone or in combination of two or more kinds.

[0036] The deodorant is not particularly limited as long as it has a deodorizing effect, and examples thereof include lauryl methacrylate, geranyl chloride, citronellyl senecionate, terpene aldehydes, pyruvate esters, zinc 2-ethylhexanoate, and zinc ricinoleate. These deodorants may be used alone or in combination of two or more kinds.

[0037] Examples of the insect repellent include camphor, naphthalene, paradichlorobenzene, isobornyl, thiocyanoacetic acid, diethyl 1,2-benzenedicarboxylate, paraform, chloropicrin, pyrethrum, empenthrin, transfluthrin, allethrin, phenothrin, and eminence. These insect repellents may be used alone or in combination of two or more kinds.

[0038] The silane coupling agent is not particularly limited. For example, vinyltrimethoxysilane, vinyltriethoxysilane, methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethylmethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, mercaptobutyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, etc. may be mentioned. These silane coupling agents may be used alone or in combination of two or more.

[0039] Examples of the colorant include known colorants generally used, such as inorganic pigments and organic pigments. Examples of the inorganic pigments include carbon black, iron oxide, titanium oxide, zinc oxide, which are also used as the filler, as well as valve handle, cadmium red, cadmium yellow, ultramarine, cobalt blue, titanium yellow, lead white, red lead, lead yellow, ultramarine blue, etc. Examples of the organic pigments include quinacridone, polyazo yellow, anthraquinone yellow, polyazo red, azo lake yellow, perylene, phthalocyanine green, phthalocyanine blue, isoindolinone yellow, etc. These colorants may be used alone or in combination of two or more.

[0040] Examples of the adhesion promoter inhibitor include fatty acid amide, long-chain alkyl graft of polyethyleneimine, soybean oil-modified alkyd resin (e.g., manufactured by Arakawa Chemical Industries, Ltd., trade name "Arakid 251", etc.), tall oil-modified alkyd resin (e.g., manufactured by Arakawa Chemical Industries, Ltd., trade name "Arakid 6300", etc.).

[0041] Examples of the light stabilizer include those commonly used hindered amine compounds.

[0042] Examples of the filler include talc, clay, glass beads, calcium silicate, silica, zeolite, diatomaceous earth, alumina, titanium oxide, iron oxide, zinc oxide, magnesium oxide, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, calcium carbonate, magnesium carbonate, synthetic organic fiber, natural fiber, wood powder, and the like.

[0043] Examples of the fragrance include hydrocarbon fragrances such as pinene and limonene; alcohol fragrances such as linalool, geraniol, citronellol, menthol, borneol, benzyl alcohol, anisyl alcohol, and β-phenethyl alcohol; phenol fragrances such as anethole and eugenol; aldehyde fragrances such as n-butyl aldehyde, isobutyl aldehyde, hexyl aldehyde, citral, citronellal, benzaldehyde, and cinnamic aldehyde; ketone fragrances such as carvone, menthone, camphor, acetophenone, and ionone; lactone fragrances such as γ-butyrolactone, coumarin, and cineole; and ester fragrances such as octyl acetate, benzyl acetate, cinnamyl acetate, butyl propionate, and methyl benzoate. These fragrances may be used alone or in combination of two or more.

[0044] Additives such as antioxidants, ultraviolet absorbers, antibacterial agents, deodorants, insect repellents, silane coupling agents, colorants, adhesion promotion inhibitors, light stabilizers, moisturizers, water absorbents, electrolyte salts, fillers, and fragrances that can be added without impairing the object of the present invention may be blended in an amount of 0 to 10 parts by mass, more preferably 0 to 8 parts by mass, based on 100 parts by mass in total of the styrene-based block copolymer (A), tackifier resin (B), mineral oil (C), and wax (D). Bleeding out is less likely to occur when the amount is 10 parts by mass or less.

[0045] The resin composition of the present invention can be prepared by uniformly mixing the various components, and the mixing means and conditions are not particularly limited. A typical preparation method includes kneading the various components using a device such as a mixing roll, a roll, a Banbury mixer, a single-screw or twin-screw extruder, a kneader, an extruder, a melt extruder, or a melting pot equipped with a stirrer, and then cooling and pulverizing the resulting kneaded product. The kneading method is not particularly limited, but melt kneading is preferable. The conditions during melt kneading may be appropriately determined depending on the types and amounts of the various components used, and are not particularly limited.

[0046] In one embodiment of the present invention, the melt-kneading is preferably carried out for 30 to 300 minutes at a temperature range of 60 to 200° C., and more preferably for 35 to 295 minutes at a temperature range of 65 to 195° C. If the melt-kneading temperature is in the range of 60 to 200° C., the various components can be melt-kneaded sufficiently. Furthermore, if the melt-kneading time is within 30 to 300 minutes, no undissolved material remains.

[0047] The shape of the resin composition of the present invention may be, for example, a block, a strand, a sheet, a plate, a pellet, etc. In order to apply the resin composition of the present invention to molding processing, the shape is preferably a block from the viewpoint of production stability of the obtained molded article.

[0048] The resin composition of the present invention is preferably applied at 80 to 150° C., and can be used with rolls that require application at a low viscosity and melting pots equipped with stirrers for melting. From this perspective, the resin composition of the present invention preferably has a viscosity of 500 to 3,000 mPa s at 120° C. If the viscosity at 120°C is below 500 mPa·s, the resin composition may drip when a large amount is applied.If the viscosity at 120°C is above 3,000 mPa·s, workability may become an issue during application.

[0049] The resin composition of the present invention can be heated and melted or its solution can be applied in various patterns such as a mirror state, a foamed state, a bead state, a spiral state, etc. using a coating machine or a hot melt coating machine commonly used for substrates such as paper, resin, non-woven fabric, etc. By aging, heating, and cooling as necessary, a resin layer can be formed, and various laminates with the resin layer laminated can be obtained. The resin composition can also be applied in multiple layers, and two types of resin compositions can be applied side by side on the same substrate. The formation of the resin layer can be carried out using a commonly used coating device. Examples of the coating device include a roll knife coater, a die coater, a roll coater, a bar coater, a gravure roll coater, a reverse roll coater, dipping, a blade coater, and the like.

[0050] Next, the laminate of the present invention will be described. The basic lamination structure of the laminate of the present invention is a single-sided laminate such as a substrate / resin layer / release film, or a double-sided laminate such as a release film / resin layer / substrate / resin layer / release film. During use, the release film is peeled off and the resin layer is attached to the adherend. The resin composition of the present invention has tack and appropriate firmness without completely solidifying during attachment, and has cohesive force to maintain the attached state.

[0051] As the material of the base material, it can be used without particular limitation. For example, as the resin film, polyester resin, polycarbonate resin, polyarylate resin, acrylic resin, polyphenylene sulfide resin, polystyrene resin, vinyl resin, polyimide resin, epoxy resin, polyethylene, polypropylene, olefin resins such as norbornene can be mentioned. The base material may be a single layer or multiple layers. In addition, non-woven fabric, woven fabric, cloth, paper, glass, metal foil, metal mesh and composites containing these can be mentioned. Further, if necessary, the surface of the base material may be subjected to adhesion-promoting treatment such as corona discharge treatment, plasma treatment, blasting treatment, chemical etching treatment, antistatic treatment, coloring treatment, etc. Furthermore, a release film can also be used as the base material, and the resin composition can be coated on the release film. There is no particular limitation on the thickness of these base materials, but 1 μm to 1000 μm is preferable from the viewpoint of workability.

[0052] The coating amount of the resin composition is 1 g / m 2 ~100 g / m 2 , preferably 2 g / m 2 ~98 g / m 2 , more preferably 5 g / m 2 ~95 g / m 2 . If the coating amount is in the range of 1 g / m 2 ~100 g / m 2 , sufficient adhesive strength is exhibited, which is preferable.

[0053] The resin layer can be used in combination with a release film or the like as necessary. There is no particular limitation on the release film. For example, polyethylene terephthalate film (hereinafter referred to as PET film), polyolefin resin films such as polyethylene, polypropylene, norbornene, PPS resin film, TAC film, acrylic resin film, or those subjected to a release treatment on these can be mentioned.

[0054] The laminate of the present invention may be configured such that the resin layer is sandwiched between a film-like base material other than the release film and the release film, between film-like base materials other than the release film, or between release films. A configuration in which the resin layer is sandwiched between a film-like base material other than the release film and the release film is preferred.

Examples

[0055] Hereinafter, the present invention will be described specifically and in detail by way of examples. However, these examples are merely one aspect of the present invention, and the present invention is not limited by these examples. In the examples, “parts” represents “parts by mass” and “%” represents “mass %”.

[0056] The softening point, melting point, penetration, and viscosity at 120°C were measured by the following methods.

[0057] <Softening point> The softening point was measured according to the method specified in JIS K 6863. That is, after allowing a specified ring filled with the resin composition to stand for 12 hours or more, it was placed in a heat medium, a specified ball was placed on the specified ring filled with the resin composition, and when the temperature of the heat medium (glycerin) was raised at a constant rate, the temperature at which the ball sank and touched the bottom plate of the ring stand due to the softening of the resin composition was read and taken as the softening point.

[0058] <Melting point> The melting point was measured using a differential scanning calorimeter (DSC-60A Plus: manufactured by Shimadzu Corporation). Specifically, about 5 mg of wax (D) was weighed on an aluminum pan, the aluminum pan was set in a DSC measurement holder, and the exothermic peak of the chart obtained under the temperature rising condition of 10°C / min was read. The melting point was taken as the temperature of the peak top.

[0059] <Penetration> The penetration was measured according to the method specified in JIS K 2235. The penetration is measured by heating and melting wax (D), placing it in a sample container, cooling it, maintaining a constant temperature in a thermostatic water bath, and vertically inserting a specified needle with a total mass of 100 g into the sample for 5 seconds. The penetration of the sample is measured to a depth of 0.1 mm of the needle's entry, and the value is expressed as a number (dimensionless) obtained by multiplying this by 10.

[0060] <Viscosity Measurement at 120°C> The viscosity at 120°C was measured using a B-type viscometer (TVB-10M, manufactured by Toki Sangyo Co., Ltd.) under the following conditions. Temperature: 120°C Sample amount: Approximately 500 g Rotor No.: 3 Rotor rotation speed: 12 rpm Rotation time: 30 seconds

[0061] (Examples 1 to 12, Comparative Examples 1 to 10) Using the amounts shown in Tables 1 and 2, a styrene block copolymer (A), tackifier resin (B), mineral oil (C), wax (D), and, if necessary, an antioxidant were added to a kneader equipped with a stirrer, and stirred at 150°C for 3 hours to obtain a resin composition.

[0062]

Table 1

[0064] The materials in Tables 1 and 2 are shown below. SBS1: SBS, styrene block content 40% by mass, triblock content 100% (product name D1155, manufactured by Clayton) SBS2: SBS, styrene block content 30% by mass, triblock content 85%, diblock content 15% (product name TR-2782, manufactured by JSR) SBS3: SBS, styrene block content 30% by mass, triblock content 85%, diblock content 15% (product name TR-2601, manufactured by JSR) SBS4: SBS, styrene block content 36.5 mass%, triblock content 35%, diblock content 65% (PB5502, manufactured by CHIMEI) SBS5: 3-branched styrene-butadiene block copolymer: styrene block content 40 mass%, triblock content 30%, diblock content 70% (HJ12-4, manufactured by Asahi Kasei) SBS6: Linear styrene-butadiene block copolymer: styrene block content 43 mass%, triblock content 40%, diblock content 60% (Asaprene T439, manufactured by Asahi Kasei) SEBS: SEBS, styrene block content 30 mass%, triblock content 100% (G-1652, manufactured by Kraton)

[0065] Tackifying resin 1: Unhydrogenated rosin-based tackifying resin, softening point 104°C (SYLVALITE RE105L, manufactured by Kraton) Tackifying resin 2: Partially hydrogenated petroleum-based tackifying resin, softening point 90°C (Alcon M-90, manufactured by Arakawa Chemical Industries) Tackifying resin 3: Hydrogenated petroleum-based tackifying resin, softening point 100°C (Alcon P-100, manufactured by Arakawa Chemical Industries) Tackifying resin 4: Unhydrogenated terpene-based tackifying resin, softening point 95°C (SYLVARES 1095, manufactured by Kraton) Tackifying resin 5: Partially hydrogenated alicyclic petroleum hydrocarbon resin, softening point 100°C (Alcon M-100, manufactured by Arakawa Chemical Industries) Tackifying resin 6: Hydrogenated tackifying resin (Sucolez SU420, trade name, manufactured by Kolon) Tackifying resin 7: Hydrogenated tackifying resin (Imerv S100, trade name, manufactured by Idemitsu Kosan), softening point 100°C Tackifying resin 8: End-block hydrogenated tackifying resin (Plastolyn 290, trade name, manufactured by Eastman Chemical)

[0066] Mineral oil 1: Paraffinic mineral oil, paraffin chain carbon number in total carbon number: 71%, naphthene ring carbon number in total carbon number: 29% (Diana Process Oil PW-90, manufactured by Idemitsu Kosan) Mineral oil 2: Paraffinic mineral oil, paraffin chain carbon number in total carbon number: 67.1%, naphthene ring carbon number in total carbon number: 32.8%, aromatic ring carbon number in total carbon number: 0.1% (Diana Process Oil PS-32, manufactured by Idemitsu Kosan Co., Ltd.) Mineral oil 3: Liquid paraffin, paraffin chain carbon number in total carbon number: 100% (Hi-Col K-350, manufactured by Kaneda Co., Ltd.) Mineral oil 4: Naphthalenic process oil (Nyflex 222B manufactured by Nynas) Mineral oil 5: Paraffin oil (Diana Freshness S-32, manufactured by Idemitsu Kosan Co., Ltd.)

[0067] Wax 1: Paraffin wax, melting point 55°C, penetration 14 (25°C) (Paraffin Wax-140, manufactured by Nippon Seiro Co., Ltd.) Wax 2: Paraffin wax, melting point 60°C, penetration 11 (25°C) (Paraffin Wax-140, manufactured by Nippon Seiro Co., Ltd.) Wax 3: Paraffin wax, melting point 69°C, penetration 15 (25°C) (Paraffin Wax-155, manufactured by Nippon Seiro Co., Ltd.) Wax 4: Polyethylene wax, melting point 102°C, penetration 2 (25°C) (Polyrez 200EL, manufactured by SCG Performance Chemicals) Wax 5: Polyethylene wax, melting point 116°C, penetration 2 (25°C) (Hi-Wax 100P, manufactured by Mitsui Chemicals, Inc.)

[0068] The abbreviations of the other components described in Table 1 and Table 2 are shown below. Antioxidant 1: Pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] Liquid polymer: Liquid polyisoprene having a carboxylic anhydride group (Kraprene LIR-403, manufactured by Kuraray Co., Ltd.)

[0069] (Evaluation) For the resin compositions prepared in Examples 1 to 12 and Comparative Examples 1 to 10, viscosity, low-temperature coatability, dry adhesion, and wet adhesion were evaluated according to the following procedures. These results are shown in Table 1.

[0070] [Viscosity] The viscosity of the resin composition was measured at 120°C. With an appropriate coating amount, those with a viscosity of 500 or more and less than 3,000 mPa·s were marked as ○. ○: 500 or more and less than 3,000 mPa·s ×: Less than 500 mPa·s or 3,000 mPa·s or more

[0071] [Low-temperature coatability] At a coating temperature of 120°C, a coating speed of 30 m / min, and a coating amount of 3 - 6 g / m 2 , with a width of 5 cm, spiral coating was performed on the non-woven fabric, and the low-temperature coatability was evaluated. ○ was judged to be practical. 〇: Spiral coating was possible. ×: Spiral coating was not possible.

[0072] [Adhesion (DRY)] The resin compositions obtained in Examples 1 - 12 and Comparative Examples 1 - 10 were spiral-coated on a non-woven fabric (18 g / m 2 ) at a coating temperature of 120°C, a coating speed of 30 m / min, and a coating amount of 5 g / m 2 ) with a width of 5 cm, and pressed for 0.01 seconds at 23°C and a pressure of 50 gf / cm 2 in the flow direction to bond with the non-woven fabric (18 g / m 2 ). Cut in a direction perpendicular to the flow direction, with a length of 15 cm and a width of 25 mm to obtain test samples. The adhesion (dry) was measured using the obtained test samples. T-peel was performed at a speed of 300 mm / min, and the average value of the adhesion of the coated part was calculated. ○ was judged to be practical. 〇: 3 N / 25 mm or more △: 2 N / 25 mm or more and less than 3 N / 25 mm ×: Less than 2 N / 25 mm Note that the resin compositions with diagonal lines in the adhesion evaluation results in Table 2 indicate that test samples could not be prepared under the aforementioned coating conditions, and the adhesion evaluation was not carried out.

[0073] [Adhesion (WET)] Using the test samples prepared by the above method, the adhesion (wet) was measured by the following method. The test samples were immersed in water and allowed to stand for 5 minutes. After drying to the extent that water droplets did not fall off, T-peel was performed at a speed of 300 mm / min, and the average value of the adhesion of the coated portion was calculated. ○ was judged to be practical. 〇: 2 N / 25 mm or more ×: Less than 2 N / 25 mm Note that the resin compositions with hatched adhesion evaluation results in Table 2 could not produce test samples under the above coating conditions, indicating that the adhesion evaluation was not carried out.

[0074] [Ball Tack] The resin compositions obtained in Examples 1 to 12 and Comparative Examples 1 to 10 were hand-coated on a 50-μm-thick PET film to a thickness of 25 μm, and the adhesive sheet was cut into a size of 25 mm in width and 250 mm in length. The release sheet was peeled off from the adhesive sheet, and the adhesive surface was fixed upward on an inclined plate with an inclination angle of 30 degrees. A PET film for a run-up was attached on the upper part, a steel ball (1 / 32 to 32 / 32 inches) was rolled on a sample with a 10-cm run-up and a 10-cm paste surface, and the number of the diameter of the ball that stopped near the center of the paste surface was recorded. The measurement was carried out in an atmosphere of 23°C and 50% relative humidity. ○ and △ were judged to be practical. The obtained adhesive sheet was prepared in a size of 25 mm in width and 250 mm in length. The release sheet was peeled off from the adhesive sheet, and the adhesive surface was fixed upward on an inclined plate with an inclination angle of 30 degrees. A PET film for a run-up was attached on the upper part, a steel ball (1 / 32 to 32 / 32 inches) was rolled on a sample with a 10-cm run-up and a 10-cm paste surface, and the number of the diameter of the ball that stopped near the center of the paste surface was recorded. The measurement was carried out in an atmosphere of 5°C or 23°C and 50% relative humidity. 3) Ball Tack The obtained adhesive sheet was prepared to have a size of 25 mm in width and 250 mm in length. The release sheet was peeled off from the adhesive sheet, and the adhesive surface was fixed upward on an inclined plate with an inclination angle of 30 degrees. A PET film for a runway was attached to the upper part, and a steel ball (1 / 32 to 32 / 32 inches) was rolled on a sample having a 10-cm runway and a 10-cm paste surface, and the number of the diameter of the ball that stopped near the center of the paste surface was recorded. The measurement was carried out at 5°C or 23°C in an atmosphere with a relative humidity of 50%. 〇: #3 or less △: #4 to 6 ×: #7 or more

[0075] [Fume] 250 ml of the resin compositions obtained in Examples 1 to 12 and Comparative Examples 1 to 10 were put into a 500-ml metal can, covered with a metal lid, and heated at 120°C for 1 hour to check for the presence or absence of fume generation. ○ was judged to be practicable. 〇: After opening the lid, no fume could be visually confirmed. ×: Fume could be visually confirmed after opening the lid

[0076] As is clear from the results in Table 1 and Table 2, the results in the comparative examples were insufficient, while the examples showed good results.

Claims

1. In a total of 100% by mass of a styrenic block copolymer (A), a tackifier resin (B), a mineral oil (C), and a wax (D), the styrenic block copolymer (A) is 3 to 15% by mass, the tackifier resin (B) is 50 to 80% by mass, the mineral oil (C) is 3 to 20% by mass, and the wax (D) is contained in an amount of 7 to 16.5% by mass, the wax (D) contains a wax (D1) having a melting point of 50°C or higher and lower than 70°C and a wax (D2) having a melting point of 102°C or higher and 130°C or lower, in a total of 100% by mass of the styrenic block copolymer (A), the tackifier resin (B), the mineral oil (C), and the wax (D), the wax (D1) is contained in an amount of 5 to 15% by mass and the wax (D2) is contained in an amount of 1 to 5.5% by mass, A resin composition, wherein in the styrenic block copolymer (A), the styrene block content is 10 to 40% by mass, the triblock content is 85 to 100% by mass, and the diblock content is 0 to 15% by mass.

2. The resin composition according to claim 1, wherein the tackifier resin (B) contains at least one of a rosin-based tackifier resin and a terpene-based tackifier resin.

3. A laminate having a resin layer formed from the resin composition according to claim 1 or 2 on at least one side of a substrate.

Images