JPH0967552A - Tackifier composition and hot-melt adhesive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a tackifier compsn. which has a high adhesive power and is excellent in color tone and resistance to thermal degradation. SOLUTION: This tackifier compsn. contains a resin component comprising an arom. hydrocarbon resin having phenolic hydroxyl groups and/or its hydrogenation product pref. in an amt. of 100 pts.wt. and a di(alkylthiomethyl)alkylphenol represented by the formula (wherein each R1 is independently 6-18C alkyl; and R2 is 1-12C alkyl) pref. in an amt. of 10 pts.wt. or lower. The hot-melt adhesive compsn. is prepd. by compounding 100 pts.wt. thermoplastic elastomer, 50-150 pts.wt. abovementioned tackifier compsn., and 10-100 pts.wt. wax or oil.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a tackifier composition and a hot melt adhesive composition.

[0002]

2. Description of the Related Art Hot melt adhesives are used in a wide range of fields such as bookbinding, packaging, and sanitary materials, and the demand for them is increasing year by year due to their low environmental problems and good workability. There is. However, as the number of difficult-to-adhesive substances has increased due to expansion of applications and surface modification of base materials, it has become difficult to obtain sufficient adhesive performance with the adhesiveness of conventional hot melt adhesives. Further, in order to provide a clean feeling, it has been required in the field of application of the hot melt adhesive to be close to colorless and odorless.

Therefore, there is a strong demand for the development of a hot melt adhesive which has improved adhesive strength and is colorless and odorless. Therefore, improvement studies of base polymers and tackifying resins have been widely conducted. Among them, as disclosed in JP-A-3-227388, a hot melt adhesive containing a phenol-modified aromatic hydrocarbon resin or a hydride thereof as a tackifier is known to have a very strong adhesive force. Has been.

However, the aromatic hydrocarbon resin having a phenolic hydroxyl group is a compound of the aromatic hydrocarbon resin in which the synthetic hydrocarbon resin, which is a constituent component of the aromatic hydrocarbon resin, reacts with phenol as described later. Since the number of conjugated systems is increased, it is more susceptible to oxidative deterioration, and the color tone is very poor as compared with the general aromatic hydrocarbon resins.

The aromatic hydrocarbon resin having a phenolic hydroxyl group is severely deteriorated by heating, and even if it is hydrogenated to improve the initial color tone, it is the same. For this reason, when this resin is used as a tackifier for hot melt adhesives, the hot melt adhesives are also markedly colored due to heat deterioration.

However, the antioxidants generally used for preventing such oxidative deterioration cannot effectively prevent the heat deterioration of the aromatic hydrocarbon resin having a phenolic hydroxyl group. Therefore, a hot melt adhesive using the resin has not been put to practical use so far because of its poor adhesiveness but poor color tone and heat stability.

[0007]

DISCLOSURE OF THE INVENTION The present invention relates to a tackifier composition comprising an aromatic hydrocarbon resin having a phenolic hydroxyl group and a hot melt adhesive composition containing the tackifier composition. The purpose is to improve the heating deterioration of.

[0008]

[Means for Solving the Problems] In order to solve the above problems, the present inventors effectively prevent heat deterioration of a tackifier composition comprising an aromatic hydrocarbon resin having a phenolic hydroxyl group. The study was made on a possible antioxidant. As a result, it has been found that the above-mentioned object can be effectively achieved by adding di (alkylthiomethyl) alkylphenol among known antioxidants. The present invention has been completed based on this new finding.

That is, the present invention provides an aromatic hydrocarbon resin having a phenolic hydroxyl value and / or a hydride thereof, and a general formula (1):

[0010]

Embedded image

A di (alkylthiomethyl) alkylphenol represented by the formula (wherein R _{1 s} independently of each other have 6 carbon atoms)
To 18 alkyl groups, R ₂ represents an alkyl group having 1 to 12 carbon atoms), a thermoplastic elastomer, the above-mentioned tackifier composition, and a wax or The present invention relates to a hot melt adhesive composition containing oil.

The aromatic hydrocarbon resin having a phenolic hydroxyl group is not particularly limited, but is generally a synthetic hydrocarbon resin obtained by cracking naphtha, especially 9
It is possible to use those obtained by polymerizing one having carbon atoms (for example, styrene, vinyltoluene, α-methylstyrene, indene, etc.) in the presence of phenols.

Further, as the phenols, general alkylphenols such as phenol or cresol, xylenol, pt-butylphenol, p-octylphenol and p-nonylphenol can be used. Of these, phenol is preferable in terms of adhesiveness. These phenols may be used alone or in combination of two or more. The amount of the phenols used is usually about 0.2 to 20 parts by weight, preferably 3 to 15 parts by weight, based on 100 parts by weight of the synthetic hydrocarbon resin.

The hydroxyl value of the obtained aromatic hydrocarbon resin having a phenolic hydroxyl group is 1 or more, preferably 20 to 100. When the hydroxyl value is less than 1, the remarkable effect of the present invention cannot be obtained. Also, the hydroxyl value is 2
The reason why 0 or more is preferable is to maintain good adhesiveness. Further, the reason why the hydroxyl value is preferably 100 or less is that the hydroxyl value of the available aromatic hydrocarbon resin having a phenolic hydroxyl group is usually about 100 or less, but the hydroxyl value exceeds 100. However, there is no particular problem.

The hydride of the aromatic hydrocarbon resin having a phenolic hydroxyl group is prepared by appropriately adjusting the conditions of the raw material aromatic hydrocarbon resin having a phenolic hydroxyl group in the presence of a hydrogenation catalyst. Then, it is obtained by carrying out a hydrogenation reaction. The hydrogenation rate of the aromatic ring of the resin is not particularly limited in the present invention, but in order to improve the initial color tone, it is preferable that the olefinic double bond in the resin is almost completely hydrogenated. If the olefinic double bond is almost completely hydrogenated, there is no particular problem in color tone even if the hydrogenation rate of the aromatic ring is 0%.

As the hydrogenation catalyst, various kinds of metals such as metals such as nickel, palladium, platinum, cobalt, rhodium, ruthenium and molybdenum or metal compounds such as oxides and sulfides thereof can be used. Such a hydrogenation catalyst may be used by supporting it on a carrier such as alumina, silica (diatomaceous earth), carbon or titania, which is porous and has a large surface area. 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. The amount of catalyst used is
It is about 0.01 to 5% by weight, preferably 0.1 to 1% by weight, of the aromatic hydrocarbon resin having a phenolic hydroxyl group as the raw material resin. If it is less than 0.01% by weight, hydrogenation tends to be difficult to proceed, and if it exceeds 5% by weight, hydrogenation tends to proceed too much.

The hydrogenation reaction is usually carried out at a hydrogenation pressure of 1
The reaction temperature is usually in the range of about 0 to 300 Kg / cm ^2.
It is performed in the range of about 50 to 300 ° C. The reaction time is usually about 1 to 7 hours. The hydrogenation reaction is carried out in a state where a hydrocarbon resin having a phenolic hydroxyl group is melted or dissolved in a solvent. As the solvent, cyclohexane, n
-Hexane, n-heptane, decalin and the like can be used.

Regarding the amount of the catalyst used and the reaction time, the batch type was used as the reaction type, but the flow type (fixed bed type, fluidized bed type, etc.) may be used as the reaction type. it can.

Further, since the hydroxyl value of the aromatic hydrocarbon resin having a phenolic hydroxyl group may decrease depending on the hydrogenation conditions and the like, the above-mentioned hydroxyl value must be determined in consideration of this. .

The softening point of the aromatic hydrocarbon resin having a phenolic hydroxyl group is usually 70 to 150 ° C, preferably 90 to 120 ° C. The number average molecular weight is usually 500 to 1600, preferably 500 to 900.
The hydride of the resin also has the same softening point and number average molecular weight.

The di (alkylthiomethyl) alkylphenol is a compound represented by the general formula (1), and among them, 2,4-di (alkylthiomethyl) -6-alkylphenol is preferable. R ₁ in the formula represents each independently an alkyl group having 6 to 18 carbon atoms, and examples thereof include a hexyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group, and an octadecyl group. Or may be a branched chain. R ₂ represents an alkyl group having 1 to 12 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, an undecyl group, and a dodecyl group, which are linear. Or it may be a branched chain. Particularly, those in which both R _1's represent an octyl group and R _2's represent a methyl group are preferred.

The tackifier composition of the present invention comprises an aromatic hydrocarbon resin having a phenolic hydroxyl group and / or a hydride thereof containing di (alkylthiomethyl) alkylphenol as an antioxidant. By the selection of both, the above-mentioned object was achieved for the first time. Di (alkylthiomethyl) alkylphenol has a particularly effective effect on the resin and / or its hydride or a hot melt adhesive containing them, but it does not necessarily have an effective effect depending on other antioxidants. It does not represent. On the other hand, even for di (alkylthiomethyl) alkylphenols, tackifying resins having a phenolic hydroxyl group of other composition, such as rosin-modified phenolic resin and phenolic resin, and hot-melt adhesives containing them Does not necessarily represent an effective effect.

The amount of the above-mentioned di (alkylthiomethyl) alkylphenol used with respect to the aromatic hydrocarbon resin having a phenolic hydroxyl group is 10 parts by weight or less of di (alkylthiomethyl) alkylphenol per 100 parts by weight of the resin. Appropriate, preferably 0.1-2
Parts by weight.

In the present invention, a hot melt adhesive composition having improved heat stability can be produced by mixing the tackifier composition with a thermoplastic elastomer and wax or oil.

Examples of the thermoplastic elastomer serving as the base polymer in the present invention include ethylene-based copolymers, styrene-conjugated diene-based copolymers, polyorphin-based copolymers and polyurethanes.

The ethylene-based copolymer is a copolymer of ethylene and a monomer copolymerizable therewith, and those conventionally used for hot-melt adhesives can be used. Examples of the monomer copolymerizable with ethylene include vinyl acetate. Vinyl acetate content is usually 20-4
It is about 5% by weight. The molecular weight of the melt index (190 ° C., load 2160 g, 10 minutes) is 10-4.
It is preferably about 00 g / 10 minutes.

The styrene-conjugated diene copolymer is S-containing styrene, isoprene and styrene.
IS type copolymer (hereinafter abbreviated as SIS), styrene-butadiene copolymer made of styrene and butadiene (hereinafter abbreviated as SB), S-BS made of styrene, butadiene and styrene. Type copolymer (hereinafter abbreviated as SBS), S-E-B-S type copolymer (hereinafter abbreviated as SEBS) consisting of styrene, ethylene, butylene and styrene, and styrene.
S-E- consisting of ethylene, propylene and styrene
A P-S type copolymer (hereinafter abbreviated as SEPS) or the like is applicable.

The polyolefin copolymer is an atactic polypropylene resin (hereinafter abbreviated as APP) or an amorphous polyalphaolefin (for example, a random copolymer obtained by copolymerizing propylene and ethylene or butene-1), which is amorphous. Polyolefin resin, manufactured by Ube Lexen Co., Ltd.) and the like.

As the wax or oil in the present invention, the wax or oil conventionally used in hot-melt adhesives can be similarly used, but it is particularly preferable to select it on the basis of each solubility characteristic and molecular weight.

As the wax, paraffin wax,
Examples thereof include synthetic waxes such as microcrystalline wax, petroleum wax, Fischer-Tropsch wax, and low molecular weight polyethylene, which may be naturally produced or synthetic.

Examples of oils include naphthenic oils, paraffinic oils, and plasticizing oils such as aromatic oils, and naphthenic oils and paraffinic oils are preferable from the viewpoint of less reduction in cohesive force. Specifically, naphthenic process oil, paraffinic process oil,
Liquid polybutene and the like can be mentioned.

The composition ratio of the hot melt adhesive composition containing the above components is not particularly limited, but in order to obtain good adhesive strength and holding power, 100 parts by weight of the thermoplastic elastomer is added. On the other hand, 50 to 150 parts by weight of the above-mentioned tackifier composition, wax or oil 10
Preferably it is 100 parts by weight. This is because when the tackifier is less than 50 parts by weight, sufficient adhesive force cannot be obtained, and when it exceeds 150 parts by weight, sufficient holding force cannot be obtained, and wax or oil is less than 10 parts by weight. In this case, the melt viscosity of the obtained adhesive composition becomes too high, and when it exceeds 100 parts by weight, sufficient holding power cannot be obtained.

In the hot melt adhesive composition of the present invention, if necessary, a thickener, a filler, a light stabilizer,
Metal deactivator, plasticizer, lubricant, flame retardant, antistatic agent,
An additive such as a pigment can be added, and an antioxidant other than the di (alkylthiomethyl) alkylphenol used in the present invention can be used in combination.

[0034]

According to the present invention, a tackifier composition comprising an aromatic hydrocarbon resin having a phenolic hydroxyl group and its hydride contains di (alkylthiomethyl) alkylphenol for a long period of time. It is possible to provide a tackifier having high adhesive strength, excellent color tone, transparency and heat deterioration. Further, by using the tackifier thus obtained, it is possible to provide a hot melt adhesive having the above characteristics. Such a hot melt adhesive composition can be widely used for various applications such as bookbinding, packaging and sanitary materials.

[0035]

The present invention will be described in more detail with reference to the following 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 composition Aromatic hydrocarbon resin having a phenolic hydroxyl group with a hydroxyl value of 73 ("Neopolymer E-100", manufactured by Nippon Petrochemical Co., Ltd., quantity) (Average molecular weight 563, softening point 90 ° C)
100 parts and 2,4-di (octylthiomethyl) -6-
0.5 parts of methylphenol (“IRGANOX 1520D”, manufactured by Ciba Geigy) is heated to about 150 ° C.,
The mixture was thoroughly mixed using a stirrer to obtain a tackifier composition. Add this tackifier composition to a 70 cc glass container.
Filled with 0 parts, left in a circulating air dryer at 180 ° C for 48 hours,
An aging measurement of heating stability (hereinafter, simply referred to as “aging measurement”) was performed. The results are shown in Table 1.

(2) Production of Hot Melt Adhesive Composition 40 parts of the tackifier composition obtained in (1) and wax ("Hi-Mic-1080", manufactured by Nippon Seiro Co., Ltd.) 2
0 parts were melt mixed at 160 ° C. Then, 40 parts of an ethylene-vinyl acetate copolymer (“Evaflex EV220”, manufactured by Mitsui DuPont Polychemical Co., Ltd.) was added and thoroughly mixed using a stirrer to obtain a uniform hot melt adhesive composition. It was 140% of this hot melt adhesive composition
Pack 50 parts in a cc glass container and put 180 in a circulating air dryer.
The sample was left to stand at 48 ° C. for 48 hours, and aging measurement was performed. The results are shown in Table 2.

Example 2 150 parts of an aromatic hydrocarbon resin having a phenolic hydroxyl group and a nickel-diatomaceous earth catalyst ("N-113", manufactured by JGC Corporation) described in (1) of Example 1 )
Charge 0.5 parts into an autoclave, hydrogen pressure 200 kg
/ Cm ² , the reaction temperature was 280 ° C, and the hydrogenation reaction was carried out under the conditions of a reaction time of 5 hours. After the reaction was completed, the obtained resin was dissolved in 300 parts of cyclohexane and the catalyst was removed by filtration. Then, the filtrate was placed in a 1-liter separable flask equipped with a stirring blade, a reflux condenser, a thermometer, a temperature controller and a pressure indicator,
The solvent is removed by gradually raising the temperature and reducing the pressure to 20 torr, the number average molecular weight 600, the softening point 97.0 ° C., the hydrogenation rate of the olefinic double bond 100%, the hydrogenation rate of the aromatic ring 8%, 98 parts of a hydride of an aromatic hydrocarbon resin having a phenolic hydroxyl group having a hydroxyl value of 70 and a Gardner color tone of less than 1 was obtained.

The hydrogenation rate was calculated from the H-spectral area of the aromatic ring appearing at around 7 ppm in ¹ H-NMR of the raw material resin and the obtained hydrogenated resin according to the following formula. Hydrogenation rate = {1- (spectrum area of hydrogenated resin /
Spectral area of raw material resin)} × 100 (%). Also,
The softening point is based on the ring and ball method of JIS K 2531.

A tackifier composition was prepared in the same manner as in (1) of Example 1 except that the above-mentioned hydride of an aromatic hydrocarbon resin having a phenolic hydroxyl group was used, and aging measurement was carried out. It was The results are shown in Table 1. Further, a hot melt adhesive composition was produced using this tackifier composition in the same manner as in (2) of Example 1, and the aging measurement was performed. The results are shown in Table 2.

Comparative Example 1 In (1) of Example 1, a rosin phenol resin having a phenolic hydroxyl group (a number average molecular weight of 62) was used in place of the aromatic hydrocarbon resin having a phenolic hydroxyl group.
2, (1) of Example 1 except that a softening point of 150 ° C. was used.
A tackifier composition was prepared in the same manner as above, and the aging measurement was performed. The results are shown in Table 1. Further, using this tackifier composition, a hot melt adhesive composition was produced in the same manner as in (2) of Example 1, and the aging was measured. The results are shown in Table 2.

Comparative Example 2 In Example 1 (1), a phenol resin (“Tamanor 100S”, manufactured by Arakawa Chemical Industry Co., Ltd.) was used in place of the aromatic hydrocarbon resin having a phenolic hydroxyl group. Was prepared in the same manner as in (1) of Example 1, and the aging measurement was performed. The results are shown in Table 1. Also, using this tackifier composition, Example 1
A hot melt adhesive composition was produced in the same manner as in (2) above, and aging measurement was performed. The results are shown in Table 2.

Comparative Example 3 In Example 1 (1), a hydride of a C9 aromatic hydrocarbon resin (number average molecular weight 710, softening point 10) was used in place of the aromatic hydrocarbon resin having a phenolic hydroxyl group.
A tackifier composition was prepared in the same manner as in (1) of Example 1 except that 0 ° C.) was used, and the aging was measured. The results are shown in Table 1. Further, using this tackifier composition, a hot melt adhesive composition was produced in the same manner as in (2) of Example 1, and the aging was measured. The results are shown in Table 2.
Shown in

Comparative Example 4 In Example 1 (1), a rosin resin (“S” was used instead of the aromatic hydrocarbon resin having a phenolic hydroxyl group).
EA-100 ", manufactured by Arakawa Chemical Industry Co., Ltd. was used to prepare a tackifier composition in the same manner as in (1) of Example 1 and to measure aging. The results are shown in Table 1.
Further, using this tackifier composition, a hot melt adhesive composition was produced in the same manner as in (2) of Example 1, and the aging was measured. The results are shown in Table 2.

Comparative Example 5 A tackifier was prepared in the same manner as in (1) of Example 1 except that the di (alkylthiomethyl) alkylphenol represented by the general formula (1) was not included in (1) of Example 1. The composition was prepared and the aging measurement was performed. The results are shown in Table 1. Further, using this tackifier composition, a hot melt adhesive composition was produced in the same manner as in (2) of Example 1, and the aging was measured. The results are shown in Table 2.

Comparative Example 6 In place of the di (alkylthiomethyl) alkylphenol represented by the general formula (1) in (1) of Example 1,
Pentaerythrityl-tetrakis [3- (3,5-di-
t-Butyl-4-hydroxyphenyl) propionate] (“IRGANOX1010”, manufactured by Ciba Geigy), except that the tackifier composition was prepared in the same manner as in Example 1 (1), and the aging was measured. It was The results are shown in Table 1. Further, using this tackifier composition, a hot melt adhesive composition was produced in the same manner as in (2) of Example 1, and the aging was measured. The results are shown in Table 2.
Shown in

Comparative Example 7 In place of the di (alkylthiomethyl) alkylphenol represented by the general formula (1) in (1) of Example 1,
2,2-thio-diethylenebis [3- (3,5-di-t
-Butyl-4-hydroxyphenyl) propionate]
("IRGANOX 1035FF", manufactured by Ciba Geigy) was used, and a tackifier composition was prepared in the same manner as in (1) of Example 1 and aging measurement was performed. The results are shown in Table 1. Further, using this tackifier composition, a hot melt adhesive composition was produced in the same manner as in (2) of Example 1, and the aging was measured. The results are shown in Table 2.
Shown in

Comparative Example 8 In place of the di (alkylthiomethyl) alkylphenol represented by the general formula (1) in (1) of Example 1,
n-octadecyl-3- (3,5-di-t-butyl-4
-Hydroxyphenyl) propionate ("IRGAN
OX1076 ", manufactured by Ciba Geigy)
A tackifier composition was prepared in the same manner as in (1) of Example 1, and the aging was measured. The results are shown in Table 1. In addition, using this tackifier composition, (2) of Example 1
A hot melt adhesive composition was produced in the same manner as in, and the aging measurement was performed. The results are shown in Table 2.

Comparative Example 9 A tackifier composition was prepared in the same manner as in (1) of Example 1 except that the di (alkylthiomethyl) alkylphenol represented by the general formula (1) was not used in Example 2. Then, the aging measurement was performed. The results are shown in Table 1. In addition, using this tackifier composition, (2) of Example 1
A hot melt adhesive composition was produced in the same manner as in, and the aging measurement was performed. The results are shown in Table 2.

Comparative Example 10 In Example 2, instead of the di (alkylthiomethyl) alkylphenol represented by the general formula (1), pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4) was used. -Hydroxyphenyl) propionate] ("I
RGANOX1010 ", manufactured by Ciba Geigy) was used, and a tackifier composition was prepared in the same manner as in (1) of Example 1, and the aging was measured. The results are shown in Table 1. Further, using this tackifier composition, a hot melt adhesive composition was produced in the same manner as in (2) of Example 1, and the aging was measured. The results are shown in Table 2.

Comparative Example 11 In Example 2, instead of the di (alkylthiomethyl) alkylphenol represented by the general formula (1), 2,2-
Thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] ("IR
GANOX 1035FF "manufactured by Ciba Geigy) was used, and a tackifier composition was prepared in the same manner as in (1) of Example 1, and the aging was measured. The results are shown in Table 1. Also, using this tackifier composition, Example 1
A hot melt adhesive composition was produced in the same manner as in (2) above, and aging measurement was performed. The results are shown in Table 2.

Comparative Example 12 In Example 2, n-octadecyl-3- (3,5-di-t-butyl-4-hydroxy) was used instead of the di (alkylthiomethyl) alkylphenol represented by the general formula (1). Phenyl) propionate (“IRGANOX10
76 "manufactured by Ciba-Geigy Co., Ltd.
A tackifier composition was prepared in the same manner as in (1) above, and aging measurement was performed. The results are shown in Table 1. Further, using this tackifier composition, a hot melt adhesive composition was produced in the same manner as in (2) of Example 1, and the aging was measured. The results are shown in Table 2.

In each aging measurement, visual evaluation was performed for each elapsed time. Table 1 shows the state of heat coloring based on the Gardner color of the tackifying resin composition after 48 hours have passed, and Table 2 shows the mist generation time and skin of the hot melt adhesive composition after 72 hours have passed. Tension occurrence time. The "haze" refers to deterioration that occurs nonuniformly throughout the adhesive composition, and the "skinning" refers to a state in which a film-like material is formed on the surface of the adhesive composition.

Next, the hot melt adhesive compositions obtained in Examples and Comparative Examples were evaluated for adhesive strength by the following method. The adhesive composition heated and melted at 180 ° C. was hot-melt coated on aluminum with a bar coder, and the aluminum was adhered to a surface-treated corrugated board having an adhesion area of 25 mm × 25 mm and a heat sealer 140.
After bonding under conditions of ℃, 2Kg and 1 second, 4 at 20 ℃
Left for hours. Then, a 180 degree peel test was performed with a tensilon at an ambient temperature of 20 ° C., and the adhesive strength was evaluated according to the following criteria according to the degree of material destruction of the corrugated board. The measurement results are shown in the rightmost column of Table 2.

Strong: The material is completely destroyed. Or tensilon measured value of 2.5 kg or more. Normal: Material is partially destroyed. Alternatively, the tensilon measurement value is 1.5 kg or more and less than 2.5 kg. Weak: Does not destroy the material. Or tensilon measured value 1.5
Less than Kg.

[0056]

[Table 1]

[0057]

[Table 2]

From Table 1, it can be said that a mixture of an aromatic hydrocarbon resin having a phenolic hydroxyl group and di (alkylthiomethyl) alkylphenol is very excellent in heating stability. Further, from Table 2, the adhesive composition containing the mixture of the aromatic hydrocarbon resin having a phenolic hydroxyl group and the di (alkylthiomethyl) alkylphenol as the tackifier has excellent heat stability without impairing the adhesive property. Can be said to be excellent.

Claims (6)

[Claims] 1. An aromatic hydrocarbon resin having (A) a phenolic hydroxyl value and / or a hydride thereof, and (B) a general formula (1): A di (alkylthiomethyl) alkylphenol represented by the formula (in which R ₁ independently represents an alkyl group having 6 to 18 carbon atoms and R ₂ represents an alkyl group having 1 to 12 carbon atoms). A tackifier composition comprising: 2. The composition ratio of (A) and (B) is (A) 1.
(B) 10 parts by weight or less with respect to 00 parts by weight of a tackifier composition. 3. The di (alkylthiomethyl) alkylphenol of (B) is 2,4-di (alkylthiomethyl).
The tackifier composition according to claim 1 or 2, which is -6-alkylphenol. 4. The tackifier composition according to claim 1, wherein R ₁ represents an octyl group and R ₂ represents a methyl group. 5. A hot melt adhesive composition containing a thermoplastic elastomer, the tackifier composition according to claim 1 and a wax or an oil. 6. The tackifier composition 5 according to claim 1, wherein the thermoplastic elastomer is 100 parts by weight.
0-150 parts by weight, and wax or oil 10-
A hot melt adhesive composition containing 100 parts by weight.