JP7259588B2 - Textile product, its manufacturing method, and adhesive set - Google Patents

Description

TECHNICAL FIELD The present invention relates to a textile product, its manufacturing method, and an adhesive set.

Moisture-curable hot-melt adhesives are sometimes used to bond fiber substrates such as woven fabrics together (eg, Patent Document 1).

Moisture-curable hot-melt adhesives used for such applications are expected to exhibit excellent adhesiveness and stretchability in textile products in which fiber substrates are bonded to each other via the cured product of the adhesive. necessary. However, there is a trade-off relationship between adhesive properties and stretchability properties, and it tends to be difficult to achieve both of these properties at a high level by improving the moisture-curable hot-melt adhesive itself. .

JP-A-10-088097

A main object of the present invention is to provide a method for producing a textile product that enables the production of a textile product having excellent adhesiveness and stretchability.

As a result of extensive studies by the present inventors in order to solve the above problems, three layers in which an adhesive layer having relatively excellent stretchability is sandwiched between two adhesive layers having relatively excellent adhesiveness The inventors have found that it is possible to manufacture a textile product having excellent adhesiveness and stretchability by using a structure, and have completed the present invention.

In one aspect of the present invention, a moisture-curable hot-melt adhesive containing a urethane prepolymer is placed on a first fiber base material to form a first adhesive layer made of the moisture-curable hot-melt adhesive. a first step of disposing a moisture-curable hot-melt adhesive containing a urethane prepolymer on the first adhesive layer to form a second adhesive layer made of the moisture-curable hot-melt adhesive; Step 2, and a third step of disposing a moisture-curable hot-melt adhesive containing a urethane prepolymer on the second adhesive layer to form a third adhesive layer made of the moisture-curable hot-melt adhesive. and placing the second fiber base on the third adhesive layer, and through the adhesive layer consisting of the first adhesive layer, the second adhesive layer, and the third adhesive layer and a fourth step of bonding the first fiber base material and the second fiber base material, wherein the urethane prepolymer used in the second step contains an elastomer constitutional unit derived from an elastomer polyol, The urethane prepolymer used in the first step satisfies either the following condition (a) or the following condition (b), and the urethane prepolymer used in the third step satisfies the following condition (c) or the following condition ( To provide a method for manufacturing a textile product that satisfies any of d).

Condition (a): Contains no elastomer structural unit.
Condition (b): The content of elastomer constitutional units, based on the total amount of polyol-derived constitutional units in the urethane prepolymer used in the first step, is equal to the content of the elastomer constitutional units used in the second step. It is less than the content of elastomer structural units based on the total amount of polyol-derived structural units in the urethane prepolymer obtained.

Condition (c): Contains no elastomer structural unit.
Condition (d): The content of elastomer constitutional units based on the total amount of polyol-derived constitutional units in the urethane prepolymer used in the third step, which contains elastomer constitutional units, is It is less than the content of elastomer structural units based on the total amount of polyol-derived structural units in the urethane prepolymer obtained.

According to such a method for manufacturing a textile product, the first adhesive layer has better adhesion than the second adhesive layer, and the first adhesive layer and the third adhesive layer have better stretchability. By using the adhesive layer consisting of the second adhesive layer and the third adhesive layer having better adhesiveness than the second adhesive layer, it is possible to produce a textile product having excellent adhesiveness and stretchability. can be possible.

The urethane prepolymer used in the first step may satisfy condition (a).

The urethane prepolymer used in the third step may satisfy condition (c).

The elastomer may be a polybutadiene polyol or a hydrogenated polybutadiene polyol.

Another aspect of the present invention comprises a first moisture-curable hot-melt adhesive containing a first urethane prepolymer and a second moisture-curable hot-melt adhesive containing a second urethane prepolymer. We provide an adhesive set that is In this adhesive set, the first urethane prepolymer contains an elastomer constitutional unit derived from an elastomer polyol, and the second urethane prepolymer satisfies either condition (e) or condition (f) below.

Condition (e): Contains no elastomer structural unit.
Condition (f): The content of elastomer constitutional units, based on the total amount of constitutional units containing elastomer constitutional units and derived from polyol in the second urethane prepolymer, is equal to the polyol in the first urethane prepolymer. It is less than the content of elastomer structural units based on the total amount of derived structural units.

The second urethane prepolymer may satisfy condition (e).

The elastomer may be a polybutadiene polyol or a hydrogenated polybutadiene polyol.

Another aspect of the present invention is a first fiber base material, a first adhesive cured product layer comprising a cured product of a moisture-curable hot melt adhesive containing a urethane prepolymer, and a moisture adhesive containing a urethane prepolymer. a second cured adhesive layer made of a cured hot melt adhesive; a third cured adhesive layer made of a cured moisture curable hot melt adhesive containing a urethane prepolymer; and a fiber base material in this order. The urethane prepolymer in the second cured adhesive layer contains an elastomer structural unit derived from an elastomer polyol, and the urethane prepolymer in the first cured adhesive layer satisfies the following conditions (a) or (b): and the urethane prepolymer in the third cured adhesive layer satisfies either the following condition (c) or the following condition (d).

Condition (a): Contains no elastomer structural unit.
Condition (b): The content of elastomer constitutional units, based on the total amount of constitutional units derived from the polyol in the urethane prepolymer in the first adhesive cured product layer, is equal to or higher than the second adhesion. It is less than the content of elastomer structural units based on the total amount of polyol-derived structural units in the urethane prepolymer in the agent-cured product layer.

Condition (c): Contains no elastomer structural unit.
Condition (d): Elastomer structural units are included, and the content of the elastomer structural units when based on the total amount of polyol-derived structural units in the urethane prepolymer in the third adhesive cured product layer is It is less than the content of elastomer structural units based on the total amount of polyol-derived structural units in the urethane prepolymer in the agent-cured product layer.

ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the textiles which can manufacture the textiles excellent in adhesiveness and stretchability is provided. Further, according to the present invention, there is provided a textile product obtained by such a method for manufacturing a textile product. Furthermore, according to the present invention, there is provided an adhesive set suitable for use in such a method for manufacturing textile products.

FIG. 1 is a schematic diagram showing one embodiment of a method for manufacturing a textile product. FIGS. 1(a), (b), (c), and (d) are schematic diagrams showing each step. FIG. 2 is a schematic cross-sectional view showing an adhesive layer having a three-layer structure in FIG. 1(b).

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described with appropriate reference to the drawings. However, the present invention is not limited to the following embodiments.

[Method for manufacturing textile products]
FIG. 1 is a schematic diagram showing one embodiment of a method for manufacturing a textile product. FIG. 2 is a schematic cross-sectional view showing an adhesive layer having a three-layer structure in FIG. 1(b). The method for manufacturing the textile product shown in FIG. 1 comprises a step of disposing a first fiber base material 1 along a support 10 (see FIG. 1(a)), and a urethane coating on the first fiber base material 1. A step of disposing a moisture-curable hot-melt adhesive containing a prepolymer (hereinafter sometimes referred to as "hot-melt adhesive") and forming a first adhesive layer 4a made of the hot-melt adhesive (first step) and a step of disposing a hot melt adhesive containing a urethane prepolymer on the first adhesive layer 4a to form a second adhesive layer 4b made of the hot melt adhesive (second step ) and a step of disposing a hot-melt adhesive containing urethane prepolymer on the second adhesive layer 4b to form a third adhesive layer 4c made of the hot-melt adhesive (third step, FIG. 1(b) and FIG. 2), and placing the second fiber base material 2 on the third adhesive layer 4c, the first adhesive layer 4a, the second adhesive layer 4b, and the third adhesive layer 4c. and a step (fourth step) of bonding the first fiber base material 1 and the second fiber base material 2 via the adhesive layer 4 composed of the adhesive layer 4c.

The first step is to form a first adhesive layer 4a made of a hot-melt adhesive containing urethane prepolymer on the first fiber base material 1 . The second step is to form a second adhesive layer 4b made of a hot-melt adhesive containing urethane prepolymer on the first adhesive layer 4a. The third step is to form a third adhesive layer 4c made of a hot-melt adhesive containing urethane prepolymer on the second adhesive layer 4b.

The first fiber base material 1 is not particularly limited as long as it contains fibers, and may be, for example, a woven fabric (such as a fabric), a knitted fabric, or a non-woven fabric. The nonwoven may be paper. The first fiber base material 1 and the second fiber base material 2 described below may be the same or different.

The 1st adhesive bond layer 4a is a layer which is more excellent in adhesiveness than the 2nd adhesive bond layer 4b. Such a layer is manufactured, for example, by adjusting the components contained in the hot-melt adhesive for forming the first adhesive layer 4a (in particular, the constituent units of the urethane prepolymer used in the first step). can do. The first adhesive layer 4a is formed, for example, by disposing a hot melt adhesive in a predetermined adhesion region within the surface of the first fiber base material 1. As shown in FIG. The first adhesive layer 4a may be formed, for example, by applying it to a predetermined adhesion region within the surface of the first fiber base material 1. As shown in FIG. The hot melt adhesive is applied to the first fiber base material 1 in a melted state by heating at 60 to 130° C., for example. The coating method is not particularly limited, and examples thereof include a method using a coating device such as a die coater, a roll coater, and a sprayer. Dispensers are suitable when the hot melt adhesive is to be applied to a narrow adhesive area. Alternatively, the first adhesive layer 4a may be formed by laminating a film-like hot-melt adhesive on the first fiber base material 1 . The hot-melt adhesive (urethane prepolymer used in the first step) for forming the first adhesive layer 4a will be described later.

The second adhesive layer 4b is a layer that is more stretchable than the first adhesive layer 4a and the third adhesive layer 4c. Such a layer is manufactured by, for example, adjusting the components contained in the hot-melt adhesive for forming the second adhesive layer 4b (in particular, the constituent units of the urethane prepolymer used in the second step). can do. The second adhesive layer 4b is formed, for example, by disposing a hot-melt adhesive on a predetermined adhesive area or the entire area within the surface of the first adhesive layer 4a. The second adhesive layer 4b may be formed, for example, by coating a predetermined adhesive area or the entire area within the surface of the first adhesive layer 4a. The method of disposing the hot-melt adhesive may be the same as the method of disposing the first adhesive layer 4a. Alternatively, the second adhesive layer 4b may be formed by laminating a film-like hot-melt adhesive on the first adhesive layer 4a. The hot-melt adhesive (urethane prepolymer used in the second step) for forming the second adhesive layer 4b will be described later.

The third adhesive layer 4c is a layer having adhesiveness superior to that of the second adhesive layer 4b. The third adhesive layer 4c may be the same as or different from the first adhesive layer 4a. Such a layer is manufactured by, for example, adjusting the components contained in the hot-melt adhesive for forming the third adhesive layer 4c (in particular, the constituent units of the urethane prepolymer used in the third step). can do. The third adhesive layer 4c is formed, for example, by disposing a hot-melt adhesive over a predetermined adhesive area or entire surface within the surface of the second adhesive layer 4b. The third adhesive layer 4c may be formed, for example, by coating a predetermined adhesive area within the surface of the second adhesive layer 4b. The method of disposing the hot-melt adhesive may be the same as the method of disposing the first adhesive layer 4a. Alternatively, the third adhesive layer 4c may be formed by laminating a film-like hot-melt adhesive on the second adhesive layer 4b. The hot-melt adhesive (urethane prepolymer used in the third step) for forming the third adhesive layer 4c will be described later.

The adhesive layer 4 consists of a first adhesive layer 4a, a second adhesive layer 4b and a third adhesive layer 4c. The minimum width of the adhesive layer 4 may be, for example, 0.1-20 mm. The thickness of the adhesive layer 4 (the thickness of the portion not soaked into the first fiber base material 1) may be 0.01 to 3 mm.

The hot-melt adhesive forming the second adhesive layer 4b contains a urethane prepolymer containing structural units derived from polyol and having an isocyanate group as a terminal group. The urethane prepolymer used in the second step contains elastomer constitutional units derived from an elastomer polyol (elastomer having more than one hydroxy group) from the viewpoint of improving stretchability.

The urethane prepolymers used in the second step are reaction products (or polycondensates) of polyols, including elastomeric polyols, and polyisocyanates.

Examples of elastomer polyols include elastomers such as polybutadiene-based elastomers, olefin-based elastomers (TPO), styrene-based elastomers, ester-based elastomers, amide-based elastomers, and vinyl chloride-based elastomers, which have more than one hydroxy group. Some things are mentioned. Among these, the elastomeric polyol may be a polybutadiene-based elastomer having more than one hydroxy group, more specifically a polybutadiene polyol or a hydrogenated polybutadiene polyol.

Polybutadiene polyol is a compound having a butadiene-derived polymer chain and hydroxyl groups at both ends of the polymer chain, and hydrogenated polybutadiene polyol is a hydrogenated polybutadiene polyol. Polybutadiene polyol and hydrogenated polybutadiene polyol may have an average of about 1.8 to 2.5 hydroxyl groups in the molecule. A polymer chain derived from polybutadiene and its hydrogenated product can act as an elastomer, and having such a polymer chain tends to easily impart stretchability to the urethane prepolymer. The urethane prepolymer may contain structural units derived from a hydrogenated polybutadiene polyol because of its superior flexibility.

Commercially available polybutadiene polyols and hydrogenated polybutadiene polyols can be used as they are. Commercially available hydrogenated polybutadiene polyols include, for example, GI-1000, GI-2000 and GI-3000 (trade names manufactured by Nippon Soda Co., Ltd.). Examples of commercially available polybutadiene polyols include G-1000, G-2000, G-3000 (trade names manufactured by Nippon Soda Co., Ltd.), Poly bd R-15HT, Poly bd R-45HT (manufactured by Idemitsu Kosan Co., Ltd. (trade name), Krasol LBH-P3000 (trade name manufactured by Clay Valley), and the like. These may be used individually by 1 type, and may use 2 or more types together.

The number average molecular weight (Mn) of polybutadiene polyol and hydrogenated polybutadiene polyol may be 500 to 100,000, 700 to 50,000, or 900 to 10,000 from the viewpoint of the balance of viscosity and adhesion. As used herein, the number average molecular weight (Mn) is a value measured by gel permeation chromatography (GPC) and converted to standard polystyrene.

From the viewpoint of improving stretchability, the content of the elastomer structural unit in the urethane prepolymer used in the second step is 10% by mass or more, 40% by mass or more, 50% by mass or more, based on the total amount of polyol-derived structural units. % by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, or 90% by mass or more, or 100% by mass.

The urethane prepolymer used in the second step may contain structural units derived from polyols other than elastomer polyols. Polyols other than elastomer polyols include, for example, polyester polyols, polyether polyols, polyacrylate polyols, polycarbonate polyols, polysiloxane polyols, polyisoprene polyols and polyolefin polyols. Polyols other than elastomer polyols may be used alone or in combination of two or more.

The content of structural units derived from polyols other than elastomer polyols in the urethane prepolymer used in the second step is 0 to 60% by mass, 0 to 50% by mass, based on the total amount of structural units derived from polyols. It may be 0-40% by weight, 0-30% by weight, 0-20% by weight, or 0-10% by weight.

Polyisocyanate can be used without any particular limitation as long as it is a compound having more than one isocyanate group. A polyisocyanate may be a compound having two isocyanate groups (diisocyanate). Examples of polyisocyanates include aromatic isocyanates such as diphenylmethane diisocyanate, dimethyldiphenylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate and p-phenylene diisocyanate; alicyclic isocyanates such as dicyclohexylmethane diisocyanate and isophorone diisocyanate; and aliphatic isocyanates. From the viewpoint of reactivity and adhesion, the polyisocyanate preferably contains aromatic diisocyanate, more preferably diphenylmethane diisocyanate. One type of polyisocyanate may be used alone, or two or more types may be used in combination.

A urethane prepolymer can be synthesized by reacting a polyol including an elastomer polyol with a polyisocyanate. When synthesizing such a urethane prepolymer, the equivalent ratio of the isocyanate group (NCO) of the polyisocyanate to the hydroxy group (OH) of the polyol (isocyanate group (NCO) equivalent of the polyisocyanate / (hydroxyl group (OH) equivalent of the polyol ), NCO/OH) may be 1.1 or more, and may be from 1.1 to 2.1. When the NCO/OH ratio is 1.1 or more, the urethane prepolymer has an isocyanate group as a terminal, and an increase in the viscosity of the urethane prepolymer can be suppressed, which tends to further improve workability. When the NCO/OH ratio is 2.1 or less, foaming is less likely to occur during the moisture curing reaction of the hot-melt adhesive, which tends to make it easier to suppress a decrease in adhesive strength.

The temperature and time for reacting the polyol including the elastomer polyol and the polyisocyanate when synthesizing the urethane prepolymer used in the second step are not particularly limited, but for example, 85 to 120° C., 0.1 minute to 48° C. It can be time.

The hot-melt adhesive forming the second adhesive layer 4b may further contain a catalyst from the viewpoint of promoting curing of the urethane prepolymer and developing higher adhesive strength. Examples of catalysts include dibutyltin dilaurate, dibutylthione octate, dimethylcyclohexylamine, dimethylbenzylamine, trioctylamine, and dimorpholinodiethyl ether. The content of the catalyst may be 0.001-0.5% by weight based on the total amount of the hot melt adhesive.

The hot-melt adhesive forming the second adhesive layer 4b may further contain a tackifying resin from the viewpoint of imparting stronger adhesiveness to the formed adhesive layer. Examples of tackifying resins include rosin resins, rosin ester resins, hydrogenated rosin ester resins, terpene resins, terpene phenol resins, hydrogenated terpene resins, petroleum resins, hydrogenated petroleum resins, coumarone resins, ketone resins, styrene resins, Modified styrene resins, xylene resins, epoxy resins and the like can be mentioned. The content of the tackifying resin may be 0.1-50% by weight based on the total amount of the hot melt adhesive.

The hot-melt adhesive forming the second adhesive layer 4b may further contain other components as necessary. Other components include, for example, antioxidants, pigments, ultraviolet absorbers, surfactants, flame retardants, fillers, photocoloring agents, thermal coloring inhibitors, fragrances, imaging agents, thermal crosslinking agents, and the like. The content of other components may be 0.001 to 10% by mass based on the total amount of the hot melt adhesive.

The viscosity of the hot-melt adhesive forming the second adhesive layer 4b while being applied to the first adhesive layer 4a is 0.01 Pa s or more at 120° C. and 0 05 Pa·s or more, or 0.1 Pa·s or more, and may be 35 Pa·s or less, 30 Pa·s or less, or 20 Pa·s or less.

The hot melt adhesive forming the second adhesive layer 4b may be in the form of a film. A film-like hot-melt adhesive can be formed, for example, by applying a hot-melt adhesive onto a support film such as a PET film. The thickness of the film hot melt adhesive may be 10 μm or more, 20 μm or more, or 30 μm or more, and may be 300 μm or less, 250 μm or less, or 200 μm or less.

The hot-melt adhesive that forms the first adhesive layer 4a contains a urethane prepolymer containing structural units derived from polyol and having an isocyanate group as a terminal group. The urethane prepolymer used in the first step satisfies either the following condition (a) or the following condition (b), and may satisfy the following condition (a).

Condition (a): Contains no elastomer structural unit.
Condition (b): The content of elastomer constitutional units, based on the total amount of polyol-derived constitutional units in the urethane prepolymer used in the first step, is equal to the content of the elastomer constitutional units used in the second step. It is less than the content of elastomer structural units based on the total amount of polyol-derived structural units in the urethane prepolymer obtained.

That is, the urethane prepolymer used in the first step does not contain an elastomer structural unit, or even if it contains an elastomer structural unit, the content of the elastomer structural unit is the same as that used in the second step. less than the urethane prepolymers used. By adjusting the elastomer constitutional units in this way, the obtained first adhesive layer 4a can be a layer with superior adhesiveness and suppressed stretchability compared to the second adhesive layer 4b.

The hot-melt adhesive that forms the third adhesive layer 4c contains a urethane prepolymer containing structural units derived from polyol and having an isocyanate group as a terminal group. The urethane prepolymer used in the third step satisfies either condition (c) or condition (d) below, and may satisfy condition (c) below.

Condition (c): Contains no elastomer structural unit.
Condition (d): The content of elastomer constitutional units based on the total amount of polyol-derived constitutional units in the urethane prepolymer used in the third step, which contains elastomer constitutional units, is It is less than the content of elastomer structural units based on the total amount of polyol-derived structural units in the urethane prepolymer obtained.

That is, the urethane prepolymer used in the third step does not contain an elastomer structural unit, or even if it does contain an elastomer structural unit, the content of the elastomer structural unit is the same as that used in the second step. less than the urethane prepolymers used. By adjusting the elastomer constitutional units in this way, the third adhesive layer 4c obtained can be a layer with superior adhesiveness and suppressed stretchability compared to the second adhesive layer 4b.

The first adhesive layer 4a and the third adhesive layer 4c may be the same or different. That is, a hot melt adhesive (particularly, the urethane prepolymer used in the first step) forming the first adhesive layer 4a and a hot melt adhesive forming the third adhesive layer 4c (particularly, the third The urethane prepolymers used in the step 3) may be the same or different.

The urethane prepolymer used in the first step is a reaction product (or polycondensate) of polyol and polyisocyanate and satisfies condition (a) or condition (b). The urethane prepolymer used in the third step is a reaction product (or polycondensate) of polyol and polyisocyanate and satisfies condition (c) or condition (d). These urethane prepolymers may contain structural units derived from polyester polyol from the viewpoint of adhesiveness.

A compound produced by a polycondensation reaction between a polyhydric alcohol and a polycarboxylic acid can be used as the polyester polyol. Polyester polyols have, for example, polyhydric alcohols having 2 to 15 carbon atoms and 2 or 3 hydroxy groups and 2 to 14 carbon atoms (including the carbon atoms in the carboxyl groups), 2 It may also be a polycondensate with a polycarboxylic acid having up to 6 carboxyl groups. Polyester polyols may be used alone or in combination of two or more.

The polyester polyol may be a linear polyester diol produced from a diol and a dicarboxylic acid, or a branched polyester triol produced from a triol and a dicarboxylic acid. Branched polyester triols can also be obtained by reacting diols with tricarboxylic acids.

Examples of polyhydric alcohols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, isomers of butanediol, isomers of pentanediol, isomers of hexanediol, 2,2- Dimethyl-1,3-propanediol, 2-methylpropanediol, 2,4,4-trimethyl-1,6-hexanediol, 2,2,4-trimethyl-1,6-hexanediol, 1,4-cyclohexane diols, aliphatic or alicyclic diols such as 1,4-cyclohexanedimethanol; aromatic diols such as 4,4'-dihydroxydiphenylpropane, bisphenol A, bisphenol F, pyrocatechol, resorcinol and hydroquinone. One type of polyhydric alcohol may be used alone, or two or more types may be used in combination. Among these, aliphatic diols are preferred, more preferably aliphatic diols having 2 to 6 carbon atoms.

Examples of polycarboxylic acids include aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, and 1,2,4-benzenetricarboxylic acid; maleic acid, fumaric acid, aconitic acid, and 1,2,3-propane. Aliphatic acids such as tricarboxylic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, cyclohexane-1,2-dicarboxylic acid, 1,4-cyclohexanediene-1,2-dicarboxylic acid Alternatively, alicyclic polycarboxylic acids and the like can be mentioned. One type of polycarboxylic acid may be used alone, or two or more types may be used in combination.

A polycarboxylic acid derivative such as a carboxylic acid anhydride or a compound in which a part of the carboxyl group is esterified can be used instead of the polycarboxylic acid. Examples of polycarboxylic acid derivatives include dodecyl maleic acid and octadecenyl maleic acid.

The polyester polyol may be an amorphous polyester polyol or a crystalline polyester polyol. Here, amorphousness and crystallinity can be judged in the state at 25°C. As used herein, amorphous polyester polyol means a polyester polyol that is amorphous at 25°C, and crystalline polyester polyol means a polyester polyol that is crystalline at 25°C. The polyester polyol may contain amorphous polyester polyol.

The number average molecular weight Mn of the polyester polyol may be 3000 or less, preferably in the range of 500 to 3000, more preferably in the range of 1000 to 3000, from the viewpoint of improving the adhesive strength of the hot melt adhesive. In addition, in this specification, a number average molecular weight is a value measured by a gel permeation chromatography (GPC) and converted into standard polystyrene.

The content of structural units derived from polyester polyol in the urethane prepolymer is 70% by mass or more, 80% by mass or more, and 90% by mass, based on the total amount of structural units derived from polyol, from the viewpoint of further improving adhesive strength. or more, or 95% by mass or more, or 100% by mass.

The urethane prepolymer used in the first step and the urethane prepolymer used in the third step may contain structural units derived from polyols other than polyester polyols. Examples of polyols other than polyester polyols include polyether polyols, polyether ester polyols, polyurethane polyols, and polycarbonate polyols. Polyols other than polyester polyols may be used alone or in combination of two or more.

The content of structural units derived from polyols other than polyester polyols in the urethane prepolymer is 0 to 30% by mass, 0 to 20% by mass, 0 to 10% by mass, or It may be from 0 to 5% by mass.

The polyisocyanate may be the same as those exemplified for the urethane prepolymer used in the second step. The conditions for synthesizing the urethane prepolymer used in the first step and the urethane prepolymer used in the third step may be the same as the conditions for synthesizing the urethane prepolymer used in the second step.

The hot-melt adhesive forming the first adhesive layer 4a and the hot-melt adhesive forming the third adhesive layer 4c are the catalysts exemplified in the hot-melt adhesive forming the second adhesive layer 4b, It may further contain a tackifying resin, other components, and the like.

The hot-melt adhesive forming the first adhesive layer 4a and the hot-melt adhesive forming the third adhesive layer 4c have a viscosity of 0.01 Pa·s or more at 120° C. from the viewpoint of coatability. , 0.05 Pa·s or more, or 0.1 Pa·s or more, and may be 35 Pa·s or less, 30 Pa·s or less, or 20 Pa·s or less.

The hot-melt adhesive forming the first adhesive layer 4a and the hot-melt adhesive forming the third adhesive layer 4c may be film-like. A film-like hot-melt adhesive can be formed, for example, by applying a hot-melt adhesive onto a support film such as a PET film. The thickness of the film hot melt adhesive may be 10 μm or more, 20 μm or more, or 30 μm or more, and may be 300 μm or less, 250 μm or less, or 200 μm or less.

The fourth step is to place the second fiber base material 2 on the third adhesive layer 4c, and form the first adhesive layer 4a, the second adhesive layer 4b, and the third adhesive layer 4c. It is a step of bonding the first fiber base material 1 and the second fiber base material 2 via the adhesive layer 4 made of.

The second fiber base material 2 may be the same as those exemplified for the first fiber base material 1 .

The first fiber base material 1 and the second fiber base material 2 are connected via the adhesive layer 4 consisting of the first adhesive layer 4a, the second adhesive layer 4b, and the third adhesive layer 4c. When bonding, the first fiber base material and the second fiber base material may be bonded while being crimped. As a method of pressure-bonding the first fiber base material and the second fiber base material, for example, a method of pressure-bonding using a pressure roll or the like can be mentioned.

The method for manufacturing a textile product includes moisture curing the adhesive layers 4 (the first adhesive layer 4a, the second adhesive layer 4b, and the third adhesive layer 4c) to obtain a cured hot melt adhesive. A step of forming a cured adhesive layer (a first cured adhesive layer, a second cured adhesive layer, and a third cured adhesive layer) may be further provided. Conditions for moisture curing of the adhesive layer 4 (the first adhesive layer 4a, the second adhesive layer 4b, and the third adhesive layer 4c) are a curing temperature of 20 to 80°C and a RH of 50 to 90%. can be appropriately adjusted so that the adhesive layer 4 is properly cured within the range of relative humidity of . The adhesive layer 4 can be cured, for example, by leaving (curing) for 24 to 120 hours at a temperature of 23° C. and 50% RH (relative humidity).

[Fiber products]
The textile product 3 is obtained by the manufacturing method described above. The textile product 3 comprises a first fiber base material 1, a first cured adhesive layer made of a cured hot-melt adhesive, and a second cured adhesive layer made of a cured hot-melt adhesive. , a third cured adhesive layer made of a cured hot-melt adhesive, and a second fiber base material 2 in this order.

[Adhesive set]
The adhesive set comprises a first moisture curable hot melt adhesive containing a first urethane prepolymer and a second moisture curable hot melt adhesive containing a second urethane prepolymer. In this adhesive set, the first urethane prepolymer contains an elastomer constitutional unit derived from an elastomer polyol, and the second urethane prepolymer satisfies either condition (e) or condition (f) below.

Condition (e): Contains no elastomer structural unit.
Condition (f): The content of elastomer constitutional units, based on the total amount of constitutional units containing elastomer constitutional units and derived from polyol in the second urethane prepolymer, is equal to the polyol in the first urethane prepolymer. It is less than the content of elastomer structural units based on the total amount of derived structural units.

The first urethane prepolymer is the same as the urethane prepolymer used in the second step, and the first moisture-curable hot-melt adhesive is the moisture-curable hot-melt adhesive used in the second step. It is the same. Therefore, redundant description is omitted here.

The second urethane prepolymer is the same as the urethane prepolymer used in the first step and the urethane prepolymer used in the third step, and the second moisture-curable hot melt adhesive is the same as the urethane prepolymer used in the first step. and the moisture-curable hot-melt adhesive used in the third step. Therefore, redundant description is omitted here.

The second urethane prepolymer may satisfy condition (e).

The elastomer may be a polybutadiene polyol or a hydrogenated polybutadiene polyol.

According to the adhesive set of this embodiment, it can be suitably used in the above-described method for manufacturing textile products.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples. However, the present invention is not limited to these examples.

(Production example 1)
<Preparation of first adhesive (first urethane prepolymer)>
100 parts by mass of hydrogenated polybutadiene polyol (manufactured by Nippon Soda Co., Ltd., trade name: GI-1000, number average molecular weight: 1500) as a polyol (elastomer) and diphenylmethane diisocyanate ( Manufactured by Tosoh Corporation, trade name: Millionate MT, number of isocyanate groups: 2) 13 parts by mass were added to a reaction vessel and mixed at 110°C for 1 hour until uniform. Then, 0.1 part by mass of dimorpholinodiethyl ether (manufactured by San-Apro Co., Ltd., trade name: UCAT-660M) as a catalyst is added, and the mixture is stirred at 110° C. for 1 hour for defoaming under reduced pressure. A urethane prepolymer No. 1 was obtained. The obtained first urethane prepolymer was used as it was as the first adhesive.

<Preparation of first adhesive film>
The first adhesive film of Production Example 1 was obtained by melting the first adhesive at 120° C., coating it on a PET film, and coating it to a thickness of 40 μm using a bar coater.

(Production example 2)
<Preparation of second adhesive (second urethane prepolymer)>
Amorphous polyester polyol (manufactured by Hitachi Chemical Co., Ltd., number of hydroxy groups: 2, number average Molecular weight: 2000) 100 parts by mass and 25 parts by mass of diphenylmethane diisocyanate (manufactured by Tosoh Corporation, trade name: Millionate MT, number of isocyanate groups: 2) as a polyisocyanate were added to a reaction vessel and heated at 110 ° C. for 1 hour until uniform. Mixed. Then, 0.1 part by mass of dimorpholinodiethyl ether (manufactured by San-Apro Co., Ltd., trade name: UCAT-660M) as a catalyst is added, and the mixture is stirred at 110° C. for 1 hour for defoaming under reduced pressure. No. 2 urethane prepolymer was obtained. The second urethane prepolymer does not contain elastomer structural units. The obtained second urethane prepolymer was used as it was as the second adhesive.

<Preparation of second adhesive film>
The second adhesive film of Production Example 2 was obtained by melting the second adhesive at 120° C., coating it on a PET film, and coating it to a thickness of 20 μm using a bar coater.

(Example 1)
<Production of textile products>
One sheet of the first adhesive film of Production Example 1 and two sheets of the second adhesive film of Production Example 2 were prepared. Each of these was cut into 10 mm width, and on a 10 mm width cloth (first fiber base material, manufactured by Toray Operontex Co., Ltd., product name: Lycra #5200), the second adhesion as the first adhesive layer An adhesive film, a first adhesive film as a second adhesive layer, and a second adhesive film as a third adhesive layer were laminated in this order. Next, on the third adhesive layer, a 10 mm wide fabric (second fiber base material, the same fabric as the first fiber base material) is placed and pressed at 120 ° C. to form a three-layer structure adhesive. A laminate having layers was obtained. The resulting laminate was allowed to stand for 1 day in an environment with a temperature of 23° C. and a humidity of 50% to cure the adhesive layer of the three-layer structure to obtain the textile product of Example 1.

<Measurement of adhesive strength>
The adhesive strength of the obtained textile product was measured using a tensile tester (EZ-Test EZ-SX, manufactured by Shimadzu Corporation) under the conditions of a measurement temperature of 25 ° C. and a tensile speed of 100 mm / min. Measured by test. Table 1 shows the results.

<Calculation of expansion recovery rate>
One sheet of the first adhesive film of Production Example 1 and two sheets of the second adhesive film of Production Example 2 were prepared. A PET film, a second adhesive film, a first adhesive film, a second adhesive film, and a PET film are laminated in this order, and pressed at 120° C. to form an adhesive layer having a three-layer structure. A laminate having The resulting laminate was allowed to stand for one day in an environment of 23° C. temperature and 50% humidity to cure the three-layered adhesive layer. The cured adhesive layer having a three-layer structure was punched into a size of 5 mm×50 mm, and the PET film was peeled off to obtain a test specimen. The test for calculating the stretch recovery rate was performed using a tensile tester (EZ-Test EZ-SX manufactured by Shimadzu Corporation) under the conditions of a measurement temperature of 25 ° C., a tensile speed of 100 mm / min, and a chuck distance of 30 mm. I went with The stretch recovery rate was calculated by the following method. The specimen was stretched to 100% at a tensile speed of 100 mm/min and then released from stress. The strain L1 when stretched to 100% and the strain L2 one minute after the stress was released were determined. The stretch recovery rate was calculated by substituting the obtained L1 and L2 into the following formula. Table 1 shows the results.
Stretch recovery rate (%) = (L1-L2) / L1 x 100

(Production example 3)
<Preparation of mixture of first adhesive (first urethane prepolymer) and second adhesive (second urethane prepolymer)>
50 parts by mass of the first urethane prepolymer of Production Example 1 and 50 parts by mass of the second urethane prepolymer of Production Example 2 were placed in a reaction vessel, and stirred under reduced pressure at 100° C. for 1 hour to produce the first urethane prepolymer. and a second urethane prepolymer were prepared.

<Preparation of mixture film>
The mixture film of Production Example 3 was obtained by melting the mixture at 120° C., coating it on a PET film, and coating it to a thickness of 80 μm using a bar coater.

(Comparative example 1)
<Production of textile products>
A laminate having a single-layer adhesive layer was obtained in the same manner as in Example 1, except that the mixture film of Production Example 3 was used as the adhesive layer. A textile product of Comparative Example 1 was obtained by curing the single-layer adhesive layer in the obtained laminate.

<Measurement of adhesive strength and calculation of stretch recovery rate>
Using the fiber product of Comparative Example 1, the adhesive strength was measured in the same manner as in Example 1. Table 1 shows the results. The stretch recovery rate of the mixture film of Production Example 3 was calculated in the same manner as in Example 1. Table 1 shows the results.

As shown in Table 1, the textile product of Example 1 bonded via a three-layer adhesive layer consisting of a first adhesive layer, a second adhesive layer, and a third adhesive layer Compared to the textile product of Comparative Example 1, which was adhered via a layered adhesive layer, the adhesive strength and stretch recovery rate were excellent. From these results, it was confirmed that the method for producing textile products of the present invention can produce textile products having excellent adhesiveness and stretchability.

DESCRIPTION OF SYMBOLS 1... 1st fiber base material, 2... 2nd fiber base material, 3... Textile product, 4... Adhesive layer, 4a... First adhesive layer, 4b... Second adhesive layer, 4c... Second 3 adhesive layers, 10... support.

Claims (8)

a first step of disposing a moisture-curable hot-melt adhesive containing a urethane prepolymer on a first fiber base material to form a first adhesive layer comprising the moisture-curable hot-melt adhesive;
a second step of disposing a moisture-curable hot-melt adhesive containing a urethane prepolymer on the first adhesive layer to form a second adhesive layer made of the moisture-curable hot-melt adhesive; ,
a third step of disposing a moisture-curable hot-melt adhesive containing a urethane prepolymer on the second adhesive layer to form a third adhesive layer made of the moisture-curable hot-melt adhesive; ,
A second fiber base material is placed on the third adhesive layer, and an adhesive layer composed of the first adhesive layer, the second adhesive layer, and the third adhesive layer is interposed therebetween. a fourth step of bonding the first fiber base material and the second fiber base material;
with
The urethane prepolymer used in the second step contains an elastomer constitutional unit derived from an elastomer polyol,
The urethane prepolymer used in the first step satisfies either the following condition (a) or the following condition (b),
The urethane prepolymer used in the third step satisfies either the following condition (c) or the following condition (d):
A method for manufacturing textile products.
Condition (a): does not contain the elastomer structural unit.
Condition (b): The content of the elastomer constitutional unit when based on the total amount of constitutional units derived from polyol in the urethane prepolymer used in the first step, which contains the elastomer constitutional unit, is equal to the second is less than the content of the elastomer structural units based on the total amount of polyol-derived structural units in the urethane prepolymer used in the step of .
Condition (c): does not contain the elastomer structural unit.
Condition (d): The content of the elastomer constitutional units, based on the total amount of polyol-derived constitutional units in the urethane prepolymer used in the third step, which contains the elastomer constitutional units, is equal to or exceeds the second is less than the content of the elastomer structural units based on the total amount of polyol-derived structural units in the urethane prepolymer used in the step of . The method for producing a textile product according to claim 1, wherein the urethane prepolymer used in the first step satisfies the condition (a). The method for producing a textile product according to claim 1 or 2, wherein the urethane prepolymer used in the third step satisfies the condition (c). The method for producing a textile product according to any one of claims 1 to 3, wherein the elastomer is polybutadiene polyol or hydrogenated polybutadiene polyol. a first fibrous base material;
a first cured adhesive layer made of a cured moisture-curable hot-melt adhesive containing a urethane prepolymer;
a second cured adhesive layer made of a cured moisture-curable hot-melt adhesive containing a urethane prepolymer;
a third cured adhesive layer made of a cured moisture-curable hot-melt adhesive containing a urethane prepolymer;
A second fiber base material is provided in this order,
the urethane prepolymer in the second adhesive cured product layer contains an elastomer constitutional unit derived from an elastomer polyol,
The urethane prepolymer in the first cured adhesive layer satisfies either the following condition (a) or the following condition (b),
The urethane prepolymer in the third adhesive cured product layer satisfies either the following condition (c) or the following condition (d):
Fiber products.
Condition (a): does not contain the elastomer structural unit.
Condition (b): The content of the elastomer constitutional units, based on the total amount of constitutional units derived from the polyol in the urethane prepolymer in the first adhesive cured product layer, including the elastomer constitutional units, is equal to the above It is less than the content of the elastomer structural units based on the total amount of polyol-derived structural units in the urethane prepolymer in the second adhesive cured product layer.
Condition (c): does not contain the elastomer structural unit.
Condition (d): The content of the elastomer constitutional units, based on the total amount of constitutional units derived from the polyol in the urethane prepolymer in the third adhesive cured product layer, including the elastomer constitutional units, is equal to the above It is less than the content of the elastomer structural units based on the total amount of polyol-derived structural units in the urethane prepolymer in the second adhesive cured product layer. An adhesive set comprising a first moisture-curable hot-melt adhesive containing a first urethane prepolymer and a second moisture-curable hot-melt adhesive containing a second urethane prepolymer,
wherein the first urethane prepolymer contains an elastomer constitutional unit derived from an elastomer polyol,
The second urethane prepolymer satisfies either the following condition (e) or the following condition (f):
glue set.
Condition (e): does not contain the elastomer structural unit.
Condition (f): The content of the elastomer constitutional units, based on the total amount of constitutional units derived from the polyol in the second urethane prepolymer, including the elastomer constitutional units, is equal to that of the first urethane prepolymer. It is less than the content of the elastomer constitutional units based on the total amount of constitutional units derived from the polyol therein. 7. The adhesive set according to claim 6, wherein said second urethane prepolymer satisfies said condition (e). 8. The adhesive set according to claim 6 or 7, wherein said elastomer is polybutadiene polyol or hydrogenated polybutadiene polyol.

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