JP6439965B2 - Adhesive composition - Google Patents

Description

  The present invention relates to a non-chlorine, one-sided coating adhesive and excellent blow-off resistance suitable for bonding an automobile interior, which is used when bonding a polyolefin molded article and a polyurethane foam-coated fabric, etc. About.

  Doors, instrument panels, ceiling materials, rear trays, pillars, and the like, which are automobile interior materials, are generally composed of molded products and skin materials. As the molded product, a polyolefin molded product is mainly used. On the other hand, as the skin material, a polyurethane foam, a fabric with a polyurethane foam, a polyolefin skin material, or the like is used. The molded product and the skin material are bonded together by a press bonding method, a vacuum forming method, or the like via an adhesive.

  Until now, adhesives based on chloroprene rubber have been the mainstream adhesive for use in automobile interiors. For example, Patent Document 1 discloses an adhesive composed of modified polychloroprene, a tackifier, and an organic solvent. Chloroprene rubber has higher heat resistance compared to other synthetic rubbers, and has a polyolefin adhesion aid such as chlorinated polyolefin, and other resins (phenol resin, petroleum resin, rosin resin, coumarone-indene resin, etc.) It has been widely used because of its high compatibility. However, since it is an adhesive containing chlorine, there is a concern about the influence on the environment, and an alternative is desired.

  As an alternative to a chlorine-based adhesive, a styrene rubber-based adhesive having a styrene block copolymer as a base polymer has been developed. For example, in Patent Document 2, a silane coupling agent is added to a styrene block copolymer. An automotive interior adhesive is disclosed. Furthermore, as an adhesive composition having adhesiveness required for this application (adhesive for automobile interior) by single-sided application, for example, Patent Document 3 discloses an adhesive using a styrene block copolymer and liquid rubber in combination. Has been.

Japanese Patent Laid-Open No. 5-140522 JP 2000-303047 A JP 2005-290339 A

  In conventional styrene rubber adhesives, polyolefin molded products (molded products) and polyurethane foamed fabrics (skin materials) are bonded by a press-bonding method (for example, single-sided coating in which adhesive is applied only to the molded product side). Then, the adhesive soaked excessively into the polyurethane foam, stress was applied to the polyurethane foam layer, and the foam layer was crushed, resulting in an appearance defect that caused the fabric surface to flutter (uneven). The irregular appearance of the irregularities can be seen by touching with the hand or by visual inspection. In addition, the schematic diagram which shows this generation | occurrence | production situation is shown in FIG. In order to suppress the occurrence of this fluttering, it is necessary to manage the upper limit of the coating amount, press-bonding force, etc., which is a limitation on the bonding work.

  On the other hand, an adhesive using a combination of styrene block copolymer and liquid rubber provides excellent adhesiveness when applied on one side, but because it penetrates well into polyurethane foam, it tends to flutter on the fabric surface. It was.

As a result of diligent research, the present inventor has found that an aromatic tackifying resin having a Z average molecular weight (Mz) of 5000 or more and an alicyclic ring, taking into consideration environmental effects using a non-chlorine styrene block copolymer as a base polymer. It has been found that an adhesive having excellent single-sided coating adhesiveness and fluff resistance can be obtained by using a tackifying resin. Details are as follows.
The present invention mainly comprises a composition obtained by adding a silane coupling agent capable of reacting with an acrylic monomer to a substance obtained by heating and stirring a styrene block copolymer having an unsaturated bond, an acrylic monomer, and a polymerization initiator. Further , 5 to 50 parts by mass of an aromatic tackifying resin having a Z average molecular weight (Mz) of 5000 or more and 40 to 100 parts by mass of an alicyclic tackifying resin with respect to 100 parts by mass of the styrene block copolymer. parts is an adhesive composition obtained by blending.
The alicyclic tackifying resin is an adhesive composition containing a terpene resin .
In a further, the aromatic-based tackifying resin is a styrene and / or adhesive composition comprising the α- methylstyrene as component.
In addition, the adhesive composition whose peeling length in a creep test (load 200g, 20 degreeC, 1 hour) is 10 mm or more as an initial stage adhesive force by the said structure is also the category of this invention.

According to the present invention, the above-described configuration can provide excellent fluff resistance by reducing the adhesive force (initial adhesive force) immediately after bonding within an allowable range. As the initial adhesive force, for example, the peel length is 10 mm or more in a creep test (load 200 g, 20 ° C., 1 hour). Moreover, the adhesive fall after curing by making initial adhesive force small is supplemented by using aromatic tackifying resin with Z average molecular weight (Mz) 5000 or more.
That is, the adhesive composition of the present invention is non-chlorine based in consideration of environmental problems, exhibits excellent adhesion to polyurethane foams, and also has excellent blow resistance, so it can be used for automobiles. It can be suitably used as an adhesive for interior materials.

It is a schematic diagram which shows the state of occurrence of fluttering due to adhesion between a molded product and a skin material.

  The styrene block copolymer having an unsaturated bond in the adhesive of the present invention is a styrene / isoprene / styrene block copolymer, a styrene / butadiene / styrene block copolymer, or the like. These styrene block copolymers can be made high molecular weight by crosslinking and / or polymerizing with a polymerization initiator. The physical properties and properties of the styrene block copolymer are not particularly limited because they vary depending on the intended physical properties, but those having MI (melt index, 200 ° C., 5 kg load) of 15 or less are preferable.

  The acrylic monomer in the present invention can be appropriately employed as long as it has an organic group capable of reacting with a silane coupling agent. Specifically, acrylic acid monomers such as glycidyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, methacrylic acid monomers such as glycidyl methacrylate, 2-ethylhexyl methacrylate, 2-hydroxypropyl methacrylate, etc. And at least 1 sort (s) chosen from these groups can be used. In addition, an acrylic monomer having no organic group capable of reacting with a silane coupling agent, such as vinyl acetate, acrylonitrile, styrene, butadiene, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, etc. It can also be added.

Examples of the polymerization initiator in the present invention include benzoyl peroxide, bis (2,4-dichlorobenzoyl) peroxide, di-t-butyl peroxide, 2,5-dimethylperoxyhexane, and t-butyl perbenzoate. Polymerization initiators comprising organic peroxides such as t-butylperoxyisopropyl carbonate, inorganic peroxides such as hydrogen peroxide, persulfates such as ammonium sulfate, diazo compounds such as azobisisobutyronitrile, etc. can do.
The amount of the polymerization initiator used is usually 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, with respect to 100 parts by mass of the styrene block copolymer. The heating temperature and the heating time vary depending on the initiator used and the like. For example, the reaction may be carried out in an organic solvent such as toluene at 70 to 110 ° C. for 1 to 24 hours under nitrogen substitution.

  The silane coupling agent capable of reacting with the acrylic monomer in the present invention has a functional group reactive with the acrylic monomer of the substance obtained by heating and stirring the styrene block copolymer, the acrylic monomer, and the polymerization initiator. For example, when the acrylic monomer is glycidyl acrylate, isocyanate silane, aminosilane and the like can be mentioned. Moreover, when an acrylic monomer is 2-hydroxyethyl acrylate, isocyanate silane etc. are mentioned. Specifically, epoxy silane such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, 3,4-epoxycyclohexylethyltrimethoxysilane, aminomethyltriethoxysilane, aminomethyldimethoxysilane , Γ-aminopropyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-ureidopropyltriethoxysilane and other aminosilanes, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyl Mercaptosilanes such as diethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropyldimethylmethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ- Socia sulfonates trimethoxysilane, .gamma. isocyanatopropyl a isocyanate silane such as triethoxysilane, it can be used at least one selected from these groups. One or two or more combinations of these acrylic monomers and silane coupling agents can be selected and used in accordance with various physical properties such as a desired curing rate.

Here, by heating and stirring the styrene block copolymer, the acrylic monomer, and the polymerization initiator, the styrene block copolymer can have a high molecular weight to ensure adhesive properties.
Furthermore, it is speculated that by adding a silane coupling agent capable of reacting with an acrylic monomer, a unique effect is obtained, and adhesiveness after curing is developed, but it is not clear at this stage.

  The acrylic monomer to be heated and stirred with the styrene block copolymer and the polymerization initiator preferably has a styrene block copolymer / acryl monomer mass ratio of 100/1 to 100/100, that is, less than 100/1, When the amount of the acrylic monomer relative to the amount of the styrene block copolymer is small, sufficient heat resistance cannot be obtained even if a large amount of the silane coupling agent is used. On the other hand, when it is more than 100/100, that is, when the amount of the acrylic monomer is large, the crosslinking density becomes too high and the stress relaxation property of the adhesive is deteriorated, so that the adhesiveness particularly at a low temperature is lowered.

  The silane coupling agent reactive with the acrylic monomer of the substance obtained by heating and stirring the styrene block copolymer, the acrylic monomer, and the polymerization initiator is a mass ratio of styrene block copolymer / silane coupling agent. Is preferably 100 / 0.1 to 100/50, and when it is less than 100 / 0.1 (when the amount of silane coupling agent relative to the amount of styrene block copolymer is small), sufficient heat resistance cannot be obtained. . On the other hand, when the ratio is more than 100/50, the crosslinking density becomes too high, the stress relaxation property of the adhesive is deteriorated, and the adhesiveness particularly at a low temperature is lowered.

Examples of the aromatic tackifying resin having a Z average molecular weight (Mz) of 5000 or more in the present invention include styrene and / or α-methylstyrene resin, aromatic petroleum resin, coumarone-indene resin and the like. In view of the effect of improving heat-resistant adhesion by reinforcing the styrene block of the polymer, it is particularly desirable to use styrene and / or α-methylstyrene resin. Moreover, from the same styrene block reinforcement effect, Z average molecular weight (Mz) is 5000 or more, More preferably, it is 10,000 or more. In addition, although the upper limit of Z average molecular weight (Mz) is not specifically limited, Preferably it is 50000 or less, More preferably, it is 30000 or less. In addition, Z average molecular weight (Mz) in this invention is a value determined by polystyrene conversion by gel permeation chromatography (GPC). For the measurement of gel permeation chromatography (GPC), a packed column for HPLC “GL-A160-S”, “GL-A150-S”, “GL” manufactured by Hitachi Chemical Co., Ltd. at a flow rate of 1.0 ml / min using tetrahydrofuran as a solvent. -A130-S "was connected and a differential refractometer was used as the detector.
As described above, the aromatic tackifying resin in the present invention is preferably styrene and / or α-methylstyrene resin. Specifically, trade names “Kristalex 1120”, “Kristalex 5140”, “Plastolyn 290” and the like manufactured by Eastman Chemical Co., Ltd. can be mentioned. In addition, these resins can use 2 or more types together.

Examples of the alicyclic tackifying resin in the present invention include terpene resins, terpene phenol resins, alicyclic hydrocarbon resins, etc. In order to obtain the adhesive strength necessary for single-side coating adhesion, terpene resins, particularly terpenes are used. The use of phenolic resin is desirable.
Commercially available products of alicyclic tackifying resins include “YS Resin PX1250”, “YS Resin PX1150”, “YS Resin PX1000”, “YS Resin PX800”, “YS Polystar U130”, “YS” manufactured by Yasuhara Chemical Co., Ltd. Polystar U115 ", trade name" Regalite R1100 "manufactured by Eastman Chemical Co., trade name" Regalite R1125 ", etc. can be used. In addition, these resins can use 2 or more types together.

  The aromatic tackifying resin having a Z average molecular weight (Mz) of 5000 or more has a mass ratio of the styrene block copolymer / the aromatic tackifying resin having a Z average molecular weight (Mz) of 5000 or more from 100/5 to 100 /. 50 is preferable, and 100/15 to 100/40 is more preferable. When it is less than 100/5, sufficient heat resistance cannot be obtained. Moreover, when more than 100/50, adhesiveness falls and single-sided coating adhesiveness falls.

  The alicyclic tackifying resin preferably has a styrene block copolymer / alicyclic tackifying resin mass ratio of 100/40 to 100/100, more preferably 100/60 to 100/80. is there. When the amount is less than 100/40, that is, when the blending amount of the alicyclic tackifying resin with respect to the styrene block copolymer is low, the tackiness is lowered and the single-sided coating adhesiveness is lowered. On the other hand, when the amount is more than 100/100, that is, when the blending amount of the alicyclic tackifying resin with respect to the styrene block copolymer is high, the tackiness becomes excessively high and the blistering resistance is lowered.

The measurement method of the creep test (load 200 g, 20 ° C., 1 hour) of the initial adhesive force of the present invention is as follows.
Using a spray gun, the adhesive was applied onto the polyolefin molded article (wet coating amount: 150 g / m ² ) and dried in a drying oven set at 60 ° C. for 2 minutes. Thereafter, the polyolefin molded article with adhesive and the fabric with polyurethane foam, which was allowed to stand in a 20 ° C. atmosphere for 1 minute, were bonded by a press-bonding method (0.1 MPa, 10 seconds).
Within 3 minutes after bonding, a load of 200 g / 25 mm in the vertical direction was applied to one end of the fabric with a polyurethane foam in an atmosphere at 20 ° C., a 1 hour creep test was performed, and the peel length was measured. By this evaluation, the penetration into the polyurethane foam can be easily evaluated, and a good correlation with the occurrence of fluttering can be obtained. In addition, in the said evaluation conditions, it turned out that fluttering can be suppressed by becoming peeling thickness 10 mm or more.

  In addition, examples of the tackifying resin include petroleum resins, rosin resins, epoxy resins, phenol resins, xylene resins, acrylic resins, butyral resins, olefin resins, chlorinated olefin resins, vinyl acetate resins, and modified products thereof. One or more types can be selected from resins and the like, and an appropriate amount can be blended within the range of achieving the task. Moreover, you may mix | blend a reaction terminator, antioxidant, a stabilizer, a coloring agent, a solvent, a catalyst, a filler etc. as needed.

  Next, although an Example and a comparative example demonstrate this invention further in detail and the result of these specific examples is shown in Table 1, this invention is not limited by these examples. In the text, “part” means all parts by mass.

[Example 1]
In a nitrogen-substituted flask, 100 parts of a styrene / butadiene / styrene block copolymer “Clayton D-1102JSZ” (manufactured by Kraton Polymer Japan) and 10 parts of glycidyl methacrylate “Acryester G” (manufactured by Mitsubishi Rayon Co., Ltd.) After putting in 300 parts of toluene and dissolving by heating and stirring at 80 ± 2 ° C., a solution of 0.5 part of benzoyl peroxide as a polymerization initiator was added dropwise and stirring was performed. The flask was heated and stirred for 3 hours while maintaining the temperature at 80 ± 2 ° C., and 0.5 part of hydroquinone was added as a stopper to stop the reaction. Thereafter, it is allowed to cool to about 40 ° C., and 30 parts of an aromatic tackifying resin “Plastolyn 290” (manufactured by Eastman Chemical Co., Ltd., Z average molecular weight (Mz) 8340), terpene phenol resin “YS Polystar U130” (manufactured by Yasuhara Chemical Co., Ltd.) ) 70 parts, 350 parts of cyclohexane, 100 parts of methyl ethyl ketone, 20 parts of aminopropyltrimethoxysilane “KBM-903” (manufactured by Shin-Etsu Chemical Co., Ltd.) were added and mixed with stirring for about 3 hours to obtain adhesive (I).

[Example 2]
In a nitrogen-substituted flask, 100 parts of a styrene / butadiene / styrene block copolymer “Clayton D-1102JSZ” (manufactured by Kraton Polymer Japan) and 10 parts of glycidyl methacrylate “Acryester G” (manufactured by Mitsubishi Rayon Co., Ltd.) After putting in 300 parts of toluene and dissolving by heating and stirring at 80 ± 2 ° C., a solution of 0.5 part of benzoyl peroxide as a polymerization initiator was added dropwise and stirring was performed. The flask was heated and stirred for 3 hours while maintaining the temperature at 80 ± 2 ° C., and 0.5 part of hydroquinone was added as a stopper to stop the reaction. Thereafter, the mixture is allowed to cool to about 40 ° C., and 30 parts of an aromatic tackifying resin “Kristalex 5140” (manufactured by Eastman Chemical Co., Ltd., Z average molecular weight (Mz) 12900), terpene phenol resin “YS Polystar U130” (manufactured by Yasuhara Chemical Co., Ltd.) 70 parts, 350 parts of cyclohexane, 100 parts of methyl ethyl ketone, 20 parts of aminopropyltrimethoxysilane “KBM-903” (manufactured by Shin-Etsu Chemical Co., Ltd.) were added and stirred for about 3 hours to obtain an adhesive (II).
The difference from Example 1 is that the aromatic tackifying resin is changed from “Plastolyn 290” (Z average molecular weight (Mz) 8340) to “Kristalex 5140” (Z average molecular weight (Mz) 12900).

Example 3
In a nitrogen-substituted flask, 100 parts of a styrene / butadiene / styrene block copolymer “Clayton D-1102JSZ” (manufactured by Kraton Polymer Japan) and 10 parts of glycidyl methacrylate “Acryester G” (manufactured by Mitsubishi Rayon Co., Ltd.) After putting in 300 parts of toluene and dissolving by heating and stirring at 80 ± 2 ° C., a solution of 0.5 part of benzoyl peroxide as a polymerization initiator was added dropwise and stirring was performed. The flask was heated and stirred for 3 hours while maintaining the temperature at 80 ± 2 ° C., and 0.5 part of hydroquinone was added as a stopper to stop the reaction. Thereafter, the mixture is allowed to cool to about 40 ° C., and 30 parts of an aromatic tackifying resin “Kristalex 5140” (manufactured by Eastman Chemical Co., Ltd., Z average molecular weight (Mz) 12900), terpene phenol resin “YS Polystar U130” (manufactured by Yasuhara Chemical Co., Ltd.) ) 40 parts, 30 parts of alicyclic hydrocarbon resin “Regalite R1125” (manufactured by Eastman Chemical), 350 parts of cyclohexane, 100 parts of methyl ethyl ketone, 20 parts of aminopropyltrimethoxysilane “KBM-903” (manufactured by Shin-Etsu Chemical Co., Ltd.) Was added and stirred for about 3 hours to obtain an adhesive (III).
70 parts of the terpene phenol resin “YS Polystar U130” in Example 2 is changed to 40 parts of the terpene phenol resin “YS Polystar U130” and 30 parts of the alicyclic hydrocarbon resin “Regalite R1125”.

[Comparative Example 1]
In a nitrogen-substituted flask, 100 parts of a styrene / butadiene / styrene block copolymer “Clayton D-1102JSZ” (manufactured by Kraton Polymer Japan) and 10 parts of glycidyl methacrylate “Acryester G” (manufactured by Mitsubishi Rayon Co., Ltd.) After putting in 300 parts of toluene and dissolving by heating and stirring at 80 ± 2 ° C., a solution of 0.5 part of benzoyl peroxide as a polymerization initiator was added dropwise and stirring was performed. The flask was heated and stirred for 3 hours while maintaining the temperature at 80 ± 2 ° C., and 0.5 part of hydroquinone was added as a stopper to stop the reaction. Thereafter, the mixture was allowed to cool to about 40 ° C., and 30 parts of an aromatic tackifying resin “YS Resin SX-100” (manufactured by Yasuhara Chemical Co., Ltd., Z average molecular weight (Mz) 4060), terpene phenol resin “YS Polystar U130” (Yasuhara Chemical) 70 parts), cyclohexane 350 parts, methyl ethyl ketone 100 parts, aminopropyltrimethoxysilane "KBM-903" (manufactured by Shin-Etsu Chemical Co., Ltd.) 20 parts, and mixed by stirring for about 3 hours to obtain adhesive (IV) It was.
The aromatic tackifying resin of Example 1 is changed from “Plastolyn 290” (Z average molecular weight (Mz) 8340) to “YS Resin SX-100” (Z average molecular weight (Mz) 4060).

[Comparative Example 2]
In a nitrogen-substituted flask, 100 parts of a styrene / butadiene / styrene block copolymer “Clayton D-1102JSZ” (manufactured by Kraton Polymer Japan) and 10 parts of glycidyl methacrylate “Acryester G” (manufactured by Mitsubishi Rayon Co., Ltd.) After putting in 300 parts of toluene and dissolving by heating and stirring at 80 ± 2 ° C., a solution of 0.5 part of benzoyl peroxide as a polymerization initiator was added dropwise and stirring was performed. The flask was heated and stirred for 3 hours while maintaining the temperature at 80 ± 2 ° C., and 0.5 part of hydroquinone was added as a stopper to stop the reaction. Thereafter, the mixture is allowed to cool to about 40 ° C., and 30 parts of an aromatic tackifying resin “Kristalex 5140” (manufactured by Eastman Chemical Co., Ltd., Z average molecular weight (Mz) 12900), terpene phenol resin “YS Polystar U130” (manufactured by Yasuhara Chemical Co., Ltd.) ) 110 parts, 350 parts of cyclohexane, 100 parts of methyl ethyl ketone, 20 parts of aminopropyltrimethoxysilane “KBM-903” (manufactured by Shin-Etsu Chemical Co., Ltd.) were added and stirred for about 3 hours to obtain an adhesive (V).
The amount of terpene phenol resin “YS Polystar U130” used in Example 2 was changed from 70 parts to 110 parts.

[Comparative Example 3]
In a nitrogen-substituted flask, 100 parts of a styrene / butadiene / styrene block copolymer “Clayton D-1102JSZ” (manufactured by Kraton Polymer Japan) and 10 parts of glycidyl methacrylate “Acryester G” (manufactured by Mitsubishi Rayon Co., Ltd.) After putting in 300 parts of toluene and dissolving by heating and stirring at 80 ± 2 ° C., a solution of 0.5 part of benzoyl peroxide as a polymerization initiator was added dropwise and stirring was performed. The flask was heated and stirred for 3 hours while maintaining the temperature at 80 ± 2 ° C., and 0.5 part of hydroquinone was added as a stopper to stop the reaction. Thereafter, the mixture is allowed to cool to about 40 ° C., and 30 parts of an aromatic tackifying resin “Kristalex 5140” (manufactured by Eastman Chemical Co., Ltd., Z average molecular weight (Mz) 12900), terpene phenol resin “YS Polystar U130” (manufactured by Yasuhara Chemical Co., Ltd.) 30 parts, 350 parts of cyclohexane, 100 parts of methyl ethyl ketone, 20 parts of aminopropyltrimethoxysilane “KBM-903” (manufactured by Shin-Etsu Chemical Co., Ltd.) were added and stirred for about 3 hours to obtain an adhesive (VI).
The amount of terpene phenol resin “YS Polystar U130” used in Example 2 was changed from 70 parts to 30 parts.

  Using the adhesives obtained in Examples 1 to 3 and Comparative Examples 1 to 3, test pieces were prepared as follows, and initial creep measurement, flapping evaluation, peel adhesion strength measurement, and heat resistant creep measurement were performed. .

(1) Test piece preparation method Using a spray gun, the adhesive was applied onto a polyolefin molded article (wet coating amount: 150 g / m ² ) and dried in a drying oven set at 60 ° C. for 2 minutes. After drying, the polyolefin molded article left for 1 minute in an atmosphere of 20 ° C. and the fabric with polyurethane foam were bonded by a press-bonding method (0.1 MPa, 10 seconds).

(2) Initial creep measurement Within 3 minutes after bonding the polyolefin molded article and the fabric with polyurethane foam, a vertical load of 100 and 200 g / 25 mm was applied to one end of the fabric with polyurethane foam in an atmosphere at 20 ° C. for 1 hour. The creep test was conducted and the peel length was measured.

(3) Abata Evaluation The appearance after 5 minutes of adhesion between the polyolefin molded article and the polyurethane foam-attached fabric was observed to confirm the presence or absence of the abutment.

(4) Measurement of peel adhesion strength Adhesive product of polyolefin molded product and fabric with polyurethane foam was cured in 20 ° C, 65% RH atmosphere for 24 hours, and 180 ° peel strength by a tensile tester in 23 ° C atmosphere The thickness was measured (tensile speed: 200 mm / min).

(5) Heat-resistant creep measurement An adhesive product of a polyolefin molded product and a polyurethane foam fabric is cured for 24 hours in an atmosphere of 20 ° C. and 65% RH, and 100 g / vertical direction at one end of the polyurethane foam fabric in an 80 ° C. atmosphere. A 24 mm creep test was performed under a load of 25 mm, and the peel length was measured.
When (2) initial creep, (4) peel adhesion strength, and (5) heat-resistant creep were evaluated as “A” when the fracture state was “interface fracture from the polyurethane foam side”, “polyurethane foam material failure "B".
In addition, (3) “A” was given in the case of “No Abata” in the evaluation, and “X” was given in the case of “With Abata”.

In the samples of Examples 1 to 3, good results were obtained in the resistance to blow and adhesion.
In Comparative Example 1 (the Z average molecular weight (Mz) of the aromatic resin is less than 5000), the initial creep was good, but the heat resistant creep was lowered. On the other hand, in Comparative Example 2 (the amount of the alicyclic tackifying resin exceeds 100 parts by mass), both initial creep and heat-resistant creep are good. However, as shown in the schematic diagram of FIG. Appearance defect) has occurred. Further, in Comparative Example 3 in which the amount of the alicyclic tackifying resin is less than 40 parts by mass, no fluttering is observed, but the heat resistant creep is lowered.

1: Fabric 2: Polyurethane foam 3: Adhesive 4: Polyolefin molded product

Claims (4)

The main component is a composition obtained by adding a silane coupling agent capable of reacting with an acrylic monomer to a substance obtained by heating and stirring a styrene block copolymer having an unsaturated bond, an acrylic monomer, and a polymerization initiator. Adhesion of 5 to 50 parts by mass of an aromatic tackifying resin having a Z average molecular weight (Mz) of 5000 or more and 40 to 100 parts by mass of an alicyclic tackifying resin with respect to 100 parts by mass of the styrene block copolymer. Agent composition.   The adhesive composition according to claim 1, wherein the alicyclic tackifying resin contains a terpene resin. The adhesive composition according to claim 1 or 2 , wherein the aromatic tackifying resin comprises styrene and / or α-methylstyrene as a component. The adhesive composition according to any one of claims 1 to 3 , wherein, as an initial adhesive force, a peel length in a creep test (load 200 g, 20 ° C, 1 hour) is 10 mm or more.

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