JP7694147B2 - Resin composition and laminate using said resin composition - Google Patents

Description

The present invention relates to a resin composition and a laminate made using the resin composition.

2. Description of the Related Art Conventionally, hot-melt adhesives have been used to bond disposable products such as paper diapers and napkins, and they are required to be easy to apply and provide strong adhesion.
The hot-molten adhesive can be applied to various components by a variety of methods. Regardless of which method is used, the hot-molten adhesive is heated and melted to an appropriate viscosity, and then applied to the various components in the form of a surface, spiral, dot, line, stripe, etc.

Various proposals have been made so far regarding hot melt adhesives for use in disposable products and disposable absorbent articles, such as those shown in Patent Documents 1 and 2 below.

The hot melt adhesive disclosed in Patent Document 1 has high peel strength and good results in terms of peel strength, loop tack, etc., but it has high viscosity and must be applied at high temperatures, which means that fumes are easily generated during application, and thermal degradation and odors become an issue when used for long periods of time.

The hot melt adhesive disclosed in Patent Document 2 has excellent thermal stability and low-temperature coating properties at 130°C, but at the lower temperature of 120°C, its viscosity is high and it is not suitable for coating methods such as spiral coating. In addition, it has low peel strength when wet, and the adhesive is very sticky after coating, which is an issue.

JP 2014-214185 A JP 2019-131687 A

The present invention aims to provide a resin composition that can be applied at low temperatures and whose adhesive strength does not decrease even when wet.

In a total of 100% by mass of the styrene-based block copolymer (A), the tackifier resin (B), the mineral oil (C), and the wax (D),
3 to 15% by mass of a styrene-based block copolymer (A),
50 to 80% by mass of a tackifier resin (B),
3 to 20% by mass of a mineral oil (C); and
The wax (D) is contained in an amount of 3 to 20 mass %,
The present invention relates to a resin composition, characterized in that the styrene block copolymer (A) has a styrene block content of 10 to 40 mass % and a diblock content of 0 to 50 mass %.

The resin composition is characterized in that the wax (D) contains a wax (D1) having a melting point of 50°C or more and less than 70°C, and a wax (D2) having a melting point of 70°C or more and 130°C or less.

The resin composition is characterized in that the tackifier resin (B) contains at least one of a rosin-based tackifier resin and a terpene-based tackifier resin.

The present invention relates to a laminate having a resin layer formed from any of the above resin compositions on at least one side of a substrate.

The present invention provides a resin composition that can be applied at low temperatures and whose adhesive strength does not decrease even when wetted with water. Furthermore, application at low temperatures reduces fumes during application, and it is possible to suppress thermal deterioration and odors when used for long periods of time, and it is possible to provide a resin composition that is not sticky even when wetted with water.

In this specification, unless otherwise specified, a numerical range specified using "~" includes the numerical values before and after "~" as the lower and upper limit values.

The resin composition of the present invention will be described.
The resin composition of the present invention comprises
It is important that the composition 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.

The styrene-based block copolymer (A) constituting the resin composition used in the present invention preferably has a triblock structure. Specifically,
Styrene-butadiene-styrene block copolymer (hereinafter also abbreviated as "SBS");
Hydrogenated styrene-butadiene-styrene block copolymer (hereinafter also abbreviated as "SEBS");
Styrene-isoprene-styrene block copolymer (hereinafter also abbreviated as "SIS"),
Hydrogenated styrene-isoprene-styrene block copolymer (hereinafter also abbreviated as "SEPS");
Styrene-butadiene-isoprene-styrene block copolymer (hereinafter also abbreviated as "SBIS");
It is preferable that the composition contains 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 increasing adhesive strength, styrene-butadiene-styrene block copolymers are preferable.
The copolymer may be carboxyl-modified, and the styrene block in the copolymer may contain a copolymer of styrene and another aromatic vinyl compound such as α-methylstyrene.

The styrene block content of the styrene-based block copolymer (A) of the present invention is 10 to 40% by mass, and preferably 13 to 37% by mass. By having a styrene block content of 10 to 40% by mass, the cohesive strength of the resin composition can be maintained.

In the present invention, the "styrene block content" refers to the proportion of styrene blocks in the styrene-based block copolymer (A).

Furthermore, it is preferable to use a styrene-based block copolymer (A) having a triblock structural portion, but it is not limited to a copolymer having only a triblock structural portion, and it may also have a diblock structural portion in part.
The styrene-based 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, the heat resistance during melting is excellent. 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 peeled off after coating.
The styrene-based block copolymer (A) may be used alone or in combination of two or more kinds.

In the present invention, the "diblock content" refers to the amount of styrene-butadiene block copolymer (hereinafter, also abbreviated as "SB") in the styrene-based block copolymer (A),
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");
This refers to the content of styrene-butadiene-isoprene block copolymer (hereinafter also abbreviated as "SBI") or hydrogenated styrene-butadiene-isoprene block copolymer (hereinafter also abbreviated as "SEEP").

When the total of the styrene-based block copolymer (A), tackifier resin (B), mineral oil (C), and wax (D) constituting the resin composition of the present invention is taken as 100% by mass, the blending amount of the styrene-based block copolymer (A) is 3 to 15% by mass. It is preferably 5 to 13% by mass. If the blending amount of the styrene-based block copolymer (A) is less than 3% by mass, the cohesive strength of the resulting resin composition tends to decrease. If the blending amount of the styrene-based block copolymer (A) exceeds 15% by mass, the viscosity becomes high, which may make low-temperature coating difficult.

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

The softening point of the tackifier resin (B) is preferably 85 to 130° C. If the softening point of the tackifier resin is 85° C. or higher, the cohesive strength can be maintained, and therefore cohesive failure is unlikely to occur during peeling. In addition, if the softening point of the tackifier resin is 130° C. or lower, the adhesive strength in the low temperature range can be easily maintained, which is preferable.
The softening point in the present invention is a temperature determined by the method specified in JIS K 6863. Details will be described in the Examples section.

When the total of the styrene 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 amount of tackifier resin (B) is 50 to 80% by mass, and more preferably 53 to 77% by mass. If the amount of tackifier resin (B) is less than 50% by mass, processability will be poor. If the amount of tackifier resin (B) is more than 80% by mass, adhesion may not be maintained.

Examples of the mineral oil (C) constituting the resin composition used in the present invention include paraffinic mineral oil, naphthenic mineral oil, aromatic mineral oil, etc. Paraffinic mineral oil is preferred from the viewpoint of hue.
In general, mineral oils are classified as follows: those in which the number of paraffin chain carbon atoms is 50% or more of the total carbon number are called paraffinic mineral oils, those in which the number of naphthene ring carbon atoms is 35 to 45% of the total carbon number are called naphthenic mineral oils, and those in which the number of aromatic carbon atoms is 30% or more of the total carbon number are called aromatic mineral oils.

When the total of the styrene 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 amount of mineral oil (C) is 3 to 20% by mass. It is preferably 5 to 18% by mass. If the amount of mineral oil (C) is less than 3% by mass, processability will be poor. Also, if the amount of mineral oil (C) is more than 20% by mass, it will be difficult to maintain cohesive force.

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. The combined use of the wax (D1) and the wax (D2) makes it easier to achieve both a good solidification rate and good adhesion.
In the present invention, the melting point is the peak top temperature when the temperature is increased at 10° C./min in a differential scanning calorimeter measurement. Details will be described in the Examples section.

Examples of 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 grafted product 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 preferred because it solidifies quickly and has high adhesive strength.

The wax (D) preferably has a penetration index at 25° C. of 0.2 to 30, more preferably 0.5 to 25. When the penetration index is within the above range, the adhesive strength can be easily increased.
The penetration in the present invention is a value determined by the method specified in JIS K 2235. Details will be described in the section of Examples.

When the total of the styrene 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 amount of wax (D) is 3 to 20% by mass. More preferably, it is 5 to 18% by mass. If the amount of wax (D) is less than 3% by mass, the coatability is poor. If the amount of wax (D) is more than 20% by mass, it becomes difficult to maintain adhesion.

In the resin composition of the present invention, when the blending amount of the wax (D) is 3 to 20 mass%, the blending amount of the wax (D1) is preferably 2 to 19 mass%, and the blending amount of the wax (D2) is preferably 1 to 18 mass%, based on a total of 100 mass% of the styrene-based block copolymer (A), the tackifier resin (B), the mineral oil (C), and the wax (D) constituting the resin composition of the present invention.
In addition, when the blending amount of the wax (D) is 5 to 18 mass%, the blending amount of the wax (D1) is preferably 3 to 18 mass%, and the blending amount of the wax (D2) is preferably 2 to 17 mass%, based on a total of 100 mass% of the styrene-based block copolymer (A), the tackifier resin (B), the mineral oil (C), and the wax (D) constituting the resin composition of the present invention.
When the amount of wax (D1) is 2% by mass or more, the adhesiveness is reduced, and when the amount is 19% by mass or less, the adhesiveness is easily maintained, which is preferable. When the amount of wax (D2) is 1% by mass or more, the solidification becomes fast, and when the amount is 18% by mass or less, the adhesiveness is easily maintained, which is preferable.

Additives such as antioxidants, UV absorbers, antibacterial agents, deodorants, insect repellents, silane coupling agents, colorants, adhesion inhibitors, light stabilizers, fillers, and fragrances may be added to the resin composition of the present invention as long as they do not impair the object of the invention.

Examples of antioxidants 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-based 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.

The above phenol-based antioxidants function as radical traps that donate hydrogen to ROO (peroxy radicals) generated during the chain growth process of autoxidation to stabilize them, and then become stable phenoxy radicals protected by ortho-position substituents to stop the chain reaction, thereby effectively suppressing thermal degradation of the resin composition. In particular, the phenol-based antioxidants are more excellent when used in combination with lactone-based antioxidants (e.g., 5,7-di-tert-butyl-3-(3,4-dimethylphenyl)-3H-benzofuran-2-one) or vitamin E-based antioxidants (3,4-dihydro-2,5,7,8-tetramethyl-2-(4,8,12-trimethyltridecyl)-2H-benzopyran-6-ol), which have a faster radical trapping reaction than phenol-based antioxidants. In addition, the above phosphorus-based antioxidants function to non-radical decompose peroxides and ROOH and stop the chain reaction of the autoxidation process, thereby effectively suppressing thermal degradation of the resin composition.

The ultraviolet absorbing agent is not particularly limited, and examples thereof include commonly used agents such as salicylic acid, benzophenone, and benzotriazole. These ultraviolet absorbing agents may be used alone or in combination of two or more types.

Examples of antibacterial agents include benzylamine antibacterial agents such as butenafine and its salts, imidazole antibacterial agents such as bifonazole, neticonazole, ketoconazole, lanoconazole, clotrimazole, miconazole, oxiconazole, tioconazole, cloconazole, omoconazole, sulconazole and their salts, allylamine antibacterial agents such as terbinafine and its salts, morpholine antibacterial agents such as amorolfine and its salts, thiocarbamic acid antibacterial agents such as liranafte, tolnaftate and tolciclate, and antibiotics such as nystatin, trichomycin, variotin, siccanin and pyrrolnitrin. These antibacterial agents may be used alone or in combination of two or more.

There are no particular limitations on the deodorant as long as it has a deodorant effect, but examples include lauryl methacrylate, geranyl chlorinate, citronellyl senecionate, terpene aldehydes, pyruvate esters, zinc 2-ethylhexanoate, zinc ricinoleate, etc. These deodorants may be used alone or in combination of two or more types.

Examples of insect repellents include camphor, naphthalene, paradichlorobenzene, isobornyl, thiocyanoacetic acid, 1,2-benzenedicarboxylic acid diethyl ester, paraform, chloropicrin, pyrethrum, empenthrin, transfluthrin, allethrin, fenothrin, eminence, etc. These insect repellents may be used alone or in combination of two or more types.

The silane coupling agent is not particularly limited, and examples thereof include vinyl trimethoxysilane, vinyl triethoxysilane, methacryloxypropyl trimethoxysilane, γ-methacryloxypropyl methyl dimethoxysilane, γ-glycidoxypropyl trimethoxysilane, γ-glycidoxypropyl methyl dimethoxysilane, γ-glycidoxypropyl methyl diethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl trimethoxysilane, γ-aminopropyl trimethoxysilane, γ-aminopropyl triethoxysilane, γ-aminopropyl methyl methoxysilane, N-(2-aminoethyl) 3-aminopropyl trimethoxysilane, N-(2-aminoethyl) 3-aminopropyl methyl dimethoxysilane, γ-mercaptopropyl trimethoxysilane, γ-mercaptopropyl triethoxysilane, mercaptobutyl trimethoxysilane, and γ-mercaptopropyl methyl dimethoxysilane. These silane coupling agents may be used alone or in combination of two or more.

Colorants include commonly used known colorants, such as inorganic pigments and organic pigments. Inorganic pigments include, for example, carbon black, which is also used as the filler, iron oxide, titanium oxide, zinc oxide, red iron oxide, cadmium red, cadmium yellow, ultramarine, cobalt blue, titanium yellow, white lead, red lead, lead yellow, and Prussian blue. Organic pigments include, for example, quinacridone, polyazo yellow, anthraquinone yellow, polyazo red, azo lake yellow, perylene, phthalocyanine green, phthalocyanine blue, and isoindolinone yellow. These colorants may be used alone or in combination of two or more.

Examples of adhesion promoters include fatty acid amides, long-chain alkyl grafts of polyethyleneimine, soybean oil-modified alkyd resins (e.g., Arakawa Chemical Industries, Ltd., product name "Arakid 251"), and tall oil-modified alkyd resins (e.g., Arakawa Chemical Industries, Ltd., product name "Arakid 6300"), etc.

Light stabilizers include commonly used hindered amines.

Examples of fillers 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 fibers, natural fibers, and wood flour.

Examples of fragrances include hydrocarbon fragrances such as pinene and limonene, alcohol fragrances such as linalool, geraniol, citronellol, menthol, borneol, benzyl alcohol, anise alcohol, and β-phenethyl alcohol, phenol fragrances such as anethole and eugenol, aldehyde fragrances such as n-butyraldehyde, isobutyraldehyde, hexylaldehyde, citral, citronellal, benzaldehyde, and cinnamic aldehyde, ketone fragrances such as carvone, menthone, camphor, acetophenone, and ionone, lactone fragrances such as γ-butyrolactone, coumarin, and cineol, 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.

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

The resin composition of the present invention can be prepared by uniformly mixing the various components described above, and there are no particular limitations on the mixing means or conditions. A typical preparation method includes kneading the various components using an apparatus such as a mixing roll, roll, Banbury mixer, single-screw or twin-screw extruder, kneader, extruder, melt extruder, or melting kettle equipped with a stirrer, and then cooling and pulverizing the resulting kneaded product. There are no particular limitations on the kneading method, but melt kneading is preferred. The conditions for melt kneading may be appropriately determined depending on the types and amounts of the various components used, and there are no particular limitations.

In one embodiment of the present invention, the melt-kneading is preferably carried out at a temperature range of 60 to 200°C for 30 to 300 minutes, and more preferably at a temperature range of 65 to 195°C for 35 to 295 minutes. If the melt-kneading temperature is in the range of 60°C 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.

The resin composition of the present invention may be in the form of, for example, a block, a strand, a sheet, a plate, a pellet, or the like. In order to apply the resin composition of the present invention to molding processing, the shape is preferably a block from the viewpoint of the production stability of the resulting molded article.

The resin composition of the present invention is preferably applied at 80 to 150° C., and can be applied to a roll that requires application at a low viscosity, or to a melting pot equipped with a stirrer for melting. From this viewpoint, the resin composition of the present invention preferably has a viscosity at 120° C. of 500 to 3,000 mPa·s.
If the viscosity at 120° C. is less than 500 mPa·s, the resin composition may drip when a large amount is applied. If the viscosity at 120° C. is more than 3,000 mPa·s, workability may become a problem during application.

The resin composition of the present invention can be formed by applying the resin composition, which has been heated and melted, or a solution thereof to substrates such as paper, resin, and nonwoven fabric in various patterns such as a mirror-like state, a foamed state, a bead state, and a spiral state, using a coating machine or a hot melt coating machine that is normally used, and then aging, heating, and cooling as necessary, thereby forming a resin layer, and obtaining various laminates in which resin layers are laminated. The resin composition can be applied in layers, or two types of resin compositions can be applied in parallel to the same substrate. The resin layer can be formed using a coating device that is normally used. Examples of coating devices include a roll knife coater, a die coater, a roll coater, a bar coater, a gravure roll coater, a reverse roll coater, a dipping coater, and a blade coater.

Next, the laminate of the present invention will be described.
The basic laminate structure of the laminate of the present invention is a single-surface laminate such as substrate/resin layer/release film, or a double-sided laminate such as release film/resin layer/substrate/resin layer/release film. When used, 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 hardness without completely solidifying during application, and has cohesive force to maintain the application state.

There are no particular limitations on the material of the substrate. For example, examples of resin films include polyester resins, polycarbonate resins, polyarylate resins, acrylic resins, polyphenylene sulfide resins, polystyrene resins, vinyl resins, polyimide resins, epoxy resins, and olefin resins such as polyethylene, polypropylene, and norbornene. The substrate may be a single layer or multiple layers. Other examples include nonwoven fabrics, woven fabrics, cloth, paper, glass, metal foils, metal meshes, and composites containing these. If necessary, the surface of the substrate may be subjected to a corona discharge treatment, plasma treatment, blast treatment, chemical etching treatment, or other easy-adhesion treatment, antistatic treatment, coloring treatment, or the like. Furthermore, a release film may also be used as the substrate, and the resin composition may be coated on the release film. There are no particular limitations on the thickness of these substrates, but a thickness of 1 μm to 1000 μm is preferable from the viewpoint of workability.

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

The resin layer can be used by laminating it with a release film, etc., if necessary. There are no particular limitations on the release film, but examples include polyethylene terephthalate film (hereinafter referred to as PET film), polyolefin resin films such as polyethylene, polypropylene, and norbornene, PPS resin film, TAC film, acrylic resin film, and films that have been subjected to a release treatment.

The laminate of the present invention may have a configuration in which the resin layer is sandwiched between a film-like substrate other than a release film and a release film, between a film-like substrate other than a release film and a film-like substrate other than a release film, or between a release film and a release film. A configuration in which the resin layer is sandwiched between a film-like substrate other than a release film and a release film is preferred.

The present invention will be described in more detail with reference to the following examples. However, these examples are merely one embodiment of the present invention, and the present invention is not limited to these examples.
In the examples, "parts" means "parts by mass" and "%" means "% by mass".

The softening point, melting point, penetration, and viscosity at 120°C were measured using the following methods.

<Softening point>
The softening point was measured according to the method specified in JIS K6863.
That is, a specified ring filled with a resin composition was left to stand for 12 hours or more, then placed in a heat medium, a specified ball was placed on top of the specified ring filled with the resin composition, and the temperature of the heat medium (glycerin) was raised at a certain rate. The temperature at which the ball sank due to softening of the resin composition and touched the bottom plate of the ring stand was read and recorded as the softening point.

<Melting Point>
The melting point was measured by 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 heat generation peak of the chart obtained under the temperature increase condition of 10° C./min was read. The melting point was taken as the temperature at the peak top.

<Penetration>
The penetration was measured according to the method specified in JIS K 2235.
The penetration is measured by heating and melting the wax (D) and placing it in a sample container, cooling it, and then keeping it at a constant temperature in a thermostatic water bath, and then inserting a needle with a total mass of 100 g vertically into the sample for 5 seconds. The penetration depth of the needle is measured to the nearest 0.1 mm, and the value is multiplied by 10 to express the penetration depth as a numerical value (absolute number).

<Viscosity measurement at 120°C>
The viscosity at 120° C. was measured using a Brookfield viscometer (TVB-10M, manufactured by Toki Sangyo Co., Ltd.) under the following conditions.
Temperature: 120℃
Sample size: about 500g
Rotor No.: 3
Rotor speed: 12 rpm
Rotation time: 30 seconds

(Examples 1 to 12, Comparative Examples 1 to 10)
The styrene-based block copolymer (A), tackifier resin (B), mineral oil (C), wax (D), and optionally an antioxidant were added to a kneader equipped with a stirrer in the amounts shown in Tables 1 and 2, and the mixture was stirred at 150° C. for 3 hours to obtain a resin composition.

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 Kraton Corporation)
SBS2: SBS, styrene block content 30% by mass, triblock content 85%, diblock content 15% (product name TR-2782, manufactured by JSR Corporation)
SBS3: SBS, styrene block content 30% by mass, triblock content 85%, diblock content 15% (product name TR-2601, manufactured by JSR Corporation)
SBS4: SBS, styrene block content 36.5% by mass, triblock content 35%, diblock content 65% (PB5502, manufactured by CHIMEI Co., Ltd.)
SBS5: 3-branched styrene-butadiene block copolymer: styrene block content 40% by mass, triblock content 30%, diblock content 70% (HJ12-4, manufactured by Asahi Kasei Corporation)
SBS6: Linear styrene-butadiene block copolymer: styrene block content 43% by mass, triblock content 40%, diblock content 60% (Asaprene T439, manufactured by Asahi Kasei Corporation)
SEBS: SEBS, styrene block content 30% by mass, triblock content 100% (G-1652, manufactured by Kraton Corporation)

Tackifying resin 1: Unhydrogenated rosin-based tackifying resin, softening point 104° C. (SYLVALITE RE105L, manufactured by Kraton Corporation)
Tackifying resin 2: Partially hydrogenated petroleum-based tackifying resin, softening point 90°C (Alcon M-90, manufactured by Arakawa Chemical Industry Co., Ltd.)
Tackifying resin 3: Hydrogenated petroleum-based tackifying resin, softening point 100°C (Arcon P-100, manufactured by Arakawa Chemical Industries, Ltd.)
Tackifying resin 4: Unhydrogenated terpene-based tackifying resin, softening point 95° C. (SYLVARES 1095, manufactured by Kraton)
Tackifier resin 5: Partially hydrogenated alicyclic petroleum hydrocarbon resin, softening point 100°C (Arcon M-100, manufactured by Arakawa Chemical Industries, Ltd.)
Tackifier resin 6: Hydrogenated tackifier resin (Sucoretz SU420, product name, manufactured by Colon Co., Ltd.)
Tackifier resin 7: Hydrogenated tackifier resin (Imarv S100, product name, manufactured by Idemitsu Kosan Co., Ltd.), softening point 100° C.
Tackifying resin 8: Endblock hydrogenated tackifying resin (Plastolyn 290, trade name, manufactured by Eastman Chemical Company)

Mineral oil 1: Paraffinic mineral oil, paraffin chain carbon number out of total carbon number: 71%, naphthene ring carbon number out of total carbon number: 29% (Diana Process Oil PW-90, manufactured by Idemitsu Kosan Co., Ltd.)
Mineral oil 2: Paraffinic mineral oil, paraffin chain carbon number of total carbon number: 67.1%, naphthene ring carbon number of total carbon number: 32.8%, aromatic ring carbon number of total carbon number: 0.1% (Diana Process Oil PS-32, Idemitsu Kosan Co., Ltd.)
Mineral oil 3: Liquid paraffin, paraffin chain carbon number out of total carbon number: 100% (Hicol K-350, manufactured by Kaneda Co., Ltd.)
Mineral oil 4: naphthenic process oil ("Nyflex 222B" manufactured by Nynas)
Mineral oil 5: Paraffin oil ("Dianaphresis S-32", manufactured by Idemitsu Kosan Co., Ltd.)

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) (Polylets 200EL, manufactured by SCG Performance Chemicals)
Wax 5: Polyethylene wax, melting point 116°C, penetration 2 (25°C) (Hiwax 100P, manufactured by Mitsui Chemicals)

The abbreviations for the other components listed in Tables 1 and 2 are as follows.
Antioxidant 1: Pentaerythritol tetrakis [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]
Liquid polymer: Liquid polyisoprene having a carboxylic acid non-hydride group (Kuraray LIR-403)

(evaluation)
The resin compositions prepared in Examples 1 to 12 and Comparative Examples 1 to 10 were evaluated for viscosity, low-temperature coatability, adhesive strength (dry), and adhesive strength (wet) according to the procedures described below. The results are shown in Table 1.

[viscosity]
The viscosity of the resin composition at 120° C. was measured.
A viscosity of 500 or more and less than 3,000 mPa·s, which allows coating with an appropriate coating amount, was rated as "good."
Good: 500 or more and less than 3,000 mPa·s Bad: Less than 500 mPa·s or 3,000 mPa·s or more

[Low temperature coatability]
The coating temperature was 120° C., the coating speed was 30 m/min, the coating amount was 3 to 6 g/m ² , and the width was 5 cm. The low-temperature coatability was evaluated.
◯: Spiral coating was possible. ×: Spiral coating was not possible.

[Adhesive strength (DRY)]
The resin compositions obtained in Examples 1 to 12 and Comparative Examples 1 to 10 were spirally coated onto a nonwoven fabric (18 g/m ² ) at a coating temperature of 120° C., a coating speed of 30 m/min, a coating amount of 5 g/m ² , and a width of 5 cm, and then pressed in the flow direction at 23° C. and a pressure of 50 gf/cm ² for 0.01 seconds to bond the nonwoven fabric (18 g/m ² ). A test sample was cut into a length of 15 cm and a width of 25 mm in the direction perpendicular to the flow direction.
The adhesive strength (dry) of the obtained test sample was measured. T-shaped peeling was performed at a speed of 300 mm/min, and the average adhesive strength of the coated area was calculated. A was judged to be practical.
◯: 3 N/25 mm or more △: 2 N/25 mm or more to less than 3 N/25 mm ×: less than 2 N/25 mm Note that resin compositions with diagonal lines in the adhesion evaluation results in Table 2 indicate that test samples could not be prepared under the above-mentioned coating conditions and adhesion evaluation was not performed.

[Adhesive strength (WET)]
Using the test samples prepared by the above method, the adhesive strength (wet) was measured by the following method.
The test sample was immersed in water and left to stand for 5 minutes. After drying to the extent that no water droplets fell off, the sample was subjected to T-peel at a speed of 300 mm/min, and the average adhesive strength of the applied portion was calculated. ○ was judged to be practical.
◯: 2 N/25 mm or more ×: less than 2 N/25 mm Note that resin compositions with a diagonal line in the adhesion evaluation results in Table 2 indicate that a test sample could not be prepared under the above-mentioned coating conditions and adhesion evaluation was not performed.

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

[Hume]
The resin compositions obtained in Examples 1 to 12 and Comparative Examples 1 to 10 were placed in a 500 ml metal can (250 ml), covered with a metal lid, and heated at 120° C. for 1 hour to check for the generation of fumes.
○: After opening the lid, no fumes were visible to the naked eye.
×: Fumes were visible when the lid was opened.

As is clear from the results in Tables 1 and 2, the results in the comparative examples were insufficient, whereas the results in the examples were good.

Claims (3)

In a total of 100% by mass of the styrene-based block copolymer (A), the tackifier resin (B), the mineral oil (C), and the wax (D),
3 to 15% by mass of a styrene-based block copolymer (A),
50 to 80% by mass of a tackifier resin (B),
3 to 20% by mass of a mineral oil (C); and
The wax (D) is contained in an amount of 7 to 16.5 mass %,
The wax (D) includes a wax (D1) having a melting point of 50° C. or more and less than 70° C. and a wax (D2) having a melting point of 102 ° C. or more and 130° C. or less,
the wax (D1) is contained in an amount of 5 to 15 mass% and the wax (D2) is contained in an amount of 1 to 5.5 mass% relative to a total of 100 mass% of the styrene-based block copolymer (A), the tackifier resin (B), the mineral oil (C), and the wax (D);
A resin composition, characterized in that in a styrene-based block copolymer (A), the styrene block content is 10 to 40 mass% , the triblock content is 85 to 100 mass% , and the diblock content is 0 to 15 mass%. The resin composition according to claim 1, characterized in that the tackifier resin (B) contains at least one of a rosin-based tackifier resin and a terpene-based tackifier resin. A laminate having a resin layer formed from the resin composition according to claim 1 or 2 on at least one surface of a substrate.