JPH10102020A - Tackifier for ethylene based copolymer and adhesive composition using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject tackifier excellent in adhesive properties, initial color tone, offensive smell by using a hydrogenated compound which is a hydrogenation product of an aromatic hydrocarbon resin composed of a polymer of C9 fraction, in a specific hydrogenating ratio. SOLUTION: This tackifier is obtained by using the hydrogenated aromatic hydrocarbon resin which is obtained by polymerizing the C9 fraction, having 5-30 % of hydrogenation degree of aromatic ring, <=1 Gardener color scale of initial color tone. The C9 fraction is ordinary obtained by naphtha cracking. The preferable softening point of the prescribed aromatic hydrocarbon resin is ordinary 70 to 150 deg.C, the number average molecular weight is 300 to 2000. The hydrogenation of the aromatic hydrocarbon resin is preferably carried out under 100 to 200 kg/cm" of hydrogen pressure, at 200 to 300 deg.C for 2 to 7 hours using nickeldiatomaceous earth catalyst as a hydrogenation catalyst. Preferably, 100 pts.wt. of ethylene based copolymer, 50 to 150 pts.wt. of the objective tackifier and 10 to 100 pts.wt. of wax are used to obtain an adhesive composition using this objective tackifier.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a tackifier for an ethylene copolymer and an adhesive composition thereof.

[0002]

2. Description of the Related Art Conventionally, an ethylene-based copolymer has been used as a base polymer, and a hydrocarbon resin such as an aliphatic petroleum resin, an aromatic petroleum resin, a terpene resin or a rosin resin or the like is used as a tackifier. There are known adhesive compositions to which various hydrogenated resins obtained by hydrogenating phenol under known conditions are generally added, and these adhesive compositions are generally required to have adhesive strength and holding power as adhesive performance. Further, when such an adhesive composition is used, for example, for cardboard packaging or bookbinding, it is usually subjected to hot-melt coating, so that in addition to adhesive performance, a change in viscosity during heating is small. It is also required that the initial color tone is nearly colorless and transparent, and that there is no odor.

[0003] However, among the tackifiers used in the above-mentioned adhesive composition, some of the tackifiers which have not been subjected to hydrogenation have a characteristic in adhesive performance, but have an initial color tone of Gardner level. Bad and bad odor. On the other hand, improvement in color tone and odor of the tackifier which has been subjected to hydrogenation is observed as compared with the non-hydrogenated tackifier. But,
The hydrogenated rosin resin is still insufficient in color tone and odor. Further, the hydride of the terpene-based resin is improved in both color tone and odor, but tends to be somewhat weak in terms of adhesive performance. As a hydride of an aromatic petroleum resin, a resin in which about 50% or more of an aromatic ring is hydrogenated is generally known. The odor and the color tone are very good, and the compatibility with the base polymer is good. It is widely used because it has an excellent balance of adhesion performance. However, the adhesive performance (adhesive strength / holding power) of hydrides of aromatic petroleum resins is weaker than non-hydrogenated resins.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a tackifier for an ethylene-based copolymer which is excellent in adhesive performance and excellent in initial color tone and odor, and an adhesive composition thereof.

[0005]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have conducted intensive studies on a tackifier used for an ethylene copolymer, and as a result, obtained by polymerizing a C9 fraction as a tackifier. A hydride of the aromatic hydrocarbon resin used, wherein the hydrogenation rate of the aromatic ring of the aromatic hydrocarbon resin is 5
% To 30% and an initial color tone of 1 Gardner or less was found to achieve the above object. The present invention has been completed based on such new knowledge.

That is, the present invention relates to a tackifier for an ethylene copolymer obtained by using a hydride of an aromatic hydrocarbon resin obtained by polymerizing a C9 fraction. Hydrogenation rate of the aromatic ring of 5% or more and 30% or less,
And an initial color tone of 1 Gardner or less, a tackifier for an ethylene-based copolymer, 100 parts by weight of an ethylene-based copolymer, and the tackifier 50 to 15
The present invention relates to an adhesive composition containing 0 parts by weight and 10 to 100 parts by weight of a wax.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The tackifier for an ethylene copolymer of the present invention can be obtained by hydrogenating an aromatic hydrocarbon resin obtained by polymerizing a C9 fraction.

[0008] The C9 fraction referred to herein generally refers to one obtained by cracking of naphtha. In the C9 fraction, styrene, vinyltoluene, α-methylstyrene, indene and the like are polymerizable monomers. And other high-boiling compounds. The aromatic hydrocarbon resin is obtained by polymerizing such a polymerizable monomer by ordinary cationic polymerization. The softening point of the obtained aromatic hydrocarbon resin is preferably about 70 to 150 ° C., and the number average molecular weight is preferably about 300 to 2,000.

The hydrogenation of the aromatic hydrocarbon resin is performed so that the hydrogenation rate of the aromatic ring is 5% or more and 30% or less. In particular, the hydrogenation rate of the aromatic ring is preferably 20% or more and 30% or less in consideration of the initial color tone, while the hydrogenation rate of the aromatic ring is preferably 10% or more and 20% in consideration of the adhesive performance (adhesive strength / holding power). % Or less is preferable. When the hydrogenation rate of the aromatic nucleus is less than 5%, the initial color tone becomes worse than 1 Gardner, and the odor is not improved because the aromatic hydrocarbon resin remains unchanged. If it exceeds 30%, the adhesive performance (adhesive strength / holding power) gradually decreases, which is not preferable.

The hydrogenation reaction is carried out in the presence of a hydrogenation catalyst such that the hydrogenation rate of the aromatic hydrocarbon resin falls within the above range (the hydrogenation rate of the aromatic ring is 5% to 30%). The conditions are adjusted as appropriate. The hydrogenation reaction rate of the aromatic ring is calculated from the area of 1 H-spectrum of proton NMR which is attributed to the aromatic ring appearing at around 7 PPM based on the following formula.

Hydrogenation rate = {1- (spectral area of hydride of aromatic hydrocarbon resin / spectral area of aromatic hydrocarbon resin)} × 100 (%)

As the hydrogenation catalyst, various catalysts such as metals such as nickel, palladium, platinum, cobalt, rhodium, ruthenium and molybdenum and metal compounds such as oxides and sulfides thereof can be used. Such a hydrogenation catalyst may be supported on a porous carrier having a large surface area, such as alumina, silica (diatomaceous earth), carbon, or titania. In the present invention, among these catalysts, it is preferable to use a nickel-diatomaceous earth catalyst from the viewpoint of easy adjustment of the hydrogenation rate within the above range and cost. If necessary, a co-catalyst such as an alkali metal, an alkaline earth metal, iron, and chromium may be used. The amount of the catalyst used is about 0.1 to 3% by weight, preferably 0.1 to 1% by weight of the aromatic hydrocarbon resin as the raw material resin. If the amount is less than 0.1% by weight, the hydrogenation tends to be difficult to proceed, while if it exceeds 3% by weight, the hydrogenation tends to proceed too much.

The conditions of the hydrogenation reaction are such that the hydrogenation pressure is usually 3
The reaction temperature is usually in the range of about 0 to 300 Kg / cm ^2.
This is performed in a range of about 50 to 320 ° C. Preferably, the hydrogenation pressure is 100-200 Kg / cm ² and the reaction temperature is 2
00-300 ° C. Hydrogenation pressure is 30 kg / cm ²
If the reaction temperature is less than 150 ° C., the hydrogenation is difficult to proceed, and the hydrogenation pressure is 300 kg / cm.
If it exceeds ² , or if the reaction temperature exceeds 320 ° C., decomposition occurs and the softening point tends to decrease. The reaction time is generally about 1 to 7 hours, preferably 2 to 7 hours. The hydrogenation reaction is performed in a state where the aromatic hydrocarbon resin is melted or dissolved in a solvent. As the solvent,
Cyclohexane, n-hexane, n-heptane, decalin and the like can be used.

The use amount of the catalyst and the reaction time have been described in the case where a batch system is employed as the reaction system. However, a flow system (fixed bed system, fluidized bed system, etc.) may be employed as the reaction system. it can.

The adhesive composition of the present invention comprises 100 parts by weight of an ethylene copolymer and 50 to 15 of the tackifier of the present invention.
0 parts by weight and 10 to 100 parts by weight of wax.

When the amount of the tackifier is less than 50 parts by weight, a sufficient adhesive force cannot be obtained, and when the amount exceeds 150 parts by weight, a sufficient holding force cannot be obtained, which is not preferable. Also,
When the amount of the wax is less than 10 parts by weight, the melt viscosity of the obtained adhesive composition is too high, and when the amount exceeds 100 parts by weight, a sufficient holding power cannot be obtained, which is not preferable.

The ethylene copolymer is a copolymer of ethylene and a monomer copolymerizable with ethylene, and may be any of those conventionally used in hot melt adhesives. Examples of the monomer copolymerizable with ethylene include vinyl acetate. The vinyl acetate content is usually 20
About 45% by weight. The molecular weight was determined to be 1 by the melt index (190 ° C., load 2160 g, 10 minutes).
It is preferably about 0 to 400 g / 10 minutes.

As the wax, those used in hot melt adhesives can be used. Specifically, petroleum waxes such as paraffin wax and microcrystalline wax, Fischer-Tropsch wax,
Synthetic waxes such as low molecular weight polyethylene waxes.

The adhesive composition of the present invention may further contain, if necessary, additives such as a filler and an antioxidant.

[0020]

According to the present invention, while maintaining the good initial color tone and odor possessed by the hydride of the aromatic hydrocarbon resin, the aromatic hydrocarbon resin which is hydrogenated by about 50% or more of the conventional hydride is used. It can be provided with a tackifier for ethylene copolymer which greatly exceeds the adhesive performance. Further, since the hydrogenation rate is low, the consumption of the amount of catalyst and hydrogen gas is small, which is advantageous from the viewpoint of cost. Further, by using the tackifier thus obtained, it is possible to provide an adhesive composition having a small change in viscosity after heating, in addition to the above properties. Such an adhesive composition of the present invention is subjected to hot melt coating, cardboard packaging,
It can be used for various purposes such as bookbinding.

[0021]

The present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples. In each example, parts are based on weight.

Example 1 (1) Production of tackifier C9 petroleum resin ("Petrodin 120" manufactured by Mitsui Petrochemical Co., Ltd., softening point 120 ° C, number average molecular weight 750) 10
0 parts and a nickel-diatomaceous earth catalyst (“N-11
3 ", manufactured by Nikki Chemical Co., Ltd.) in an autoclave, hydrogen pressure 200 kg / cm ² , reaction temperature 290
The hydrogenation reaction was carried out at a temperature of 5 ° C. for a reaction time of 5 hours.
After completion of the reaction, the obtained resin was dissolved in 300 parts of cyclohexane, and the catalyst was removed by filtration. Thereafter, a hydrogenated resin filtrate and an antioxidant (“Irganox 1010”, Japan) were placed in a 0.5-liter separable flask equipped with a stirring blade, a Liebig condenser, a thermometer, a temperature controller and a pressure indicator. 0.35 parts) (200 ° C., 20 torr)
The solvent is removed by gradually raising the temperature and reducing the pressure until C9-based low hydrogenated light colored petroleum resin having a number average molecular weight of 700, a softening point of 101 ° C., an initial color tone of 50 Hazen, and a hydrogenation ratio of aromatic ring of 8% (tackifier) ) 94 parts were obtained. The softening point is JIS K
2531 Ring and ball method.

(2) Preparation of adhesive composition 40 parts of the tackifier obtained in the above (1) and a wax (“Hi-Mic-1080”, manufactured by Nippon Seiro Co., Ltd.) 2
0 parts were melt mixed at 160 ° C. Thereafter, 40 parts of an ethylene-vinyl acetate copolymer ("Evaflex EV220", manufactured by Mitsui Dupont Chemical Co., Ltd.) was gradually added to prepare an adhesive composition.

Example 2 (1) Production of Tackifier C9 petroleum resin ("Petrodin 120" manufactured by Mitsui Petrochemical Co., Ltd., softening point 120 ° C., number average molecular weight 750) 10
0 parts and a nickel-diatomaceous earth catalyst (“N-11
0.6 "(manufactured by Nikki Chemical Co., Ltd.) in an autoclave, hydrogen pressure 200 kg / cm ² , reaction temperature 290
The hydrogenation reaction was carried out at a temperature of 5 ° C. for a reaction time of 5 hours.
After completion of the reaction, the obtained resin was dissolved in 300 parts of cyclohexane, and the catalyst was removed by filtration. Thereafter, a hydrogenated resin filtrate and an antioxidant ("Irganox 1010", Japan) were placed in a 0.5-liter separable flask equipped with a stirring blade, a Liebig condenser, a thermometer, a temperature controller and a pressure indicator. 0.35 parts) (200 ° C., 20 torr)
The solvent is removed by gradually raising the temperature and reducing the pressure until the C9 series hydrogenated light-colored petroleum resin with a number average molecular weight of 710, a softening point of 103 ° C., an initial color tone of 30 Hazen, and a hydrogenation rate of the aromatic ring of 25% (tackifier) ) 94 parts were obtained.

(2) Preparation of adhesive composition In Example 1 (2), except that the tackifier obtained in Example 2 (1) was used as the tackifier,
An adhesive composition was prepared in the same manner as in Example 1 (2).

Example 3 (1) Production of Tackifier C9 petroleum resin (“Petrodin 100”, manufactured by Mitsui Petrochemical Co., Ltd., softening point 100 ° C., number average molecular weight 700) 10
0 parts and a nickel-diatomaceous earth catalyst (“N-11
3 ", manufactured by Nikki Chemical Co., Ltd.) in an autoclave, hydrogen pressure 200 kg / cm ² , reaction temperature 265
The hydrogenation reaction was carried out at a temperature of 5 ° C. for a reaction time of 5 hours.
After completion of the reaction, the obtained resin was dissolved in 300 parts of cyclohexane, and the catalyst was removed by filtration. Thereafter, a hydrogenated resin filtrate and an antioxidant (“Irganox 1010”, Japan) were placed in a 0.5-liter separable flask equipped with a stirring blade, a Liebig condenser, a thermometer, a temperature controller and a pressure indicator. 0.35 parts) (200 ° C., 20 torr)
The solvent was removed by gradually raising the temperature and reducing the pressure until the number-average molecular weight was 700, the softening point was 101 ° C., the initial color tone was 200 Hazen,
96 parts of a C9 type low hydrogenated light petroleum resin (tackifier) having an aromatic ring hydrogenation rate of 5% was obtained.

(2) Preparation of adhesive composition In Example 1 (2), except that the tackifier obtained in Example 3 (1) was used as the tackifier,
An adhesive composition was prepared in the same manner as in Example 1 (2).

Comparative Example 1 (Preparation of Adhesive Composition) In Example 1 (2), as a tackifier, hydrogenated C9 petroleum resin "Alcon M-100" (manufactured by Arakawa Chemical Industries, Ltd. An adhesive composition was prepared in the same manner as in (2) of Example 1 except that a point of 100 ° C., a number average molecular weight of 690, an aromatic ring hydrogenation rate of 60%, and an initial color tone of 30 Hazen were used.

Comparative Example 2 (Preparation of Adhesive Composition) In Example 1 (2), a styrene-modified terpene resin “YS Resin TO-105” (manufactured by Yasuhara Chemical Co., Ltd., softening point 105 ° C.) was used as a tackifier. , A number average molecular weight of 790, and an initial color tone of 2 Gardner), and an adhesive composition was prepared in the same manner as in Example 1 (2).

Comparative Example 3 (Preparation of Adhesive Composition) In Example 1 (2), a partially hydrogenated terpene resin “Clearon M-105” (manufactured by Yasuhara Chemical Co., Ltd., softening point 105 ° C.) was used as a tackifier. , Number average molecular weight 7
80, an initial color tone of 30 Hazen), and an adhesive composition was prepared in the same manner as in Example 1 (2).

Comparative Example 4 (Preparation of Adhesive Composition) In Example 1 (2), a C9 petroleum resin "Petrosin 100" (manufactured by Mitsui Petrochemical Co., Ltd.) was used as a tackifier.
An adhesive composition was prepared in the same manner as in Example 1 (2) except that the softening point was 100 ° C, the number average molecular weight was 700, and the initial color tone was 11 Gardner).

Comparative Example 5 (Preparation of Adhesive Composition) In Example 1 (2), pure monomer resin “FTR6100” (manufactured by Mitsui Petrochemical Co., Ltd., softening point 100 ° C., number average) was used as a tackifier. (2) of Example 1 except that a molecular weight of 720 and an initial color tone of 60 Hazen) were used.
In the same manner as in the above, an adhesive composition was prepared.

Comparative Example 6 (Preparation of Adhesive Composition) In Example 1 (2), a rosin-based resin “Superester A-100” (manufactured by Arakawa Chemical Industries, Ltd., softening point 100) was used as a tackifier. ° C, number average molecular weight 720, initial color tone 5 (Gardner), except that (2) of Example 1 was used.
In the same manner as in the above, an adhesive composition was prepared.

The adhesive compositions obtained in Examples and Comparative Examples were evaluated by the following tests. Table 1 shows the evaluation results.

(Adhesive Strength) The adhesive composition heated and melted at 180 ° C. was hot-melt coated on aluminum with a bar coater. This aluminum was adhered to a cardboard as an adherend with an adhesive area of 25 mm × 125 mm using an iron heated to 150 ° C., and then left at 20 ° C. for 24 hours. Then, at the temperature of 5 ℃ ・ 20 ℃ ・ 35 ℃ ・ 50 ℃,
A 180-degree peel test was performed using Tensilon to measure the adhesive strength (kg / 25 mm) to the cardboard. In addition, the broken material means that there is no peeling at the bonding surface and the cardboard itself is destroyed, and the partial material breaking means that there is a portion peeled off at the bonded surface and a portion where the cardboard itself is broken. .

(Holding force) The adhesive composition heated and melted at 180 ° C. was hot-melt coated on aluminum with a bar coater. This aluminum was adhered to a cardboard as an adherend with an adhesive area of 25 mm × 25 mm using an iron heated to 150 ° C., and then left at 20 ° C. for 24 hours. afterwards,
The falling time when a load was applied under the conditions of 60 ° C. and 1.0 kg was measured. The longer the fall time (minutes), the better the holding power.

(Odor) The odor of the adhesive composition heated and melted at 180 ° C. was evaluated by a sensory test according to the following criteria. ：: good, no unpleasant odor Δ: Somewhat unpleasant odor is felt. X: Bad, unpleasant odor like sticky nose.

[0038]

[Table 1]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C09J 125: 00)

Claims (2)

[Claims] 1. A tackifier for an ethylene copolymer obtained by using a hydride of an aromatic hydrocarbon resin obtained by polymerizing a C9 fraction, wherein the tackifier for an aromatic ring of the aromatic hydrocarbon resin is used. A tackifier for an ethylene-based copolymer having a hydrogenation ratio of 5% or more and 30% or less and an initial color tone of 1 Gardner or less. 2. An adhesive composition comprising 100 parts by weight of an ethylene copolymer, 50 to 150 parts by weight of the tackifier according to claim 1, and 10 to 100 parts by weight of a wax.