JP2006008761A - Hot-melt adhesive composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hot-melt adhesive composition with improved heat resistance and a hardly-disintegratable hot-melt adhesive composition suitable for recycling. <P>SOLUTION: To 100 pts.wt. of a mixture comprising 20-90 wt% of an ethylene-vinyl acetate-vinylsilane copolymer in which the vinyl acetate content based on JIS K 6924-1 (1997 edition) is 20-50 wt% and the vinylsilane content is 0.01-2 wt% and 10-80 wt% of a hydrogenated tackifier, is added 0.01-1 pt.wt. of a silanol condensation catalyst, followed by crosslinking the ethylene-vinyl acetate-vinylsilane copolymer in the presence of water to obtain the hot-melt adhesive composition. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a hot melt adhesive composition with improved heat resistance and a hardly tearable hot melt adhesive composition suitable for recyclability.

  An ethylene-vinyl acetate copolymer is used as a raw material for hot melt adhesives because of its high tackiness. A hot melt adhesive is composed of an ethylene-vinyl acetate copolymer, a tackifier, and a wax, and is widely used in fields such as packaging, bookbinding, plywood, and woodwork. The amount of hot melt adhesive used is increasing year by year due to its short solidification time after application and the absence of solvent.

  In the bookbinding field, a method called “wireless binding” that allows easy bookbinding without string binding is widely used for bookbinding of telephone books, timetables, paperback books, magazines, and the like.

  On the other hand, measures have been promoted to collect and reuse paper that has been incinerated as conventional waste as waste paper, in order to reduce the amount of municipal waste that has become serious, such as the recent procurement of raw paper resources and the lack of capacity at final disposal sites. Yes. As a major obstacle to recycling used paper, the inclusion of hot-melt adhesive for bookbinding is mentioned. Since the adhesive melts in the used paper recycling process, the hot melt adhesive cannot be completely removed and deteriorates the quality of the recycled paper. When recycled, it takes time and effort to cut the back cover portion. Therefore, it is desired to develop a hardly tearable hot melt adhesive.

  In addition, conventional hot melt adhesives have a problem of a decrease in adhesive strength at a high temperature after bonding, and an improvement in heat resistance is required. As a method for improving the heat resistance of a hot melt adhesive, a method of crosslinking a polymer to be used with silane is known. As a silane crosslinking method, a method of grafting a silane compound onto a polyolefin (for example, see Patent Documents 1 and 2), a method of copolymerizing a polyolefin and a silane compound (for example, see Patent Document 3), and the like are known. In the grafting method, the reaction is performed using peroxide, the temperature conditions are limited, and gels are likely to be generated. Also, since the production process needs to be modified after the polyolefin is once produced, it takes time and costs. There was a problem.

  On the other hand, in the method of copolymerization, although there is a track record when the vinyl acetate content is 18% by weight or less, there is no vinyl acetate content of 20% by weight or more used for hot melt adhesives. Even in a copolymer of 18% by weight or less, there was a problem that when a tackifier was added, it was crosslinked during mixing.

Japanese Patent Publication No.55-160074

Japanese Examined Patent Publication No. 62-23795 Japanese Patent Publication No.56-8447

  An object of the present invention is to provide a hot melt adhesive composition having improved heat resistance and a hardly tearable hot melt adhesive composition suitable for recyclability.

  As a result of intensive investigations in view of such points, the present inventor has obtained a mixture comprising a specific ethylene-vinyl acetate-vinylsilane copolymer, a hydrogenated tackifier, and a silanol condensation catalyst in the presence of moisture. The present invention is completed by finding a hot-melt adhesive composition having excellent heat resistance and excellent recyclability suitable for recycling by crosslinking a vinyl-vinylsilane copolymer. It came to.

  That is, the present invention relates to an ethylene-vinyl acetate-vinylsilane copolymer having a vinyl acetate content of 20 to 50% by weight and a vinylsilane content of 0.01 to 2% by weight based on JIS K6924-1 (1997 edition). After adding 0.01 to 1 part by weight of a silanol condensation catalyst to 100 parts by weight of a mixture comprising 20 to 90% by weight and 10 to 80% by weight of a hydrogenated tackifier, ethylene-vinyl acetate is added in the presence of moisture. -It relates to a hot-melt adhesive composition characterized by crosslinking a vinylsilane copolymer.

  Hereinafter, the present invention will be described in detail.

  The ethylene-vinyl acetate-vinyl silane copolymer used in the hot melt adhesive composition of the present invention is not particularly limited as long as it is a copolymer containing ethylene, vinyl acetate, and vinyl silane. Examples include methoxysilane, vinyltriethoxysilane, and vinyltriacetoxysilane. Among these, an ethylene-vinyl acetate-vinyltrimethoxysilane copolymer is preferable.

  In addition to ethylene, vinyl acetate, and vinyl silane, ethylene-vinyl acetate-vinyl silane copolymer is added with other copolymerizable monomers as long as the physical properties of the hot melt adhesive composition of the present invention are not impaired. Examples of the copolymerizable monomer include (meth) acrylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate; ) Unsaturated carboxylic acids such as acrylic acid, maleic acid and fumaric acid; and unsaturated glycidyl compounds such as glycidyl acrylate, glycidyl methacrylate and itaconic acid monoglycidyl ester.

  The vinyl acetate content of the ethylene-vinyl acetate-vinylsilane copolymer used in the hot melt adhesive composition of the present invention is 20 to 50% by weight, preferably 25 to 45% by weight. When the vinyl acetate content is less than 20% by weight, the adhesiveness of the hot melt adhesive composition is lowered, and when it exceeds 50% by weight, the mechanical strength of the hot melt adhesive composition is lowered.

  The vinylsilane content of the ethylene-vinyl acetate-vinylsilane copolymer is 0.01 to 2% by weight, preferably 0.01 to 1% by weight. If the vinylsilane content is less than 0.01% by weight, the hot melt adhesive composition is insufficiently crosslinked, and if it exceeds 2% by weight, it is difficult to stably produce an ethylene-vinyl acetate-vinylsilane copolymer. Become.

  Further, the melt mass flow rate (MFR) at 190 ° C. according to K 6924-1 (1997 edition) of an ethylene-vinyl acetate-vinyl silane copolymer is preferably 1 to 3000 g / 10 min, particularly preferably 10 to 10%. The range is 1,000 g / 10 min.

  The ethylene-vinyl acetate-vinylsilane copolymer may be produced by any copolymerization method as long as the copolymer can be obtained. For example, ethylene, vinyl acetate, vinylsilane, generally radical polymerization in a stirring autoclave. A polymerization initiator such as an azo-based initiator compound or an organic peroxide compound used for the polymerization, and a chain transfer agent generally used for radical polymerization are supplied under conditions of a polymerization pressure of 50 to 300 MPa and a polymerization temperature of 100 to 250 ° C. The copolymerization can be carried out under

  The blending amount of the ethylene-vinyl acetate-vinyl silane copolymer in the blend of the ethylene-vinyl acetate-vinyl silane copolymer and the hydrogenated tackifier of the hot melt adhesive composition of the present invention is 20 to 90% by weight, Preferably it is the range of 40-80 weight%. If the blending amount is less than 20% by weight, crosslinking of the hot melt adhesive composition becomes insufficient, and if it exceeds 90% by weight, the coating workability of the hot melt adhesive composition is deteriorated.

  The hydrogenated tackifier used in the hot melt adhesive composition of the present invention is a hydrogenated double bond in the tackifier, particularly with an ethylene-vinyl acetate-vinylsilane copolymer. In order to prevent crosslinking reaction during mixing, the hydrogenation rate is preferably 90 to 100%. Examples of the hydrogenated tackifier include hydrides such as aliphatic hydrocarbon resins, decyclic hydrocarbon resins, aromatic hydrocarbon resins, terpene resins, rosin resins, styrene resins, and the like. Can be used alone or as a mixture. Specifically, as hydrides of decyclic hydrocarbon resins, Alcon (made by Arakawa Chemical Co., Ltd.), rosin hydrates such as ester gum (made by Arakawa Chemical Co., Ltd.), Pine Crystal (Arakawa Chemical) As a hydride of a polyterpene resin, a product such as Clearon (manufactured by Yasuhara Chemical Co., Ltd.) can be used.

  The blending amount of the hydrogenated tackifier in the blending of the ethylene-vinyl acetate-vinylsilane copolymer and the hydrogenated tackifier of the hot melt adhesive composition of the present invention is 10 to 80% by weight, and among them, the adhesion From the viewpoint of strength and coating workability, it is preferably 20 to 50% by weight.

  Examples of the silanol condensation catalyst used in the hot melt adhesive composition of the present invention include dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dioctoate, dioctyltin dilaurate, and stannous acetate. The compounding amount of the silanol condensation catalyst is 0.01 to 1 part by weight with respect to 100 parts by weight of the mixture comprising the ethylene-vinyl acetate-vinylsilane copolymer and the hydrogenated tackifier, and among these, 0.05 to Particularly preferred is 0.5 part by weight. If it is less than 0.01 part by weight, the effect as a condensation catalyst is small, and if it exceeds 1 part by weight, it is not preferable from the economical aspect.

  The hot melt adhesive composition of the present invention is characterized in that the ethylene-vinyl acetate-vinylsilane copolymer is crosslinked in the presence of moisture, and the moisture used is water itself or water-containing one. Any compound can be used as long as it is. As a crosslinking method, for example, the ethylene-vinyl acetate-vinylsilane copolymer can be crosslinked by leaving it in a high humidity environment of 30 RH% to 100 RH% for 1 to 7 days.

  In the hot melt adhesive composition of the present invention, a wax is further added to a mixture comprising an ethylene-vinyl acetate-vinylsilane copolymer, a hydrogenated tackifier, and a silanol condensation catalyst for viscosity adjustment and workability improvement. The wax used is not particularly limited and may be any wax as long as it is generally used in a hot melt adhesive composition. Specific examples include petroleum oils such as paraffin wax and microcrystalline wax. Synthetic waxes such as polyethylene wax, Fischer-Tropsch wax, polypropylene wax, and atactic polypropylene; natural waxes such as wood wax, carnauba wax, and beeswax, and the like can be used alone or as a mixture. The blending amount of the wax is 1 to 50 parts by weight with respect to 100 parts by weight of the blend composed of the ethylene-vinyl acetate-vinylsilane copolymer, the hydrogenated tackifier, and the silanol condensation catalyst, from the viewpoint of adhesiveness. It is preferable that it is 10-30 weight part.

  In the hot melt adhesive composition of the present invention, after adding a silanol condensation catalyst and further a wax to a mixture comprising an ethylene-vinyl acetate-vinylsilane copolymer and a hydrogenated tackifier before being brought into contact with moisture and crosslinked. The melt viscosity before crosslinking at 180 ° C. in accordance with JAI-7 (1991 edition) is preferably 500 to 50,000 mPa · s from the viewpoint of coating properties. Considering workability and the strength of the adhesive, it is particularly preferably 1,000 to 30,000 mPa · s.

  In addition, the melt viscosity after crosslinking by adding a silanol condensation catalyst and a wax to a mixture comprising an ethylene-vinyl acetate-vinyl silane copolymer and a hydrogenated tackifier and then bringing it into contact with moisture and crosslinking is defined as the melt viscosity after crosslinking. The melt viscosity after crosslinking at 180 ° C. according to JAI-7 (1991 edition) is preferably 5,000 mPa · s or more. Moreover, it is preferable that it is 1.5 times or more of the melt viscosity before bridge | crosslinking.

  A melt obtained by adding a silanol condensation catalyst to a mixture of an ethylene-vinyl acetate-vinyl silane copolymer of the hot melt adhesive composition of the present invention and a hydrogenated tackifier, and further bringing a wax into contact with water, followed by crosslinking. Mass flow rate (MFR) is defined as MFR after crosslinking, and the MFR after crosslinking at 190 ° C. in accordance with JIS K-6924-1 (1997 edition) is preferably 0.01 g / 10 min or more.

  The hot melt adhesive composition of the present invention is obtained by adding a silanol condensation catalyst or a wax to a mixture comprising an ethylene-vinyl acetate-vinylsilane copolymer and a hydrogenated tackifier, and then adding ethylene in the presence of moisture. -It can be obtained by crosslinking a vinyl acetate-vinyl silane copolymer. As a method of mixing ethylene-vinyl acetate-vinylsilane copolymer, hydrogenated tackifier, silanol condensation catalyst, or wax, short or twin screw extruder, open roll mill, Banbury mixer, kneader, kneader ruder, melting It is possible to carry out at a mixing temperature of 150 to 200 ° C. using a mixing tank or the like under a mechanical mixing condition; using a hot melt applicator or a method of mixing at the time of extrusion. For example, when using a solution mixing tank, it can be kneaded at 180 ° C. for 1 hour.

  If necessary, the hot-melt adhesive composition of the present invention may be phenol-type oxidized such as tetrakis (methylene-3- (3,5di-t-butyl-4-hydroxyphenyl) propionate) methane for improving the heat stability. Antioxidants such as phosphorus-based and thioether-based agents; lubricants such as stearamide to improve compatibility; dyes; weathering agents; anti-blocking agents; inorganic fillers and the like can be blended.

  The hot melt adhesive composition of the present invention is used as a hot melt adhesive for bookbinding, packaging and woodworking.

  As described above, the hot melt adhesive composition obtained in the present invention is a hot melt adhesive composition that can be hardly shredded suitable for improvement in heat resistance and recyclability.

  EXAMPLES Next, although an Example and a comparative example demonstrate this invention, this invention is not limited to these Examples.

  The test methods used in the following examples and comparative examples were measured and evaluated by the following methods.

1. Synthesis of Ethylene-Vinyl Acetate-Vinyl Silane Copolymer Copolymerization was performed as follows using a tank reactor. Ethylene, vinyl acetate, vinyltrimethoxysilane, n-butane, glycidyl methacrylate and initiator (compound name: t-butylperoxypivalate) were continuously fed into the reactor as shown in Table 1, The mixture was stirred at 164 MPa, a temperature of 165 ° C., and a rotation speed of 1,500 rpm to obtain an ethylene-vinyl acetate-vinyltrimethoxysilane copolymer. The vinyltrimethoxysilane content was dissolved in heated xylene and reprecipitated with methanol. After measuring SiO ₂ with a fluorescent X-ray apparatus (manufactured by Rigaku Corporation, 3080E3), the vinylsilane content was calculated. . The vinyl acetate content and the glycidyl methacrylate content were calculated by measuring ¹ H-NMR at room temperature in deuterated chloroform using a nuclear magnetic resonance measuring apparatus (manufactured by JEOL, trade name: JNM-GSX270 type). The results are shown in Table 1.

２．耐熱接着性試験
接着力測定器（ＪＴトーシ（株）製、ＡＳＭ−１５Ｎ）を用いて、ＪＡＩ−７（１９９１年版）に準拠した耐熱接着性法（Ｃ法）を用い、エチレン−酢酸ビニル−ビニルシラン系共重合体、水素化粘着付与剤及びシラノール縮合触媒、およびさらにワックスの混合物からなる試験片を作製した。得られた試験片をタバイ製恒温恒湿槽（ＰＬＡＴＩＮＯＵＳ ＬＵＣＩＦＥＲ ＰＬ−２Ｇ）の中（温度４０℃、湿度８０％の条件下）で１週間放置しエチレン−酢酸ビニル−ビニルシラン系共重合体を架橋し、ホットメルト接着剤組成物の試験片を作成した。更に温度２３℃、湿度５０％で２４時間放置後、ＪＡＩ−７（１９９１年版）に準拠した耐熱接着性試験を実施した。

2. Heat-resistant adhesion test Using a heat-resistant adhesive method (Method C) compliant with JAI-7 (1991 edition) using an adhesive force measuring device (manufactured by JT Toshi Co., Ltd., ASM-15N), ethylene-vinyl acetate- A test piece comprising a mixture of a vinylsilane copolymer, a hydrogenated tackifier, a silanol condensation catalyst, and a wax was prepared. The obtained test piece was allowed to stand in a constant temperature and humidity chamber (PLATINUS LUCIFER PL-2G) (temperature 40 ° C., humidity 80%) for 1 week to crosslink the ethylene-vinyl acetate-vinylsilane copolymer. Then, a test piece of the hot melt adhesive composition was prepared. Further, after being allowed to stand at a temperature of 23 ° C. and a humidity of 50% for 24 hours, a heat-resistant adhesion test according to JAI-7 (1991 edition) was performed.

3. Measurement of Melt Mass Flow Rate (MFR) Measurement was performed at 190 ° C. according to JIS K6924-1 (1997 edition).

4). Measurement of melt viscosity It measured on condition of 180 degreeC based on JAI-7 (1991 edition).

5. Measurement of softening point A test piece of a hot-melt adhesive composition obtained in the same manner as in the heat-resistant adhesive test was further left for 24 hours at a temperature of 23 ° C. and a humidity of 50%, and in accordance with JAI-7 (1991 edition). The softening point was measured.

6). Shredding test Based on "Testing method for hard-to-break hot melt" approved by Japan Adhesive Industry Association, it was performed as follows.

(1) Preparation of test film (size: 3 × 3 cm, thickness: 0.8 mm)
A mixture of an ethylene-vinyl acetate-vinylsilane copolymer, a hydrogenated tackifier, a silanol condensation catalyst, and a wax is pressed with a press machine (NF-50 single-acting hydraulic molding machine, manufactured by Shindo Metal Industry Co., Ltd.). After forming a film of a predetermined size by press molding at 130 ° C., it is allowed to stand for 2 days at a temperature of 40 ° C. and a humidity of 80% to crosslink the ethylene-vinyl acetate-vinylsilane copolymer, A test film for the melt adhesive composition was prepared.

(2) Disaggregation A tappy pulp disaggregator (TAPPI-T20, manufactured by Toyo Seiki Seisakusho Co., Ltd.) containing 2 L of water at a temperature of 30 ° C. and 10 ml of caustic soda solution (concentration 50 g / L) was used. The three films were put in and disaggregated for 30 minutes at a rotational speed of 3000 rpm. Thereafter, the disaggregated slurry was received in a bucket together with the washing water, and the total amount was about 5 L.

(3) Flat screen processing 1 (10 cut screen)
A flat screen (manufactured by Yasuda Seiki Seisakusho, DKFW233) was used, the screen plate was cut into 10 cuts (size: 30 × 25 cm, thickness: 0.25 mm), and the water flow was adjusted to 10 L / min. The disaggregated slurry was put into a 10-cut flat screen and screened for 5 minutes. The accept portion was collected with a wire having an opening of 100 μm or less (the reject portion was discarded), and the accept portion was received in a bucket to make a total volume of about 5 L with diluted water.

(4) Flat screen processing 2 (6-cut screen)
A flat screen (manufactured by Yasuda Seiki Seisakusho, DKFW233) was used, the screen plate was made into 6 cuts (size: 30 × 25 cm, thickness: 0.15 mm), and the water flow was adjusted to 10 L / min. The 10-cut flat screen treated accept slurry was put into a 6-cut flat screen and screened for 6 minutes.

(5) Residue collection The reject was scraped off with a razor or the like and collected in a glass beaker (the accept was discarded). While the residue collected in the beaker was appropriately diluted with water, suction filtration was performed using a Buchner funnel so that the residue was uniformly dispersed on the filter paper.

(6) Hot melt adhesive melting / transfer After drying at 105 ° C. for 30 seconds, one sheet of PPC paper (copy paper) is stacked with the residue sandwiched between them, and processed for 2 minutes with a rotary dryer set at 120 ° C. The filter paper was dried and the hot melt adhesive was melted and transferred to PPC paper. The filter paper was peeled off immediately after transfer.

(7) Dyeing An aqueous dye was applied to the bonding surface side of the PPC paper with a brush.

(8) Evaluation The number of white spots where staining per area of A4 size repelled was counted visually. The measurement was repeated three times, and the average value of the count number was 20 or less and the maximum value was 30 or less, and the case that did not satisfy the above condition was marked as x.

7). Raw materials The ethylene-vinyl acetate copolymers, tackifiers, waxes, antioxidants and silanol condensation catalysts used in Examples and Comparative Examples are shown in Table 2, Table 3, Table 4, Table 5, and Table 6, respectively. .

実施例１
エチレン−酢酸ビニル−ビニルシラン系共重合体（Ａ−１）６０重量部、粘着付与剤（Ｂ−１）４０重量部、酸化防止剤（Ｄ−１）０．５重量部及びシラノール縮合触媒（Ｅ−１）０．１重量部を加えた後、１８０℃に設定したビーカー内で混練し混合物を得た。前記２．耐熱接着性試験及び６．細裂試験の項に記載のように、得られた混合物を用い耐熱接着性試験用試験片及び細裂試験用フィルムを作成した後、それぞれの条件下にてエチレン−酢酸ビニル−ビニルシラン系共重合体を架橋しホットメルト接着剤組成物を得、その性能を評価した。その結果を表７に示す。

Example 1
60 parts by weight of ethylene-vinyl acetate-vinylsilane copolymer (A-1), 40 parts by weight of tackifier (B-1), 0.5 part by weight of antioxidant (D-1) and silanol condensation catalyst (E -1) After adding 0.1 weight part, it knead | mixed in the beaker set to 180 degreeC, and obtained the mixture. 2. 5. Heat adhesion test and After preparing a test piece for heat-resistant adhesion test and a film for tear test using the obtained mixture as described in the section of the tear test, an ethylene-vinyl acetate-vinyl silane copolymer is prepared under the respective conditions. The coalescence was crosslinked to obtain a hot melt adhesive composition, and its performance was evaluated. The results are shown in Table 7.

Example 2
The ethylene-vinyl acetate-vinylsilane copolymer was changed from (A-1) to (A-2), and a hot melt adhesive composition was obtained and evaluated in the same manner as in Example 1. The results are shown in Table 7.

Example 3
The tackifier of Example 1 was changed from (B-1) to (B-2), and a hot melt adhesive composition was obtained and evaluated in the same manner as in Example 1. The results are shown in Table 7.
Example 4
The tackifier of Example 1 was changed from (B-1) to (B-3), and a hot melt adhesive composition was obtained and evaluated in the same manner as in Example 1. The results are shown in Table 7.

Comparative Example 1
After adding ethylene-vinyl acetate copolymer (A-4) 60 weight part, tackifier (B-1) 40 weight part, and antioxidant (D-1) 0.5 weight part, it sets to 180 degreeC. The resulting mixture was kneaded in a beaker to obtain a mixture. A hot melt adhesive composition was obtained in the same manner as in Example 1, and the performance was evaluated. The results are shown in Table 7. Since an ethylene-vinyl acetate copolymer containing no vinylsilane was used and no silanol condensation catalyst was used, the heat resistance was not improved.

Comparative Example 2
The tackifier of Example 1 was changed from (B-1) to (B-4), a hot melt adhesive composition was obtained in the same manner as in Example 1, and the performance was evaluated. The results are shown in Table 7. Since a non-hydrogenated tackifier was used, the melt viscosity before crosslinking increased and workability deteriorated.

Example 5
50 parts by weight of ethylene-vinyl acetate-vinylsilane copolymer (A-3), 30 parts by weight of tackifier (B-1), 10 parts by weight of wax (C-1), 10 parts by weight of wax (C-2) Then, 0.5 part by weight of antioxidant (D-1) and 0.1 part by weight of silanol condensation catalyst (E-1) were added, and then kneaded in a beaker set at 180 ° C. to obtain a mixture, Example 1 Similarly, a hot melt adhesive composition was obtained and its performance was evaluated. The results are shown in Table 7.

Comparative Example 3
50 parts by weight of ethylene-vinyl acetate copolymer (A-5), 30 parts by weight of tackifier (B-1), 10 parts by weight of wax (C-1), 10 parts by weight of wax (C-2) and antioxidant After adding 0.5 parts by weight of the agent (D-1), the mixture was kneaded in a beaker set at 180 ° C. to obtain a mixture, a hot melt adhesive composition was obtained in the same manner as in Example 1, and the performance was evaluated. . The results are shown in Table 7. Since an ethylene-vinyl acetate copolymer containing no vinyl silane was used and no silanol condensation catalyst was used, the tear test did not pass.

Claims (7)

An ethylene-vinyl acetate-vinylsilane copolymer having a vinyl acetate content of 20 to 50% by weight and a vinylsilane content of 0.01 to 2% by weight in accordance with JIS K6924-1 (1997 edition) is 20 to 90% by weight. And 0.01 to 1 part by weight of a silanol condensation catalyst to 100 parts by weight of a mixture consisting of 10 to 80% by weight of a hydrogenated tackifier, and then ethylene-vinyl acetate-vinylsilane copolymer in the presence of moisture A hot melt adhesive composition characterized by cross-linking the coalescence. The presence of moisture after adding 1 to 50 parts by weight of wax to 100 parts by weight of a mixture comprising the ethylene-vinyl acetate-vinylsilane copolymer according to claim 1, a hydrogenated tackifier, and a silanol condensation catalyst. The hot-melt adhesive composition according to claim 1, wherein the ethylene-vinyl acetate-vinyl silane copolymer is crosslinked underneath. 3. The hot melt adhesive composition according to claim 1, wherein the ethylene-vinyl acetate-vinyl silane copolymer is an ethylene-vinyl acetate-vinyl silane-unsaturated glycidyl compound copolymer. The hot-melt adhesive composition according to any one of claims 1 to 3, wherein the hydrogenation rate of the tackifier is 90 to 100%. JAI-7 (1991 edition) after adding a silanol condensation catalyst and a wax to a mixture comprising an ethylene-vinyl acetate-vinylsilane copolymer and a hydrogenated tackifier before being brought into contact with moisture to crosslink. The hot melt adhesive composition according to claim 1, wherein the melt viscosity at 180 ° C. (melt viscosity before cross-linking) is 500 to 50,000 mPa · s. Conforms to JAI-7 (1991 edition) after adding a silanol condensation catalyst and a wax to a mixture comprising an ethylene-vinyl acetate-vinylsilane copolymer and a hydrogenated tackifier, and then bringing into contact with moisture and crosslinking. The melt viscosity at 180 ° C. (melt viscosity after crosslinking) and the melt mass flow rate (MFR) at 190 ° C. (MFR after crosslinking) in accordance with JIS K6924-1 (1997 edition) are formulas of (a) to (c) The hot melt adhesive composition according to any one of claims 1 to 5, wherein:
(A) Melt viscosity after crosslinking (mPa · s) ≧ 5,000
(B) Melt viscosity after crosslinking (mPa · s) ≧ melt viscosity before crosslinking (mPa · s) × 1.5
(C) MFR after crosslinking (g / 10 min) ≧ 0.01 The hot melt adhesive composition according to claim 1, wherein the hot melt adhesive composition is used for bookbinding.