JP2002173654A - Hot-melt adhesive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hot-melt adhesive composition exhibiting excellent adhesion of a metal to the same or different metal, and excellent water-resistant adhesive properties of the metal to a glass and of the glasses to each other. SOLUTION: This hot-melt adhesive composition is characterized in that the composition comprises (a) 10-90 wt.% styrenic thermoplastic elastomer, (b) 5-70 wt.% saponification product of an ethylene-vinyl acetate copolymer, (c) 5-70 wt.% copolymer of ethylene and acrylic acids, and (d) 0-50 wt.% polyethylene. The adhesive film comprising the hot-melt adhesive composition has no stickiness on the surface and can be easily treated. The metal foil obtained by laminating the hot-melt adhesive composition can adhere to the surface or the like of a glass, and can have water resistance superior to that of the conventional one.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hot-melt adhesive composition having excellent water resistance in bonding between same or different metals, bonding between metals and glass, and bonding between glasses.

[0002]

2. Description of the Related Art A hot-melt adhesive is an adhesive made of a thermoplastic resin that melts when heated, is applied to the surface of an adherend, and then cools to exhibit an adhesive function between the adherends. Excellent workability and economy. Common hot-melt adhesive application methods include applying the molten adhesive by applying pressure by a pump and discharging from a nozzle, applying the molten adhesive with a roll coater, and bonding in a film shape. A method in which an agent is sandwiched between the adhesive surfaces of the adherends and heated is used.

[0003] The adherends to be bonded are metal, resin, rubber,
There are a wide variety of paper and wood. The environment in which the bonded products are used ranges from a mild indoor environment to a high-temperature, high-humidity outdoor environment. In recent years, improvement in water resistance has been particularly demanded along with expansion of the application range of hot melt adhesives.

As a method for improving the water resistance of a hot melt adhesive in bonding inorganic materials such as glass and metal, a method of applying a silane coupling agent to the surface of an adherend, a method of grafting a silane coupling agent to an adhesive resin, and the like. Methods of denaturation or addition and mixing are known. However, the method of improving the water resistance by applying the adhesive after applying the silane coupling agent to the surface of the adherend is very complicated. On the other hand, hot melt adhesives in which a silane coupling agent has been graft-modified or added and mixed have poor storage stability, and have many problems particularly in storage and handling in a film state.

[0005]

In bonding metal to glass, glass to glass, and metal to glass, ethylene / vinyl acetate copolymer, saponified ethylene / vinyl acetate copolymer, maleic anhydride graft copolymer of polyethylene, etc. Is known to be a good hot melt adhesive,
The water resistance is very poor and the application range is very limited. An object of the present invention is to improve water resistance in hot-melt bonding between metals, between glasses, and between metal and glass.

[0006]

Means for Solving the Problems The present inventors have searched for various resin compositions and found that component (a) is 10 to 90% by weight,
Component: 5 to 70% by weight, component (c): 5 to 70% by weight,
It has been found that excellent water resistance can be obtained by using a specific composition composed of component (d): 0 to 50% by weight, and the present invention has been completed.

Hereinafter, the present invention will be described in more detail.
(A) used in the present invention has an intrinsic viscosity [η] of 1
It is not particularly limited as long as it is the above, carboxyl-modified styrene-based thermoplastic elastomer,
Examples include a block copolymer of a styrene-based compound and a conjugated diene compound, a hydrogenated product of a block copolymer of a styrene-based compound and a conjugated diene compound, and an epoxidized styrene-butadiene copolymer. As a monomer for producing a styrene-based block polymer, not only styrene but also α-methylstyrene and the like are used.

The block copolymer of a styrene compound and a conjugated diene compound includes styrene-butadiene block copolymer, styrene-butadiene-styrene block copolymer (hereinafter abbreviated as SBS), and styrene-isoprene block copolymer. Styrene-isoprene-styrene block copolymer (hereinafter abbreviated as SIS), styrene-butadiene-isoprene block copolymer, styrene-butadiene-isoprene-styrene block copolymer, and the like. Examples of the epoxidized styrene-butadiene copolymer include an epoxidized styrene-butadiene copolymer and an epoxidized styrene-butadiene-styrene copolymer (hereinafter abbreviated as epoxidized SBS). Examples of the hydrogenated product of the block copolymer of a styrene-based compound and a conjugated diene compound include a hydrogenated product of a styrene-butadiene-styrene block copolymer (hereinafter abbreviated as SEBS).
And hydrogenated styrene-isoprene-styrene block copolymers (hereinafter abbreviated as SEPS). Among these styrene-based thermoplastic elastomers, a hydrogenated product of a block copolymer of a styrene-based compound and a conjugated diene compound or an epoxidized styrene-butadiene copolymer is preferably used.

[0009] As a specific example of (a), for example, as SIS, Kariflex TR-110 manufactured by Shell Chemical Co., Ltd.
7, TR-1111, TR-1112, TR-111
7, JSR SIS 5000, SIS 5002,
SIS 5505 and the like. As SBS, Kariflex TR-1101 and TR-1 manufactured by Shell Chemical Co., Ltd.
102, KRATO manufactured by Clayton Polymer Japan
ND-1101, D-1155, D-KX405 and the like. As SEBS and SEPS, Asahi Kasei Corporation's Tuftec H1062, H1052, H1041, H
1272, KRAT manufactured by Clayton Polymer Japan
ON G-1650, G-1652, G-1720 and the like. Examples of the epoxidized SBS include Epofriend A-1005 manufactured by Daicel Chemical Industries, Ltd.

As (b) used in the present invention, a commercially available ethylene-vinyl acetate copolymer saponified by a known method is preferably used, and among these, a vinyl acetate content of 10 to 10 is preferably used. Preferably, 50% by weight of a vinyl acetate copolymer is saponified.
85% is preferable, and 40-80% is a more preferable range. The melt flow rate (hereinafter abbreviated as MFR) of the saponified ethylene / vinyl acetate copolymer (hereinafter abbreviated as EVOH) is not particularly limited.
00 g / 10 min (190 ° C.), preferably 0.1 to 100
g / 10 minutes (190 ° C.) is a more preferable range.

As a specific example of (b) used in the present invention, for example, Technolink DR-55 manufactured by Taoka Chemical Co., Ltd.
R-100, K-431, Tosoh Mersen H-
6051, H-6820, H-6822X, Dumilan D-219, C-2280 manufactured by Takeda Pharmaceutical Co., Ltd., and the like.

(C) used in the present invention is a generally commercially available ethylene / methacrylic acid copolymer (hereinafter referred to as EM).
AA), ethylene / acrylic acid copolymer and the like are preferably used. The content of the acrylic acid (c) is not particularly limited, but is preferably 5 to 25% by weight. When the content of the acrylic acid (c) is 5% by weight or less, the adhesive strength is reduced. On the other hand, when the content is 25% by weight or more, the melting point of the resin is lowered and the heat resistance of the hot melt adhesive is lowered.
Although the MFR of (c) is not particularly limited, it is 0.1 to 500 g.
/ 10 min (190 ° C.), preferably 0.1 to 100 g / 1
0 minutes (190 ° C.) is a more preferred range.

Specific examples of (c) used in the present invention include, for example, Nuclel AN4214C, N1035, N1214, N1 manufactured by DuPont-Mitsui Polychemicals.
525, TR5000, TR5100 manufactured by Exxon
And the like.

As the (d) used as required in the present invention, a commercially available high-density or low-density polyethylene is preferably used, and the MFR of the high-density or low-density polyethylene is 0.1 to 200 g / 10 min. (190 ° C.) is a preferable range.

Specific examples of (d) used in the present invention as necessary include, for example, Exelen VL, Sumikasen-L, Sumikasen E, Sumitomo Chemical Co., Ltd., and Petrocene, manufactured by Tosoh Corporation.

The mixing ratio of (a), (b), (c) and (d) used in the hot melt adhesive composition of the present invention is as follows:
(A) component: 10 to 90% by weight, (b) component: 5 to 70%
% By weight, component (c): 5 to 70% by weight, component (d): 0
５０50% by weight. The preferred range of the mixing ratio is as follows: component (a): 15 to 70% by weight, component (b): 15
-60% by weight, component (c): 15-60% by weight, (d)
Ingredients: range from 0 to 40% by weight.

In the case of (b) and (c) used in the present invention, even if any of the components are missing, the adhesive strength and the water resistance under normal conditions are remarkably reduced. By mixing the required amount of (a), the adhesive strength and water resistance under normal conditions can be improved. When (d) is added as required, the film-forming property is improved, but when the amount is too large, the adhesive strength is lowered.

The hot melt adhesive composition of the present invention comprises
If necessary, other thermoplastic resin, rubber, adhesive, plasticizer,
Filler, lubricant, anti-blocking agent, antioxidant,
Etc. can be appropriately compounded.

The hot melt adhesive composition of the present invention is melt-kneaded by a known method using a roll, a Banbury mixer, a twin-screw kneader, a single-screw extruder, a twin-screw extruder, a kneader, or the like. Manufactured.

The adhesive film comprising the hot melt adhesive composition of the present invention can be easily produced by a known T-die processing or inflation processing. Since the adhesive film of the present invention has no tackiness on the surface, it is easy to handle.

The metal foil to which the hot-melt adhesive composition of the present invention is bonded is manufactured by laminating the hot-melt adhesive composition of the present invention on a metal foil using a hot roll or a urethane-based adhesive. can do. When the metal foil to which the hot melt adhesive composition of the present invention is bonded is adhered to a glass surface or the like, it is possible to have better water resistance than before.

[0022]

The present invention will be described below with reference to examples. Examples 1 to 4 EMAA, EVOH, SEBS at the ratios shown in Table 1,
The mixture was melt-kneaded using a twin-screw kneader to obtain a hot melt adhesive composition. These adhesive compositions were formed into a film having a thickness of about 300 μm at a temperature of 190 ° C. using a press forming machine. Using the obtained adhesive film, a 25 mm wide, 150 mm long, 0.3 mm thick aluminum test piece (manufactured by Nippon Test Panel Osaka) and a 25 mm wide, 100 mm long, 3 mm thick tempered glass test piece ( Nippon Test Panel Osaka Co., Ltd.) were bonded under the conditions of a pressing pressure of 0.03 MPa, a temperature of 190 ° C., and a time of 15 minutes. Normal 180 ° peel strength (pulling speed 50 mm / min, 25 ° C.) [hereinafter referred to as “normal peel strength”] of the adhesive test specimen, and 180 ° peel strength in a wet normal state after immersion in 25 ° C. water [hereinafter immersed in 25 ° C. water] Strength and abbreviation] were measured and are shown in Table 1. The strength retention (%) is obtained by dividing the immersion strength in water at 25 ° C by the normal peel strength and multiplying by 100.
And described in Table 1. Example 5 A hot melt adhesive composition was obtained by melt-kneading EMAA, EVOH and SIS at the ratios shown in Table 1 using a twin-screw kneader. These adhesive compositions were formed into a film and bonded in the same manner as in Examples 1 to 4, to obtain a normal peel strength and 25%.
The immersion strength in water at ℃ was measured, and the strength retention (%) was calculated from the results. Example 6 A hot-melt adhesive composition was obtained by melt-kneading EMAA, EVOH, and epoxidized SBS at the ratios shown in Table 2 using a twin-screw kneader. These adhesive compositions were prepared in Example 1
Film forming and bonding were performed in the same manner as in Nos. To 4, and the normal peel strength and the immersion strength in water at 25 ° C. were measured. The strength retention (%) was calculated from the results, and is shown in Table 1. Examples 7 and 8 EMAA, EVOH, SEBS, and PE were melt-kneaded at the ratios shown in Table 2 using a twin-screw kneader to obtain a hot melt adhesive composition. These adhesive compositions were prepared in Examples 1 to
The film was formed and bonded in the same manner as in Example 4, and the normal peel strength and the immersion strength in water at 25 ° C. were measured. The strength retention (%) was calculated from the results. Comparative Example 1 Only EMAA was formed into a film having a thickness of about 300 μm at a temperature of 190 ° C. using a press forming machine. Using this adhesive film, adhesion was carried out in the same manner as in Examples 1 to 4, and the normal peel strength and the immersion strength in water at 25 ° C. were measured. The strength retention (%) was calculated from the results, and is shown in Table 2. Comparative Example 2 Only EVOH was formed into a film having a thickness of about 300 μm at a temperature of 190 ° C. using a press forming machine. Using this adhesive film, adhesion was carried out in the same manner as in Examples 1 to 4, and the normal peel strength and the immersion strength in water at 25 ° C. were measured. The strength retention (%) was calculated from the results, and is shown in Table 2. Comparative Example 3 A hot melt adhesive composition was obtained by melt-kneading polyamide (hereinafter abbreviated as PA), EVOH, and SEBS at the ratios shown in Table 2 using a twin-screw kneader. These adhesive compositions were prepared using a press molding machine at a temperature of 190 ° C and a thickness of about 300
It was formed into a μm film. Using this adhesive film, adhesion was performed in the same manner as in Examples 1 to 4, and normal peel strength and 2
The immersion strength at 5 ° C. in water was measured, and the strength retention (%) was calculated from the results.

[0023]

[Table 1]

N-1525: Nucrel N-1525
(Ethylene methacrylic acid copolymer manufactured by Mitsui DuPont Chemical Co., Ltd., methacrylic acid content 15% by weight, MFR 25
g / 10 min) N-1207C: Nucrel N-1207C (ethylene-methacrylic acid copolymer manufactured by Du Pont-Mitsui Chemicals,
Methacrylic acid content 12% by weight, MFR 7g / 10
K-431: Technolink K-431 (a saponified ethylene / vinyl acetate copolymer manufactured by Taoka Chemical Co., Ltd. (saponification ratio: 60)
%), MFR 5 g / 10 min) K-400: Technolink K-400 (a saponified ethylene-vinyl acetate copolymer manufactured by Taoka Chemical Co., Ltd. (saponification rate: 60)
%), MFR 2 g / 10 min) H-1051: Tuftec H-1051 (hydrogenated product of styrene-butadiene-styrene block copolymer manufactured by Asahi Kasei Corporation, MFR 1 g / 10 min (230 ° C.)) FS240: Sumikasen-L FS240 (Polyethylene manufactured by Sumitomo Chemical Co., Ltd., MFR 2 g / 10 min, density 0.919
g / cm ² ) GA701: Sumikacene-L GA701 (polyethylene manufactured by Sumitomo Chemical Co., Ltd., MFR 8 g / 10 min, density 0.920)
g / cm ² ) Quintac 3450: Styrene-isoprene block copolymer manufactured by Zeon Corporation

[0025]

[Table 2]

A1010: Epo Friend A1010
FS240: Sumikasen-L FS240 (Sumitomo Chemical Co., polyethylene, MFR 2 g / 10 min, density 0.919)
g / cm ² ) GA701: Sumikacene-L GA701 (polyethylene manufactured by Sumitomo Chemical Co., Ltd., MFR 8 g / 10 min, density 0.920)
g / cm ² ) Macromelt 6239: Polyamide manufactured by Henkel Japan

Example 9 A mixture having the same composition ratio as in Example 1 was melt-kneaded using a twin-screw extruder, and passed through a T-die to a thickness of 50 μm.
m adhesive T-die film was obtained. This was bonded under the conditions shown in Table 3, and the normal peel strength and the immersion strength in water at 25 ° C. were measured, and the strength retention (%) was calculated from the results. Example 10 A composition having the composition ratio of Example 1 was melt-kneaded using a twin-screw extruder, and an adhesive inflation film having a thickness of 50 μm was obtained using an inflation film forming machine. This was bonded under the conditions shown in Table 3, and the normal peel strength and the immersion strength in water at 25 ° C. were measured, and the strength retention (%) was calculated from the results.

[0028]

[Table 3]

Example 11 A metal foil sheet was prepared by passing the inflation film used in Example 10 and an aluminum foil having a thickness of 50 μm through a hot roll and bonding them. This was adhered to glass (3 × 25 × 100 mm) under the adhesion conditions shown in Table 4, the normal peel strength and the immersion strength in water at 25 ° C. were measured, and the strength retention (%) was calculated. Comparative Example 4 An inflation film was prepared in the same manner as in Example 10 using only EVOH in the same manner as in Comparative Example 2;
In the same manner as in the above, an inflation film and an aluminum foil having a thickness of 50 μm were passed through a hot roll and bonded to form a metal foil sheet. This was adhered to glass (3 × 2) under the bonding conditions shown in Table 4.
(5 × 100 mm), the normal peel strength and the immersion strength in water at 25 ° C. were measured, and the strength retention (%) was calculated.

[0030]

[Table 4]

[0031]

According to the present invention, it is possible to obtain a hot-melt adhesive composition excellent in adhesion between metals of the same or different types, water-to-glass, and water-to-glass adhesion. The adhesive film made of the adhesive composition has no tackiness on the surface, and thus is easy to handle. Further, when the metal foil to which the hot melt adhesive composition of the present invention is bonded is bonded to a glass surface or the like, it can have better water resistance than before.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (Reference) C09J 129/02 C09J 129/02 133/02 133/02 153/02 153/02 163/08 163/08 ( 72) Inventor Eiji Matsuda 4-2-1, Nishi-Mikuni, Yodogawa-ku, Osaka-shi F-term (reference) in Taoka Chemical Industry Co., Ltd. DF011 DM011 EC211 GA05 GA07 GA11 JA09 JB01 LA07 MA02 MA05

Claims (6)

[Claims] (1) The following component (a): 10 to 90% by weight,
A hot melt adhesive composition comprising (b) component: 5 to 70% by weight, (c) component: 5 to 70% by weight, and (d) component: 0 to 50% by weight. (A) Styrene-based thermoplastic elastomer (b) Saponified ethylene / vinyl acetate copolymer (c) Copolymer of ethylene and acrylic acid (d) Polyethylene 2. The hot melt adhesive composition according to claim 1, wherein (a) is a hydrogenated product of a block copolymer of a styrene compound and a conjugated diene compound or an epoxidized styrene butadiene copolymer. 3. The hot melt adhesive composition according to claim 1, wherein (b) is a partially saponified ethylene / vinyl acetate copolymer having a vinyl acetate content of 10 to 50% by weight. 4. The content of acrylic acid (c) is 10 to 3
The hot melt adhesive composition according to claim 1, which is 0% by weight. 5. An adhesive film comprising the hot melt adhesive composition according to claim 1. 6. A metal foil bonded with the hot melt adhesive composition according to claim 1.