JPS58189273A - Composition for foamed hot-melt adhesive - Google Patents

Abstract

PURPOSE:To provide the titled compsn. with stable foamability, showing effective sealing performance when applied to rough surfaces, by incorporating a surface-active fluorine compd. (or an organosilicon compd.) with a thermoplastic resin. CONSTITUTION:100pts.wt. thermoplastic resin which melts at 70-250 deg.C and becomes fluid, selected from an addn. polymer [e.g., ethylene (co) polymer, acrylic resin] and an ester-type condensation polymer (e.g, bolyester prepared by condensation of an acid component consisting mainly of terephthalic acid and a diol component such as ethylene glycol) is mixed with about 0.001-5pts.wt. surface- active fluorine compd. (e.g., perfluoroalkylethylene oxide adduct) and/or organosilicon compd. (e.g., dimethylpolysiloxane/polyethylene oxide copolymer) under heating and melted to form a compsn. for foamed hot-melt adhesives.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a composition for hot melt adhesives, and more particularly to a composition for hot melt adhesives that exhibits stable foaming properties, adheres to uneven surfaces, and exhibits effective sealing functions. It is about things.

Many techniques for foaming and utilizing resins have been known in the past. For example, techniques for using expanded polystyrene as a packaging material and foaming urethane for use as molded products are widely practiced. The use of these foams is based on the properties of the resin that makes up the foam or the attributes resulting from the foaming method, and therefore, in many cases, the range of uses for foams is largely determined by the type of resin used. ing. Therefore, in the development of uses for foams, resins with properties suitable for the intended use are selected, and efforts are being made to foam them. Japanese Patent Publication No. 54-15967
In the invention disclosed in the publication, polyethylene,
Efforts have been made to add surfactants to polypropylene, ethylene-vinyl acetate copolymers, polyesters, and polyamides to form foam in the molten state, which can then be used in hot-melt adhesives.

In this publication, the stability of the foam of the molten resin is improved by using a hydrocarbon surfactant consisting of a lipophilic group and a hydrophilic group, but this alone is not necessarily sufficient to stabilize the foam.
One method is to add inorganic fine powder to prolong the life of the foam.

However, since finely powdered inorganic substances have the disadvantage of inhibiting the abrasion of hot melt foam coating equipment, the amount added is limited to a very small amount, and if possible, it is preferable not to use inorganic substances.

The present inventor has conducted various studies on surfactants that are suitable for hot melt foam coating equipment and improve the stability (life span) of molten resin foam without using inorganic substances.
The present invention was completed based on the discovery that fluorine-based surfactants and/or organosilicon-based surfactants are very effective.

That is, the present invention comprises a thermoplastic resin selected from the group consisting of addition polymers and ester condensation polymers that are solid at room temperature and exhibit fluidity when melted at temperatures of 70 to 250°C, and fluorine having surface-active properties. The present invention provides a foamed hot melt adhesive composition comprising a compound and/or an organosilicon compound.

The thermoplastic resin used in the present invention is a polymer produced by a known method, and exhibits fluidity by melting at a temperature of 70 to 250°C. Preferably 70-2
The melt viscosity measured by a B-type viscometer at a temperature of 50° C. is 5 Q O,Q Q Q ape or less, more preferably 100.000 apa or less.

Monomers used in the production of such addition polymers include olefins such as ethylene and propylene, acrylic acid,
Methyl acrylate, enal acrylate, propyl acrylate, butyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, lauryl acrylate, 2-ethylhexyl acrylate, acrylonitrile, methacrylaterile.

Acrylic yarn binding materials such as acrylamide and methacrylamide, styrene, and 0-methylstyrene.

m-methylstyrene, p-methylstyrene, ethylstyrene, α-vinylstyrene, α-chlorostyrene, α-
Alkenyl aromatic monomers such as bromostyrene, vinyl monomers such as vinyl chloride, JIiL vinyliso7, vinyl bromide, vinyl acetate, vinyl pyrrolidone, and vinyl stearate.

Diene yarn pickers such as butadiene, isoprene, and chloroprene are exemplified. These heptamers may be copolymerized by mutual pressure, and if necessary, they may be copolymerized with crotonic acid, itaconic acid, maleic acid, methylmaleic acid, fumaric acid, vinylbenzoic acid, or the like.

Preferred addition polymers include polyethylene, atactic polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl acetate-vinyl alcohol copolymer, ethylene-vinyl acetate-vinyl chloride copolymer, and maleic acid. Modified ethylene-vinyl acetate copolymer, acrylic acid modified ethylene-vinyl acetate copolymer,
polyisobutylene modified ethylene-vinyl acetate copolymer,
Ethylene-ethyl acrylate copolymer, ethylene-isobutyl acrylate copolymer, ethylene-acrylic acid copolymer.

Ethylene-acrylic acid-acrylamide-acrylic ester copolymer, ethylene-propylene-acrylic acid copolymer, ethylene-propylene-styrene block copolymer, polyisobutylene, polyvinyl butyral, polyvinyl ether, poly-α-methyl Styrene, polyvinyl alcohol, vinyl acetate-crotonic acid copolymer.

Vinyl acetate phthalic anhydride copolymer, vinyl acetate-vinyl pyrrolidone copolymer, polyacrylic ester, acrylic ester-acrylonitrile copolymer, methacrylic ester-acrylic acid copolymer, vinylidene chloride
Methacrylic acid ester copolymer, vinylidene chloride-acrylonitrile copolymer, polybutadiene, polyisoprene, polychloroprene, styrene-butadiene copolymer, styrene-isoprene-styrene block copolymer,
Styrene-butadiene-styrene block copolymers and the like.

Further, the dicarboxylic acid component used in the production of the ester type condensation polymer of the present invention is an aliphatic, alicyclic or aromatic one, such as oxalic acid.

Malonic acid, dimethylmalonic acid, succinic acid, altaric acid, adipic acid, trimethyladipic acid.

Pimelic acid, 2,2-dimethylgeltaric acid, acelaic acid. Sebacic acid, fumaric acid, maleic acid, itaconic acid, 1,5-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,5-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, phthalic acid, terephthalic acid , isophthalic acid, 1,4-naphthalene dicarboxylic acid, 2,5-naphthalene dicarboxylic acid,
2°6-7tale dicarboxylic acid, biphenyldicarboxylic acid, and ester-forming derivatives thereof are used. Examples of diol components include ethylene glycol, 1.2-7'ropanediol, 1. ! I-propanediol, 1,4-butanediol, 2,4-dimethyl-
2-ethylhexane-1,S-diol, neopentyl glycol, 2-ethyl-2-butyl-+, 5-furopanediol, 1,5-bentanediol, 1,6-
Hexanediol% 1.8-octanediol, 1
, 10-decanediol, 2,2.2-)rimether-1.6=hexanediol, 1,4-cyclohexane dimetatool, p-xylylene glycol, diethylene glycol 1. Examples include triethylene glycol, polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.

Polyesters having various features can be obtained by appropriately combining the above-mentioned sicicalibonic acid or its ester-forming derivative with a diol. In the present invention, the ester type condensation polymer preferably used is a terephthalic acid component with one or more components such as isophthalic acid, adipine w11 sebacic acid, etc. added, and ethylene glycol, diethylene glycol, I, 4-7" tanediol, neopentyl glycol It is a polyester that is polymerized by adding one type or two or more types of diols such as.

Additives such as tackifier resins, plasticizers, softeners, waxes, oils, antioxidants, and other fillers can be added to the above thermoplastic resin (base polymer) as needed. Tackifier resins are used to improve the wettability and workability of pot melt adhesives, and include rosin, U-784, f-rupene resin, terpene phenol resin, aliphatic petroleum resin, and aromatic resin. Petroleum resin, hydrogenated and copolymerized petroleum resin, dicyclohentacyene M stone fd
i resin, coumaron-indene resin, styrene resin,
It is selected from among isoprene-based resins and the like in consideration of compatibility with the pace polymer, softening point, thermal stability, and adhesiveness.

Plasticizers and cutting agents are added to improve wettability to adherends, low-temperature flexibility, impact resistance, etc., and dioctyl phthalate, dibutyl phthalate, polybutene, liquid polyisoprene, polyisobutylene, etc. are used. .

Wax and oil reduce melt viscosity, prevent blocking,
It is added to adjust oven time, etc., and /<y fin wax, microcrystalline wax, polyethylene wax, polypropylene wax, and other modified waxes are used. As antioxidants, hindered phenols, triazine derivatives, dialkylphenol sulfides, etc. are used. The types and proportions of these additives are appropriately selected depending on the intended use of the adhesive.

The fluorine compound used in the present invention has surfactant ability. In the present invention: ・Surface activity refers to the ability to lower the surface tension of the thermoplastic resin described in L in a molten state.

Since the fluorine compound according to the present invention must have surface-active ability, its chemical structure has a perfluoroalkyl group and a lipophilic group portion and/or a hydrophilic group portion. The fluorine compound may be one in which hydrogen in an organic group is replaced with fluorine by an electrolytic fluorination method, or may be obtained by low polymerizing an ethylenically unsaturated compound fluorinated by a telomerization method or an oligomerization method. It may be something.

For example, generally known fluorinated surfactants and fluorinated oligomeric surfactants represented by the following general formula are often used in the present invention.

Rf802 - N - (2
o+mH+ (OH2)zOP O5M2 + -O
H20H20bo 5M +÷. H2) 7cooM, l
Yoya. J) 7N' (R) sLlm LZ I ~5
t is an integer of 1 to 5, M is hydrogen or a cation, and L is an anion. ) RfSoSM (2) (R1 in the formula
, M are the same as formula (1)) R, t, M are the same as formula (1)) L are the same as formula (1), Y are the same as formula (3)) Rf-0 moaH2cH20) Stone W. ... (5) (in the formula Rf
, m are the same as equation (1), and W is El and Rf.

l is an integer from 1 to 50, R and L are the same as in formula (1)) af-
aH2aH2=V −・−・(6)CH2N)I2
O3(OH20H20)-gH, -0壬CH2CH2■
-,803M.

-8OH%+20ONH2CH2G[(2S06M or -5aH2cooc2H4'i!i'(CH3) 5L
and m, M, and L are the same as in formula (1)) Among these, those having a nonionic or anionic parent group are preferable from the viewpoint of thermal stability.O The organosilicon compound used in the present invention is There must be 8 in the molecule
Although the compound has an l-0-8i bond, it is preferable that the compound further has an anionic, ionic, or nonionic hydrophilic group in addition to this bond. As anionic hydrophilic groups, sulfonic acid groups, sulfate groups, carboxylic acid groups, phosphoric acid groups, etc. are used in alkali gold with 6 ions and ammonium ions as counter ions, and as nonionic hydrophilic groups, hydroxyl groups, amino groups, etc. , a polyoxyalkyl group, and an amine oxide group, and as the cationic parent group, a group having quaternary nitrogen is used. When the molecular core is polysiloxane, the viscosity at 25°C is 20,000.
Polysiloxanes of cps or less and having various hydrophilic groups introduced therein as appropriate may also be used. For example, commonly known alkylpolysiloxanes such as dimethylpolysiloxane and methylhydrodienepolysiloxane, amine-modified polysiloxanes, alcohol-modified polysiloxanes, carboxyl-modified polysiloxanes, logisane, fluorine-modified polysiloxanes, polyether-modified polysiloxanes, and polysiloxanes. Sulfonates, carboxylic acid groups of polysiloxane, aminosulfonates of polysiloxane, etc. are used. In addition, when the core of the molecule is a carbon chain, it has a 5i-0-8i bond in the molecule, a hydrophilic group is bonded to the chain, and nitrogen, oxygen, silicon, nitrogen, oxygen, silicon, A generally known material containing sulfur or the like is used.

The amount of the fluorine compound or organosilicon compound added to the thermoplastic resin is o, o O+~5 P)iR (heavy part/100 parts by weight of resin), preferably 0.00'5~l
It is PHR. If the amount added is smaller than o, oO+PHR, the foam stability during foaming will be poor, and if it is greater than 5PI(R), it will have a negative impact on the physical properties of the resin, such as causing a decrease in resin strength.

The fluorine compound or organosilicon compound according to the present invention is added and mixed by heating and melting the thermoplastic resin. Mixing is carried out using a generally known heated stirring tank, related mixer, milling roll, extruder, or the like. The composition according to the invention can be produced in this way. After production, the composition may be used as is, or it may be cooled and kept in storage, or it may be cooled and pulverized and stored, and then used in the amount required for the poem that needs to be used. You can also use

It is also effective to use the composition C6 in the present invention by introducing foam in a molten state and applying, injecting, or molding the foamed state.

The gas constituting the bubbles may be nitrogen, carbon dioxide, or air. Other inert gases can also be used. Bubbles may be introduced by melting the composition according to the invention, blowing gas, and applying pressure if necessary. Another method is to use a blowing agent and mix it into the composition of the present invention at a temperature below the temperature at which the blowing agent releases gas, and then raise the temperature during use to above the gas release temperature of the blowing agent. It is also possible to introduce In this case, generally known blowing agents are used, such as nitroso blowing agents such as dinitrosopentamethylenetetramine, azo thread blowing agents such as diazocarboxylic acid amide, p.

〆-oxybisbenzenesulfonylhydrazide and 5,
Examples include aromatic hydrazide blowing agents such as 5-disulfonylhydrazide diphenylsulfon. The blowing agent is selected to have a decomposition temperature higher than the softening point of the thermoplastic resin, and is used in an amount of 0.5 to 15 parts by weight per 100 parts by weight of the resin.

The foaming hot melt adhesive composition according to the present invention may be foamed using equipment, but in this case, the equipment may be disclosed in Japanese Unexamined Patent Publication Nos. 54117544 and 1983.
The hot-melt applicator of the heating and pressurizing type disclosed in Japanese Patent Application Laid-open No. 15967 and Japanese Patent Application Laid-open No. 17645/1988 is highly praised. Using this applicator, an inert gas such as nitrogen gas, carbon dioxide gas, or air can be dissolved or dispersed in the melt of the composition of the present invention under high pressure, and foamed by discharging it into normal pressure. If a foaming machine is not used, the foaming agent is melted and mixed with the composition of the present invention at a temperature below the decomposition temperature, formed into a thread, string, film, web, powder, etc., and placed on a substrate. It can also be used for hot melt applications by heating and foaming.

The foamed hot melt adhesive composition of the present invention exhibits various useful functions because the foam after foaming is extremely stable, and depending on the type of thermoplastic resin, it forms a soft or hard foam. . For example, it can be used as a sealant, but if the composition according to the present invention is foamed and filled into a gap, it will adhere and harden in the gap, forming a foam structure consisting of closed cells and filling the gap. to seal. When a hard resin such as terephthalic acid-based polyester is used as a sealant, it will not collapse even under considerable force, so it is used as a sealant for buildings by eaves houses with a good insulation effect and excellent sealing performance. enable. When a soft resin such as a rubber-based polymer is used as a sealing material, it has excellent vibration and shock absorbing power, and can also be used as a sealing material that can follow large deformations.

Since the foam formed by foaming the foamed hot melt 1 adhesive composition according to the present invention has a high chikuntropic property, it does not lean when applied to the surface of a kite. Therefore, even for products that had to be applied on a horizontal surface with the adherend lying on its side,
It can be applied in a vertical position, simplifying the work process.

By applying the foaming pot-melt adhesive composition according to the present invention and then press-bonding it, it is possible to fully exhibit its excellent function as a hot-melt adhesive with extremely high adhesion ability.

That is, if the composition is foam-coated on one adherend and the other adherend is overlapped and pressed together before it cools down, when the foam collapses, the composition spreads out substantially. The adhesive area becomes larger. As a result, the adhesive force is also greater than that of conventional non-foaming hot melt adhesives. Adhesive 1T on the contrary
When the i1 product is kept constant, the single foam hot melt adhesive spreads more easily, so the number of companies using the adhesive can be reduced, and the adhesive layer can be made thinner.

The thinner adhesive k is suitable for bonding parts that require dimensional accuracy and flexibility. Yet again. It has good filling properties for porous materials and uneven surfaces, and good permeability when pressed, resulting in great adhesion, and is suitable for substrates with complex surface shapes, such as wood, lumber, leather, and honeycomb structures. Effective for adhering bodies, corrugated structures, etc. Another feature of the foamed hot melt adhesive composition according to the present invention is that the foam's heat insulating effect allows for a longer open time, making it possible to bond over a wide area, which was previously thought to be impossible.

Hereinafter, the present invention will be explained in further detail with reference to Examples.

Example 1 4031 d parts of ethylene-vinyl acetate copolymer (Evaflex $220 manufactured by Mikata Polychemical Co., Ltd.), hydrogenated rosin glycerin ester (Ester Gum H manufactured by Hazuki Kagaku Kogyo 4-width)
) 60 parts by weight, 1 part by weight of antioxidant (Irganox +0+0, manufactured by Ciba Geigy), 0.5 parts by weight of perfluoroalkyl ethylene oxide adduct (Megafac F-142D, manufactured by Dainippon Ink & Chemicals, Ltd.) are separable. The mixture was charged into a flask and stirred at 200° C. for 50 minutes in a nitrogen atmosphere to melt and mix. Further, after degassing under reduced pressure of about 100 raaH9, the pressure was returned to normal, and the mixture was taken out into a flat vat and cooled. The thus obtained hot melt adhesive composition had a softening point (ring and ball method) of 78°C and a melt viscosity of 7,000 ape at 180°C using a B-type viscometer. The composition was discharged and foamed using a hot-melt adhesive applicator (Nordson Corp., Formmelt model FM-101) under the following conditions to examine the stability of the foam and examine its adhesive properties.

Temperature = 180°C Dissolved gas: Nitrogen (only for foaming type) Discharge pressure: 80 to 55 Kp/c++2 The foam stability of the hot melt adhesive melt produced by foaming was measured by the following method. That is, a graduated cylinder of 100 TLl was fixed in an oil bath maintained at 180° C., and a constant volume of hot melt adhesive was discharged into the cylinder under the above foaming conditions, and the bubbles were observed to disappear over time. Immediately after dispensing, the diameter is 1, and the volume after the bubbles have completely disappeared is 1.
Let ゜Vt, V be, and express the volume of bubbles as a percentage as shown in the following equation.

The time when the value of %Foam becomes 50 is defined as the half-life of the foam. The hot melt adhesive composition of this example had a foam half life of 155 minutes at 180°C.

Aluminum plates that have been degreased with acetone are overlapped so that the overlapped area is 2.5 cIIL
Foaming applied. Then, after the predetermined time (open time) has passed, overlap another aluminum plate and immediately
It was pressed for 10 seconds at a pressure of Kf/cf. Using the same pressure and without introducing nitrogen gas, the hot melt adhesive was applied without foaming in the same way as when applying conventional hot melt adhesives, and the aluminum plates were bonded together. We compared the difference in power. Table 1 shows the results of measuring the shear adhesive strength at 25° C. and a tensile rate of 20 mm/n in accordance with JI8 K6850.

Table 1 Looking at the adhesive surface after shear adhesive strength measurement, it was observed that the adhesive spread more in the foamed adhesive than in the non-foamed adhesive. Comparing the adhesive strength at the same oven time, the foam coating system is stronger. Furthermore, if we look at the open time for the same adhesive strength, it is clear that the foam coating system has a longer open time.

Comparative Examples 1 and 2 The same formulation as in Example 1 but containing no surfactant at all (Comparative Example 1) and a small amount of 1.0 parts by weight of polyoxyethylene octylphenol ether instead of the perfluoroalkyl ethylene oxide adduct. Powdered silica (Aerosil 200 manufactured by Nippon Aerosil Kaga) to which an Oi heavy filter was added (Comparative Example 2) was foamed in the same manner as in Example 1, and the half-life of the foam was measured. The results are shown in Table 2.

1 Table 2 Compared to the no-fly life of the foam of Comparative Examples 1 and 2, the half-life of the foam of the composition using the fluorosurfactant of Example 1 is much longer, and the stability of the foam is It can be seen that there has been a marked improvement.

Example 2 Atactic polypropylene (Chiba Fine Chemical Co., Ltd. Sun Attack) qa heavy ffi part, polyisobutylene (
Exxon Chemical MS Vistanetx LM-Ms) 10 polydisperse parts, Tinuvin po as a stabilizer, 5ffi plate part, Irganox 10101 weight part (all manufactured by Ciba Geigy), dimethylpolysiloxane polyethylene oxide copolymer (manufactured by Toshiba Silicone M, Silicone XFA42
A foamed hot melt adhesive composition was obtained by roll kneading 0.5 times the weight of 0.00) at a temperature of 60 to 120°C. The softening point of the composition is 115°C, and the melt viscosity at 160°C is 51
The composition was prepared in the same manner as in Example 1, nitrogen gas was introduced at 16 +3'C, and foaming was performed at a pressure of 65 Kg/chi to examine the stability of the foam. Bubble's half-f is 11
It was 8 minutes.

Next, Example 1
In the same manner as above, foamed and non-foamed coatings were applied so that the same coating was VC, and wrinkled, and the shear adhesive strength was measured.

The results are shown in Table 5.

Table 5 It can be seen that foam coating, as in Example 1, provides greater adhesive strength and longer open time.

Example 5 Dimethyl terephthalate, dimethyl isophthalate, dimethyl adipate, and 1,4-butanediol in a molar ratio of 5
5.25:20.150 in a separable flask, and 40% titanium isopropinate as a catalyst.
0 ppm was added, and transesterification reaction was carried out in a nitrogen atmosphere at 150 to 220°C for 1 hour, then at 220°C for 2 hours, and methanol was distilled off. The temperature was further increased from 220°C to 240°C over 1 hour, and at the same time the pressure was gradually reduced to 01+u+Hg. and 240
A polycondensation reaction was carried out for 2 hours under the conditions of 'C, O, + nan H9 to obtain a -C polyester.

1 part by weight of an antioxidant (Irganox 1olo manufactured by Teva Kaigy Co., Ltd.) and an organosilicon type ii'ji activator (Silicone F-2 manufactured by Shin-Etsu Chemical Co., Ltd.) were added to 100 parts of this polyester.
, 50) Pour parts of o and s weight into a separable flask and stir for 50 minutes at 220'C in a nitrogen atmosphere.
The mixture was melt-mixed.

Then, defoaming was performed in the same manner as in Example 1 to obtain a foamed hot melt adhesive composition. The softening point of the composition is 155°C, 2
The melt viscosity at 15°C was IIS, 000 cps.

The composition was prepared in the same manner as in Example 1, nitrogen gas was introduced, and 2
15℃, 70Kp/cr! Foaming was performed under these conditions. 2
The half life of the foam measured at 15° C. in the same manner as in Example 1 was 516 minutes.

Next, the composition was filled into a 60 cc aluminum cup while foaming, and a test piece was immediately inserted into the cup to cool and solidify. And after being left at 25°C for 2 days, 2 o tp
The test piece was pulled out from the aluminum cup at a pulling speed of an/min. Table 4 shows the pull-out strength for various test pieces.

Table 4 The polyester foam layer was destroyed in both cases.

Since the strength of polyester resin is high, the pull-out strength is also high. The expansion ratio is about 5 times. Therefore, it is more advantageous than filling and sealing with a conventional non-foaming hot melt adhesive. Because polyester has a high softening point, it is suitable for use as a filler or sealant in areas where heat resistance of 80 to 120 degrees Celsius is required.

Example 4 Styrene-butadiene-snarene block copolymer (Turuprene T-414 manufactured by Asahi Kasei Kogyo 1″4) s5mkHG
i5, terpene resin (Picolite made by Esso Chemical ■ ^++
5) 28 mm parts, 555 parts by weight of paraffin wax (Nippon Oil Corporation Paraffin 155), 2 parts of antioxidant (TSKURAK T xq p manufactured by Ohmukai Shinko Kagaku Co., Ltd.),
Perfluoroalkyl phosphate ester (Dainippon Ink Chemical Industry Co., Ltd. Megafac F-19+) 0.5 weight M
The mixture was kneaded in a Banbury mixer at 100 to 180°C to obtain a rubber-elastic hot melt adhesive composition.

The softening point of this composition was 117°C, and the melt viscosity at 180°C was ++, OOOcps.

The hot melt adhesive was discharged and foamed at 180° C. and 75 Ky/crll in the same manner as in Example 1, and the half life of the foam was 215 minutes. Next, the mixture was filled into an aluminum cup in the same manner as in Example 5, and a test piece was immediately inserted therein to cool and solidify. Then, the pull-out strength of various test pieces was measured under the same conditions as in Example 5)
The results shown in Table 5 were obtained. Bueo foaming ratio is 4.
It was 5 times more.

Table 5 Failure occurred in the Botmelt adhesive foam layer, or the rubbery foam layer exhibited significant elongation before failure. Therefore, it is promising as a sealing material for areas with large cedar trees.

Example 5 40 parts by weight of ethylene-ether acrylate copolymer (Union Carbide Co., Ltd. #!D?DA2504), 40 parts by weight of aliphatic petroleum resin (Inton A-100 manufactured by Nippon Zeon ■)
Heavy foot part, microcrystalline wax with a melting point of 90℃ (
Microwax +90Y manufactured by Mopil Petroleum Flavor) 20 parts by weight, M-blocking agent (Irgasox+o+o manufactured by Tepa Geigy) + m1 part, Fluorine surfactant (Dainippon Ink Industries, Inc. Megafac F-+77) 0.1 Parts by weight were charged into a separable flask and melted and mixed in the same manner as in Example 1. The softening point of the composition is 87°C, 180°C.
The melt viscosity at °C was 19, QOOcps.

Similar to Example 1, aoKp/d at 180°C
The half-life of the foam discharged at the discharge pressure is 15
It was 1 minute. Next, under the same conditions, the composition was foam-coated in a linear manner at a rate of 4717 m on an aluminum foil having a thickness of 100 μm, and after a predetermined time (open time) had elapsed, another sheet of aluminum foil was overlapped and immediately crimped.

Aluminum foils were bonded to each other in the same manner using non-foamed yarns in which nitrogen gas was not introduced. 25℃ according to JIS K 6854
Table 6 shows the peel strength when T-peel was performed in the application direction of the hot melt adhesive at a tensile speed of , 50 ram/min.

Table 6 When the open time is 1 second, there is no difference between the foamed coating system and the non-foamed coating system, but when the open time is longer, the T-peel strength of the foamed coating system is greater. The spread width of the adhesive after peeling is larger in the foam coating system, and this is thought to be the reason why the strength is greater than that in the non-foaming system.

Applicant's agent Kaoru Furutani

Claims (1)

[Claims] 1. A thermoplastic resin selected from the group consisting of addition polymers and ester condensation polymers that are solid at room temperature and exhibit fluidity when melted at a temperature of 70 to 250'C, and a fluorine compound having surface-active ability and/or or a foamed hot melt adhesive composition comprising an organic silicon compound.