JPH093422A - Hot melt adhesive composition - Google Patents

Abstract

PURPOSE: To obtain a hot melt adhesive composition good in adhesive force in a wide region ranging from a low temperature region to a high temperature region by adding a crystalline terpene phenol compound in a specific amount of an adhesion-imparting agent. CONSTITUTION: A terpene phenol compound having a crystallizing property and obtained by reacting diterpene, limonene or α-pinene with phenol in the presence of an acidic clay catalyst in toluene solvent at 60-120 deg.C is contained in an amount of 1-60wt.% (preferably 1-40wt.%) as an adhesion-imparting agent. A hot melt adhesive comprises a base polymer such as PE, an adhesion- imparting agent such as rosin, and a wax such as Fisher-Tropsch wax.

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 adhesive strength from a low temperature range to a high temperature range.

[0002]

2. Description of the Related Art Hot-melt adhesives used for binding, packaging, woodworking, plywood, shoes, and parts assembly are usually base polymers, tackifiers, and if necessary waxes and softeners. , An antioxidant, a filler, a coloring agent and the like are mixed.

The nature of conventional hot melt adhesives is
Heat resistance is poor, and in order to improve that point, EVA (ethylene-vinyl acetate copolymer) with low MI (melt index) is used, wax with high crystallinity is used, and phenol-modified high softening point adhesion is used. There are methods such as using an imparting agent.

However, in the case of the conventional hot melt adhesive, the hardness of the adhesive itself improves the heat resistance, and the adhesive strength in the low temperature range is extremely lowered.

On the contrary, in order to improve the adhesive strength in a low temperature range, there are methods such as using EVA having a high MI, wax having a low crystallinity, and a tackifier having a low softening point. However, in that case, heat resistance cannot be obtained, and there is a demand for a hot melt adhesive having good adhesive strength from a low temperature region to a high temperature region.

Conventionally, as tackifying resins, aliphatic petroleum resins, alicyclic petroleum resins, aromatic petroleum resins, rosin resins, terpene resins (terpene resins, terpene phenol resins) and their hydrogenated resins Amorphous resins such as are used, and a high softening point resin is used to improve the adhesive strength in the high temperature range, and a low softening point resin is used to improve the adhesive strength in the low temperature range. However, as long as an amorphous resin is used, a hot melt adhesive having excellent adhesive strength from a low temperature range to a high temperature range cannot be obtained.

[0007]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a hot melt adhesive having good adhesive strength from a low temperature region to a high temperature region.

[0008]

[Means for Solving the Problems] In order to solve the above problems, the present invention provides a hot melt adhesive containing 1 to 60% by weight of a crystalline terpene phenol compound as a tackifier in the adhesive composition. The present invention provides a hot melt adhesive composition.

The hot melt adhesive will be described in detail below. The hot melt adhesive is mainly (A)
It is made up of components of a base polymer, (B) tackifier and (C) wax.

The base polymer of the component (A) used in the hot melt adhesive composition may be a polymer usually used in hot melt adhesives and is not particularly limited, and examples thereof include the following.

1) polyethylene 2) ethylene-vinyl acetate copolymer (EVA) 3) modified EVA such as saponified EVA and graft modified EVA
Polymer 4) Ethylene / (meth) ethyl acrylate (EEA)
Ethylene / (meth) acrylate copolymer such as 5) Ionomer resin obtained by partially neutralizing ethylene / (meth) acrylic acid copolymer 6) Ethylene / propylene copolymer, ethylene / propylene / (meth) acrylic acid Terpolymer 7) Reaction product of a dimer acid, which is a dimer of a fatty acid such as soybean oil, tung oil, and tall oil, which is a reaction product of polyamide / diacid-based acid and a diamine, with an alkyldiamine such as ethylenediamine or diethylenetriamine. Products and nylons such as nylon 12. 8) Polyester 9) Propylene-based polymer; atactic polypropylene, etc. 10) Copolymer consisting of vinyl aromatic compound and conjugated diene compound and hydrogenated product thereof; specifically, styrene / butadiene random copolymer, styrene / isoprene Random copolymer, butadiene / polystyrene block copolymer, polystyrene / polyisoprene block copolymer, polystyrene / polyisoprene / polystyrene triblock copolymer, polystyrene / polybutadiene / polystyrene triblock copolymer, poly (α-methyl) Examples thereof include styrene) / polybutadiene / poly (α-methylstyrene) triblock copolymers and hydrogenated products thereof. 11) Other polymers; vinyl acetate copolymer-based polymers, vinyl acetate-crotonic acid copolymer-based polymers, vinyl acetate-phthalic anhydride copolymer-based polymers, vinyl acetate-vinylpyrrolidone-based polymers, cellulose derivative-based polymers, polymethylmethacrylate Examples thereof include polymer, polyvinyl ether polymer, polyurethane polymer, thermosetting resin polymer, syndiotactic polypropylene, ethylene-propylene polymer and the like. Of these, ethylene-vinyl acetate copolymer and modified EVA polymer are preferably used.

In the hot melt adhesive composition, these base polymers may be used alone or in combination of two or more.

The tackifier, which is the component (B) of the hot melt adhesive composition, is added in order to adjust the viscosity of the base polymer when it is melted and to improve the hot tack and wettability. The tackifier may be any one as long as it can improve the hot tack and wetting of the base polymer, and is not particularly limited.

Specific examples of the tackifier which is the component (B) include rosin, modified rosin or ester compounds thereof, terpene resin, aliphatic petroleum resin, alicyclic petroleum resin, aromatic petroleum resin. Examples of suitable tackifiers include a copolymerized petroleum resin of an aliphatic component and an aromatic component, a low molecular weight styrene resin, an isoprene resin, an alkylphenol resin, a coumarone / indene resin, and a hydrogenated resin of each. These tackifiers may be used alone or in combination of two or more.

The crystalline terpene phenol compound, which is the component (B) of the hot melt adhesive composition of the present invention, is obtained by synthesizing terpenes and phenols.

Examples of the crystalline terpene phenol compound as the component (B) include terpenes such as α-pinene, β-pinene, dipentene and Δ ³ -calene, and two or more kinds thereof may be used in combination. it can. Examples of phenols include phenol, cresol, xylenol, propylphenol, nonylphenol, methoxyphenol, bromophenol, hydroquinone, resorcinol,
Examples thereof include dihydroxynaphthol, naphthol, methylnaphthol and the like, and two or more kinds can be used in combination. These combinations are not particularly limited.

Production of these crystalline terpene phenol compounds can be carried out according to known methods. For example, in solution polymerization method, aluminum chloride as a catalyst, Friedel-Crafts catalyst such as boron fluoride, acid clay,
Examples thereof include acidic catalysts such as sulfuric acid, phosphoric acid, and ion exchange resins. Examples of the solvent include aromatic hydrocarbon solvents such as toluene, xylene and benzene. The reaction temperature can be synthesized in the range of 20 ° C to 200 ° C. Specifically, it can be obtained by reacting α-pinene or dipentene with phenol at 60 ° C to 120 ° C in a toluene solvent under an acidic clay catalyst. The obtained terpene phenol compound is a compound of terpene: phenol = 1: 1, 1: 2 or 2: 2 and has crystallinity because the molecular weight distribution is extremely narrow. The above-mentioned crystalline terpene phenol compounds are classified according to the difference in the ratio of terpene: phenol, and are classified into YP-90, YP
-90L, YP-90J, YS resin 85, YP-10
It is commercially available from Yasuhara Chemical Co., Ltd. under the trade name of 0L and can be easily obtained.

The terpene fail compound having crystallinity in the hot melt adhesive composition may be used alone or in combination of two or more.

The wax which is the component (C) of the hot melt adhesive composition lowers the working temperature and melt viscosity at the time of melt coating of the hot melt adhesive, improves the stringiness, and adjusts the open time. It is added for the purpose of preventing blocking after coating, but any type of wax can be used as long as it has good compatibility with the base polymer and tackifier, and there is no particular limitation. Not done.

Specific examples of the wax which is the component (C) include petroleum waxes such as paraffin and microcrystalline wax, and synthetic waxes such as Fischer-Tropsch and low molecular weight polyethylene wax. These waxes may be used alone or in combination of two or more, but Fischer-Tropsch wax and polyethylene wax are preferably used.

The hot melt adhesive composition of the present invention contains a crystalline terpene phenol compound as a tackifier in an amount of 1 to 60% by weight in the adhesive composition. 1% by weight of crystalline terpene fail compound
If it is less than this, it means that sufficient adhesive force cannot be obtained. If it exceeds 60% by weight, the cohesive force of the adhesive itself cannot be obtained. It is preferably used in the range of 1 to 40%.

The hot-melt adhesive composition contains, in addition to the above base polymer, a tackifier containing a crystalline terpene phenol compound, and a wax, various compounding agents, if necessary, within a range not impairing the object of the present invention. For example, you may mix | blend a softener, a stabilizer, a filler, an antioxidant, etc.

[0023]

[Function] In a hot melt adhesive, a terpene phenol compound having crystallinity as a tackifier is contained in the adhesive composition in an amount of 1 to 60% by weight, so that the hot melt adhesive has excellent adhesive strength from a low temperature region to a high temperature region. The agent can be prepared.

[0024]

EXAMPLES Examples will be described below, but the present invention is not limited to the examples. The crystalline terpene phenol compound YP used in Examples 1 to 3 below.
-90L is synthesized as follows, for example. After charging 564 g of phenol and 34 g of acid clay in a four-necked flask having an internal volume of 1 liter equipped with a thermometer, a stirrer, a dropping funnel and a cooling tube, while maintaining the temperature at 80 ° C.,
136 g of limonene was added dropwise over 4 hours, and then stirred for 2 hours to cause a reaction. Next, the acid clay was removed from the mixed solution by filtration, the obtained reaction solution was washed twice with distilled water, and then the mixture was kept at 250 ° C. for 30 minutes under a reduced pressure of 5 mmHg to remove residual phenol and by-products. Obtained by distilling off.

Example 1 40 g of ethylene-vinyl acetate copolymer (Sumitate MB-11 manufactured by Sumitomo Chemical Co., Ltd.), aromatic modified terpene resin (YS resin TR105 manufactured by Yasuhara Chemical Co., Ltd.) 36
g, 4 g of a crystalline terpene phenol compound (YP-90L manufactured by Yasuhara Chemical Co., Ltd.), and 20 g of microcrystalline wax (Esmax 180 manufactured by Toa Fuel Industry Co., Ltd.) were melt mixed at 170 ° C. to prepare a hot melt adhesive composition. The obtained hot melt adhesive composition was applied to an aluminum foil (100 μm) by ADOS HOT SHOT G
A sample was prepared by applying 1 mmφ at 170 ° C. using UN, applying an open time of 2 seconds, pressurizing with 2 kg for 2 seconds, and cutting into a 25 mm width. The sample was subjected to an adhesive force and a peel creep test, and the melt viscosity of the adhesive composition was measured. The results are shown in Table 1. The test method of the sample and the melt viscosity measurement method were as follows. (1) Adhesive force measurement Equipment used: Shimadzu Autograph AGS-10KND Tension direction; T-type peeling Tension speed; 300 mm / min Measurement temperature; 0 ° C, 23 ° C, 60 ° C (2) Peeling creep measurement Load direction; T-type peeling Load: 100g Measuring temperature: 50 ° C (3) Melt viscosity measurement Equipment used: Tokyo Keiki Co. B8H type viscometer Measuring temperature: 170 ° C

Example 2 A hot melt adhesive composition was prepared in the same manner as in Example 1 except that the combination ratio of YS resin TR105 and YP-90L was changed, and an adhesive force and a peel creep test were conducted.
The melt viscosity of the adhesive composition was measured. The results are shown in Table 1.

Comparative Example 1 A hot melt adhesive composition was prepared in the same manner as in Example 1 except that YS resin TR105 was used instead of YP-90L, and the melt viscosity was measured and the adhesive strength and peel creep were measured. The test was conducted. The results are shown in Table 1.

Comparative Example 2 Instead of YS resin TR105 and YP-90L, disproportionated rosin ester (Superester A manufactured by Arakawa Chemical Industry Co., Ltd.)
A hot melt adhesive composition was prepared in the same manner as in Example 1 except that -100) was used, and the melt viscosity was measured and the adhesive strength and the peel creep test were performed. The results are shown in Table 1.

Example 3 40 g of an ethylene-vinyl acetate copolymer (Sumitate KC-10 manufactured by Sumitomo Chemical Co., Ltd.), 40 g of a crystalline terpene phenol compound (YP-90L manufactured by Yasuhara Chemical Co.),
A hot melt adhesive composition was prepared in the same manner as in Example 1 using 20 g of microcrystalline wax (Smax 180 manufactured by Toa Fuel Industry Co., Ltd.) to prepare a sample. The sample was tested for adhesion and peel creep, and
The melt viscosity of the adhesive composition was measured. The results are shown in Table 2.

Comparative Example 3 A hot melt adhesive composition was prepared in the same manner as in Example 3 except that an amorphous terpene phenolic resin (YS Polystar-S145 manufactured by Yasuhara Chemical Co., Ltd.) was used instead of YP-90L. Then, the melt viscosity was measured, and the adhesive strength and peeling creep test were performed. Table 2 shows the results.

Comparative Example 4 A hot melt adhesive composition was prepared in the same manner as in Example 2 except that a disproportionated rosin ester (Superester A-100 manufactured by Arakawa Chemical Industry Co., Ltd.) was used instead of YP-90L. After the preparation, the melt viscosity was measured, and the adhesive strength and peeling creep test were performed. Table 2 shows the results.

[0032]

[Table 1]

[0033]

[Table 1]

[0034]

[Table 2]

[0035]

The hot melt adhesive composition of the present invention comprises:
Since it has an appropriate melt viscosity, it can exhibit excellent adhesive strength from low temperature to high temperature while maintaining good workability.

Claims (2)

[Claims] 1. A hot-melt adhesive composition comprising a crystalline terpene phenol compound as a tackifier in an amount of 1 to 60% by weight in the adhesive composition. 2. The crystalline terpene phenol compound comprises dipentene or limonene or α-pinene and phenol under acidic clay catalyst at 60 ° C. in a toluene solvent.
The hot melt adhesive composition according to claim 1, which is a terpene phenol compound obtained by reacting at 120 ° C.