JPS6096676A - Hot-melt adhesive composition - Google Patents

Abstract

PURPOSE:To provide a hot-melt adhesive having good adhesion to both non- polar and polar materials, by blending a tackifying resin with a specified polymer component contg. an unsaturated carboxylic acid-modified polymer. CONSTITUTION:In a hot-melt adhesive compsn. consisting of 100pts.wt. polymer component (A) composed of 25-75wt% lowly crystalline to non-crystalline ethylene/alpha-olefin copolymer having an ethylene content of 20-50mol% and an alpha- olefin content of 50-80mol% and 75-25wt% ethylene/unsaturated carboxylic ester copolymer and 25-200pts.wt. at least one tackifying resin (B) selected from among terpene resin, aliph. petroleum resin and alicyclic petroleum resin, said adhesive compsn. characterized in that at least one member of said polymer component is modified by an unsaturated carboxylic acid or its derivative and the compsn. has a viscosity of 50Pa.S (180 deg.C) or below.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a hot melt adhesive composition.

More specifically, an ethylene copolymer in which at least one of the polymer components consisting of an ethylene-α-olefin copolymer and a ethylene-unsaturated carboxylic acid ester copolymer is modified with an unsaturated carboxylic acid or a derivative thereof. This is a hot melt adhesive composition comprising a 9W tackifier resin as an essential component of a hot melt adhesive nohes polymer, and the melt viscosity of the composition is 50.
The present invention relates to a hot melt adhesive composition characterized in that Pa, 5 (180° C.) or less.

Conventionally, hot melt adhesives are made by melt-mixing a base polymer, a tackifying resin, and further, if necessary, a wax, a plasticizer, an antioxidant, a filler, and the like. Usually, the base polymer for hot melt adhesives is ethylene-
Vinyl acetate copolymer (gvh), ethyl V-acrylic acid ester comonopolymer (ggA), atactic polypropylene (APPPP lipolyamide A), polyester (PET), styrene-butadiene stene (SB)
Thermoplastic polymers such as S) and styrene-inopunsutin (S) are used. Among them, EVA and B
Compared to other base polymers, CEiA's ethylene copolymer has excellent compatibility with tackifier resins, waxes, etc., and has excellent adhesive properties, flexibility, OT flexibility, cold resistance, and hot melt fluidity. Because of its excellent properties, it has been widely used as a base polymer for hot melt adhesives.

EVA yaff1f! fA (H-based polymer hot adhesive has excellent adhesion to porous base materials such as paper, wood, and fibers/) Rolling, packaging (cardboard,
It is widely used for applications such as carton bag making), bookbinding (perfect binding and case binding), woodworking (for edge pasting), plywood (for core core), and shoemaking (toe core). F16 fields where hot melt adhesives are expected to grow in the future include the field of product assembly/prep for automobiles, electrical equipment, building materials, etc., and the field of various packaging materials mainly for liquid containers.
Non-polar materials such as polyolefins (e.g. Eva lc% PP) and polyesters (e.g. PET), which are generally said to be difficult-to-adhesive materials.

Extreme materials such as PBT), acrylonitrile, polycarbonate, nylon, and soft PVO1 metals (e.g. At and steel) are generally used alone, but are often used in combination, and are non-polar and polar materials. Bottmelt adhesive is used to bond well to both sides.

[Problem of invention]

With conventional gvAgggA-based hot melt adhesives, a
However, it is difficult to guarantee that these materials have satisfactory adhesion performance, and for these applications, the surface of the base material must be treated in advance by some method (for example, chemical treatment, corona treatment, plasma i treatment, etc.). After processing, chloroprene-based,
M machine bath agent type adhesives such as nitrile rubber type, EBOKI 7 type, and urethane type adhesives are used. However, when using these organic (6-component adhesives), a drying process is required.

In addition, there are problems such as deterioration of the working environment due to m-agent vapor, danger of fire, S environment contamination, and solvent recovery, so the development of a hot melt adhesive that does not have these drawbacks has been awaited.

[Prior art]

JP-A-55-13718 discloses a new adhesive composition that easily provides a laminate of a polymer and a polyolefin synthetic resin that is difficult to bond to a polyolefin synthetic resin. A resin composition is disclosed in which at least one of the compositions consisting of an olefin copolymer and an ethyne-vinyl acetate copolymer I-) is graft-modified with an unsaturated carboxylic acid or an acid anhydride. However, the resin composition described in this publication has a Suhani Wara Melt Index of 0.1 to 100 (
D -r-f L/ /-α-olefin copolymer tS
Ethylene with melt intex 0.5~1oo
Using a hinyl acetate copolymer as a raw material, 0.05 to 3 weight of unsaturated carbo/acid and its acid anhydride are all grafted.
The iil iJW composition has a melt viscosity of about 80 Pa.
, i (180'C) or higher, and is hardly applicable to hot melt applicators. When used in a hot melt applicator, the melt viscosity of the μ composition should normally be less than about 50 E'a,e (180°C).

Moreover, according to JP-A No. 55-t36981, vesicles 7 are graft-modified with 7 trocarboxylic acids and 1 co-melted indenox 5-5
00 ethylene-α-olefin copolymer rubber 30-70
A hot-melt pressure-sensitive adhesive composition containing 70 to 30% by weight of tackifying resin has been proposed, which has excellent tack, adhesive strength, and holding power, and has good spreadability. In the detailed description, in order to achieve all the objects of the present invention, the ethyl V/content is preferably 40 to 85 mol, especially 60 to 85 mol.
It is stated that an ethylene-α-olefin/copolymer rubber having a high ethylene content of 83 molty is particularly preferred. However, compositions using this copolymerized rubber as a pace polymer also lack light in terms of adhesive strength, as shown in the comparative examples below.

Ethylene-n used as a pace polymer in A1 hot melt adhesive in Mayu Kotobuki Sho 57-3712
Part or all of the acid vinyl copolymer may be replaced with an ethylene-α-olefin copolymer having a specific Mooney viscosity or a
By replacing the ethylene-alpha-olefin-diolefin copolymer with an ethylene-alpha-vinyl acid copolymer, the ethylene-alpha-olefin copolymer is the only e-pace polymer compared to the hot melt adhesive.

It is described that the low-temperature adhesive strength of low-temperature brittle processing is significantly improved, and that it is effective for adhering dense aluminum, polyglobylene, polynisglue, etc.

However, the adhesive strength exemplified here is not sufficient as shown in the later comparative example.

In MafC, Japanese Patent Publication No. 56-39831, α, β-unsaturated carboxylic acids and a Solic acid anhydride? Daraft-modified modified ethyl acrylate V/-ethyl acrylate coconjugate 10 to 95 weights unmodified ethyl acrylate V/-ethyl acrylate conjugate 90 to 5
Weight percent sword compositions have been proposed. This system also has too high a melt viscosity and cannot be applied to ordinary hot melt applications.

On the other hand, the present invention is applicable to hot melt applicators and can be applied to polyolefin materials or a polyolefin material and other materials (e.g., polyester, acrylonitrile, polycarbonate, nylon, metal, etc.). The purpose of this invention is to provide a hot melt adhesive that satisfies the adhesive strength of Practical Novel T-type peel strength of approximately 3fff/25B or more, and is based on the above-mentioned conventional technology. .

The present inventors have focused on these points, in particular, a true melt adhesive that has good adhesion to both polar materials such as polyglobin and polar materials such as polyester, acrylonitrile resin, polycarbonate, nylon, vinyl chloride, and metal. As a result of intensive studies to develop adhesives, we found that a specific ethine-containing compound (I″Mf) was selected as a pace polymer for true melt adhesives.
It consists of a low-crystalline 1, amorphous ethynone-α-onophine copolymer and ethylene-vinyl ester copolymer, at least one of which is an unsaturated carboxylic acid or its acid. As an essential component of the base polymer,
And Tokisada's tackifying resin gold dil! A hot melt adhesive composition with a melt viscosity that can be applied to a hot melt applicator is suitable for the above purposes. −＾
rba d de I nifra de addition wo Rtsut (Kigansho 58-1601
No. 43). After that, as a result of careful consideration, the above Echi V.
By using an ethylene-ζ saturated carboxylic acid ester copolymer instead of an ethene/vinyl ester copolymer, it is more effective against both nonpolar and polar materials than when using the entire ethene/vinyl ester copolymer. It was discovered that high adhesive strength could be obtained by using this method, and the present invention was finally completed.

[Structure of the invention] In other words, the first μA (aJ ethi V n empty 20
-50 molar ratio, α-onophine fi sensitive so -50 molar ratio of low crystalline or non-crystalline ethylene-α-onophine co-point composition 25-75% by weight tl)J ethylene-Futsujiwa carbo 7 75~25 tonne weight% power・
I-) Consisting of 100 parts of the ingredients, B orben resin,
Aliphatic petroleum resin J=-manufactured resin JR group petroleum resin Eli selected small quantity/meng Kuto one kind of tackifier resin 25~20
In the hot-melt adhesive composition composed of 0 Posebe Totame et al., at least one of the superposition components is modified with an unsaturated carboxylic acid or a derivative thereof, and the melt viscosity of the composition is 5 Q Pa, θ. (180℃) or less
According to a second aspect of the present invention, the hot melt adhesive composition further contains 75 parts by weight or less of wax in addition to the first composition.

The ethylene-α-onfin used in the present invention is one having a monomer ζ and has a dithinone content of 20 to 50 molar, preferably 30 to 45 molar.

A suitable melt index is 0.1 to 1000. As α-olefin, apropylene/, buty/-1
, Pe/ten-1, Hexe7-1. octene-111 and t
Among them, propynon, buty/-1
,4! jIIC propinone seems to be good. α in copolymer
-Onophine content is 50 to 80 mol, preferably 55 to 70 mol. In hot melt adhesive compositions in which the ethylene content is outside the above-mentioned range, ethylene-〇-V-fin co-containing material is used as one of the polymer components, polyolefins, especially polyglobylene materials, polyesters, and polar materials such as nylon, are used. It has weak adhesive strength and is unsuitable as a base polymer for hot melt adhesives.

Ethylene orocarbo used in invention/(fi
Examples of x-stell copolymerized Amagi include ethyne/-(meth)methyl acrylate copolymer, edele/-(meth)ethyl acrylate copolymer, ethyl V-(meth)acrylic Budel copolymer, and ethylene-acrylic. Examples include 2-ethylhexyl condensate and the like. Among these, ethylene-ethyl acrylate copolymers are preferred, and ethyl acrylate-containing ethyl acrylate copolymers having a Jt of 5 to 20 moles and a melt index of 1 to 1,000 are particularly preferred.

Next, ethylene-α-olefin copolymer ethyne/
- Melt Intex, which is a heavy sweat component in which at least one component consisting of an unsaturated carbonyl ester copolymer has been modified, a tackifier resin, and a wax whole-egg fixed hot melt adhesive composition. The melt viscosity of 5 g Pa, θ
(180°C) or less. Since the melt index of the base poly 1- of the hot melt adhesive is usually less than il l OOO, it is preferable that the melt index of the polymer component is also in this category 1.

Next, the ratio of the ethylene-α-olefin copolymer and the ethylene-unsaturated carboxylic acid ester copolymer is 25 to 75% by weight, especially 30 to 75% by weight of the former.
A range of 70% by weight is preferred. If the proportion of the ethyl V-α-olefin copolymer is less than 25 times, the adhesion to polyolefin will decrease, and 1
7'C75 weight: If it is t% or more, the C melt viscosity is high, leading to low tO hot melt applicator suitability (workability). Therefore, it is necessary to set the blending ratio of the ethylene-α-olefin copolymer in a range of 25 to 75 times.

When an ethylene-alpha-olefin copolymer is produced, an ethylene-alpha-olefin copolymer is produced, and an ethyl-unsaturated carboxylic acid ester co-polymerizes at least a small amount of the polymeric acid.On the other hand, an unsaturated carboxylic acid or its derivative It is necessary to carry out graft modification in a similar manner, and as a result, LD exhibits a remarkable adhesion effect compared to compositions made of other polymer components as shown in the examples.

As monomers used for graft modification (hereinafter referred to as graft monomers), the following unsaturated carboxyl/acid derivatives can be mentioned. Specifically, unsaturated carboxylic acids include, for example, acrylic acid, methacrylic acid, maleic acid, fumaric acid, chloro/acid, itaconic acid, citraconic acid, and the like. Derivatives of unsaturated carboxylic acids include acid anhydrides, esters, amides, imides, metal salts, etc., such as maleic anhydride, traconic anhydride, itaconic anhydride, methyl acrylate, methyl methacrylate, and acrylic anhydride. Ethyl acid, ethyl methacrylate, butyl acrylate, butyl methacrylate, glycidyl acrylate, glycidyl methacrylate, monoethyl maleate, diethyl maleic acid ester, monoethyl fumarate, dimethyl fumarate, monomethyl itaconate Esters, Ilco/acid diethyl esters, acrylamide, methacrylamide, manic acid monoamide, maleic diamide, maleia 1-, N-
Monoethylamide, maleic acid-NIN-diethylamide, maleic acid-N-monobutyramide, maleic acid-NIN-d-
N+N-dibutylamide, fumaric acid monoamide, fumaric diamide, fumaric-N-monoethylamide, fumaric 7-N+N-diethylamide, fumaric acid-N-monobutylamide, 7mal d-N+N-dibutylamide, manimide, N -butylmaleimide, N-phenylamanoimide, sodium acrylate, sodium methacrylate, potassium acrylate, potassium methacrylate, and the like. Among these, the most important are carboxylic acids.
C is most preferably an acid anhydride, particularly maleic acid or anhydride.

All of the various known methods can be used to graft the graft monomer onto the ethylene copolymer. For example, an ethylene copolymer and the necessary amount of graft monomer are dissolved in a solvent such as xylene or toluene, and an organic peroxide such as benzoyl peroxide, lauryl peroxide, or cumyl peroxide is added to this solution. A radical initiator such as azobisnitrile is added, and the temperature is increased above the decomposition temperature of the radical initiator, usually (at 150 to 300°C for 1 minute to 5 minutes).
The graft reaction can be carried out by heating and stirring for a period of time. The graft reaction can also be carried out without using a solvent. For example, after uniformly dispersing the required number of graft monomers and radical initiators into pellets of ethylene copolymer, the kneading equipment of an extruder is used.
Grafting can also be carried out by heating for 1 minute to 5 hours at a temperature higher than the decomposition temperature of the radical initiator.
The graft ratio (hereinafter referred to as graft ratio) is preferably adjusted so that it is in the range of 0.1 to 5 folds.
If high adhesion cannot be obtained at 1 ton or more, and if the draft ratio exceeds 5% by weight, the required amount of radical initiator will also increase, and ↓ of KEA is radical In the case of a type of ethylene copolymer that is used as an initiator to crosslink, the melt index of the graft polymer decreases too much and the melt viscosity of the hot melt adhesive composition is too high.
11/)
. On the other hand, in the case of a type of ethylene copolymer that can be decomposed by a radical initiator, such as a 2-V-propylene copolymer with a high propylene content, during the graft reaction,
Partial decomposition of the main chain occurs and an increase in the melt index is observed, and the melt viscosity of the hot melt adhesive composition decreases, resulting in improved workability and easier wetting of the temporary bond, resulting in higher adhesive strength. i4 is suitable as a base polymer for hot melt adhesives. In this case, even if the a-grafting ratio is small, the performance of the a-very high V-bell is superior in terms of adhesive strength. In addition, the relationship between the grafting rate and adhesive strength is that the adhesive strength almost reaches saturation at a grafting rate of 3 to 5%.
Even if graft modification is performed with five layers or more, there is no advantage in terms of adhesion and it is preferable because of cost considerations.
It's ugly.

In the present invention, selection of the tackifying resin is an important condition. Some tackifying resins commonly used in hot melt adhesives include, for example, Logi/Okobiso derivatives, terpenes It, aft, terpene-phenolic resins,
Examples include aromatic petroleum resins, aliphatic petroleum resins, alicyclic petroleum resins, copolymer petroleum resins, coumaron-indene resins, styrene resins, etc., but in the present invention, graft-modified resins can be used. Ethylene-α-O V-fin copolymer a, b
However, due to their compatibility and adhesion with the ethylene-unsaturated carboxylic acid ester co-assembly, terbe resins, aliphatic petroleum resins, and alicyclic petroleum resins are used in a limited manner. . When these specific tackifying resins are used as shown in the Examples below, they exhibit a marked effect compared to the use of other tackifying resins.

Such a tidying-imparting resin contains 25 to 200 parts per 100 parts of the polymer component, preferably 50 to 15 parts per 100 parts of the polymer component.
If there is no perspiration within the range of 0, the desired performance will be poor outside this range.

One of the important features of the hot melt adhesive composition of the present invention (1) is that it can be applied using a hot melt applicator; For example, the adhesive composition may contain 100 parts of the polymer component and 2 parts of the tackifying resin.
It consists of 5 parts by weight of a two-component system with a viscosity of 50 Pa,
The melt index of the polymer component must be approximately 80 or higher in order to keep it below s'! 'L, bar (-none. Also, it consists of 100 parts by weight of a polymer component and 200 parts by weight of a tackifier resin, and its viscosity is 5 QPa. In order to maintain θ less than 1', It is necessary to have 8 degrees.

[Second invention] In this process, the melt index of the polymer component (a) is increased by adding the lamination-imparting fat to the composition of the present invention. This restriction should be fully relaxed to allow the use of polymer components with a wide range of melt indexes as possible.
) A three-component system may be used in which wax is added as a viscosity-lowering agent, and this is the second invention.

Examples of waxes used in this case include petroleum waxes such as paraffin wax and microcrystalline wax, and sweet acid waxes such as polyethylene wax and polypropino/wax. Among these, polyethylene wax, polyglobin/wax, etc.
Although the degree of decrease in melt viscosity is smaller than when using other waxes, it is preferable because it exhibits high adhesion to polypropylene as the adherend 4.

The following three points are mentioned as the effects of combining all waxes. The first point, a hot melt adhesive composition, lowers the melt viscosity of the adhesive and improves wetting and workability. This is to prevent stickiness and blocking properties. In the case of the present invention, depending on the type of tackifying resin used, the tackiness of the resin containing μ wax may be so high that it may not be suitable as a hot melt adhesive.

When the total amount of wax is mixed in the hot melt adhesive composition of the present invention, it is preferred that the total amount of wax is 75 parts or more based on approximately 100 tons of the combined component. If the amount of wax distributed is too large, the adhesion strength will be low.
stomach.

(Other Additives) In addition to the polymer component, tackifier resin, and wax, the hot melt adhesive composition of the present invention may contain various modifiers and additives as necessary. May be blended.

10 Examples include plasticizers such as liquid polyphthalate, dioctyl phthalate, and cyphthyl phthalate, phenolic compounds, etc.
These are antioxidants such as sulfur compounds, ultraviolet absorbing AIJ, calcium carbonate, talc, and other fillers.

The amount of these additives to be distributed is arbitrary.

(Method for producing the composition) As a complete method for preparing the hot melt adhesive composition of the present invention, a1 the above-mentioned polymer component and tackifying resin.

and waxes, additives, etc. used as necessary.
The mixture is heated and melted while stirring to homogenize it, and depending on the application, it is formed into granules, 7-node shapes, 5-node shapes, rod shapes, etc. while cooling. This tunnel N4 root connection.

The adhesive fiber is heated and melted again using an ordinary hot melt applicator, and after being melt-applied to an adherend, it is pressed and bonded to another adherend. It is also possible to melt and coat various adherends using a hot coater such as a roll coater or an extrusion coater.

As shown in the above description and the Examples and Comparative Examples described below, the ribbed frame of the present invention, a low crystalline polyester with a specific ethylene content, a non-crystalline ethyl-V non-α-olefin conjugate, and an ethylene-non-N At least one of the polymer components from the specific allocation of the carboxylic acid ester copolymer is modified with an unsaturated carboxylic acid or a derivative thereof.
, a modified ethylene copolymer is used as an essential component of the base polymer, and a specific tackifying resin is added to it. (2) It is possible to obtain good adhesion to polypropylene materials (VC) even among polyolefins due to the synergistic effect of both IL1 and (2) to achieve low viscosity and low temperature = J [ability] that can be applied to hot melt applicators. We have succeeded in developing a highly refined hot melt adhesive composition.

This is of great industrial significance in that it has enabled the industrialization of hot-melt adhesion of polyolefin materials and other materials, which has been difficult to achieve in the past.

The hot melt adhesive composition of the present invention will be specifically explained by referring to all examples.

[Method of planning hot melt adhesive composition] Example J? Performance evaluation of a hot melt adhesive composition in a comparative example was carried out with no imperfections.

ill Adhesive Crab Hot Melt Adhesive Composition = Kai 160'
Melt in a heating bath at C and heat press to create a sheet 17 with a thickness of 0.31 + 1 JI. Apply this adhesive to one side of the adherend, and use a heat sealer to create a sheet 17 with a width of 25 mm and a cool temperature of 120 mm. ℃ (7-ml (both upper and lower surfaces), 7-ml pressure aii/; after heating at 7-g for a cooling time of 10 seconds, tensile speed 300/ml using an Instron tensile tester)
In the mountain, T-type peel strength was measured at a measurement temperature of 23°C.

In addition, as a broken adherent, an untreated polypropylene film (a film formed by inflation molding using polypropylene manufactured by Mikata Petrochemical Co., Ltd. as a raw material) with a thickness of 2 o o ) tm,
Bo1 Noester Film (Tokyo VS Lumirror) Made using a soft aluminum plate.

(2) Melt viscosity: 180°C of hot melt adhesive composition
Melt viscosity iB type rotational viscosity 1·(measured with a meter).

(3) Low temperature 0T ura property: Japan Adhesive Industry Association standard (: Jkr
7-1980) Low-temperature d-engineered aluminum alloys were investigated by the VC approved method.

(4) Non-stick: 300% of hot melt adhesive composition
μIll Sheet surface tack & engineering 23
'C is rated as 2 missing with 2 finger tucks O If the O tack is rl Poor Δ 4 pieces with a slight tack x If there is a significant tack Example 1 [Anhydrous Ma V / Enemy degeneration Manufacturing method of ethenone-probi-V/conjugate] Ethylene 40 molti, furopylene 60 molti, melt index 1.5 (190'C, 2160fti employment)
5 kp of ethylene-propynone copolymer (hereinafter abbreviated as pgR-1), 60 mesh in powder form, 601 mesh of ethylene-propynone copolymer, 2,5-dimethyl-2 as a radical initiator.
,5-bis(1-butylperoxy7)hexene-36,
7 and t4 were mixed in elementary atmosphere F to form a homogeneous mixture.

Next, this mixture was passed through an extruder with a diameter of 30 (L/J) =
32, using Dalmage screw) All flights are 260
Pellet gold was obtained by extrusion at a resin temperature of ℃. Unreacted monomers were removed by washing with this benthic acetone. In this way, obtained I-1 nine
The melt index of the globin copolymer (hereinafter abbreviated as MAR-PI!1R-1) was 28, and the melt index was determined using 4 vol of manoic anhydride graft and 1.1 weight.

[Preparation method of hot melt adhesive composition] MAR-PER-1 obtained by the above method, flO heavy part and ethyl V-ethyl acrylate cotate (manufactured by Mitsui Polychemical Co., Ltd., Mitsui EIlcA, A-704) , wV2ri government% (9,3
Molch), melt index 210, hereafter KKA-1
) 50 parts by weight, terpene resin (manufactured by Onna Oil Co., trade name: YS Nojin Pxtoooo) io as adhesive 4 resin
o parts by weight, as a wax, rough-in wax with a softening point of 155F (manufactured by Nippon Kinran Co., Ltd., trade name Luvax 1266)
BHT (z, 6-
G-turfy IJ-butyl-P-cresol) Zt
After putting the entire IT part into a kneader, it was heated and kneaded for 2 hours at 160°C, and a hot melt adhesive composition (+- prepared and evaluated) was prepared.
I did it. Melt viscosity of the composition Cl 3.5 Pa
, s. Evaluation-ill [[IResults are shown in Table 1.

Example 2 In the method for producing a maleic anhydride dredged V/-propylene copolymer in Example IK, the use of maleic anhydride (Ir120!t) and the use of a radical initiator (Ir120) was carried out. The process was carried out in the same manner as μ execution column 1 except that the melt index was 25, the maleic anhydride grafting rate was 2,
2 pieces of manoic anhydride-modified ethyl-probi-V/conjugated melon (MAI (abbreviated as -PKR-2) were obtained. MA) i, PKR-2 MA
A hot melt adhesive was prepared and its performance was planned in the same manner as in Example 1 except that f(-f' was used in place of KR-1. The melt viscosity of the composition was 14.OPa, θ and Evaluation results 'Ii--shown in Table 1.

Example row 3 Ethynone content 40 molt, propylene content 60 molt,
Ethylene-propy V/copolymer 8 with melt index 15
body (hereinafter abbreviated as pgR-2) 200? (f-pre6t)■
After charging the xynones of . (Xynon solution) and 2,5-tmethyl-2
, 5-bis(t-butylperoxy)hexa/131 and gold were added dropwise with stirring over 44 hours, and the reaction was continued for an additional 2 hours. Then cool to mold temperature,
Reacted with acetone *J (+: After precipitating and further washing, maninic anhydride modified ethylene-propylene copolymer (hereinafter referred to as M・NH-PER-3) total 47t0 with a melt index of a10 and maninic anhydride. Graft rate u3.1
It was a huge amount. MAR-Pf obtained in this way
Preparation of hot melt adhesive in the same manner as in Example 1 except that CR-3i was used in place of MAR-P in Example 1. A machining performance evaluation was conducted.

The melt viscosity of the composition was 20.5 Pa, θ. Review 1
The results are shown in Table 1.

Example 4 In the method for producing an 7noic anhydride-modified ethylene-propylene copolymer in Example 1, instead of PER-1, ethylene with an Ena V/concentration of 50 mol, a butene-1 content of 50 mol, and a melt index of 13 was used. - Manoic anhydride-modified ethylene-butene with a melt index of 15 and a maleic anhydride grafting rate of 1.0% except that a buty7-1 copolymer (hereinafter abbreviated as KBR-1) was used. -1 co-composite (hereinafter abbreviated as MAR-IBR-1) was superior. MAf obtained in this way (-KBR
-1 Gold MAH-PER-1
In the same manner as in column 1, hot melt adhesive preparation and performance evaluation were performed. Composition: Melt viscosity: 20. OPa,
I met with θ. Table 1 shows the planning results.

Example 5 Instead of using a terpene resin as the tackifying resin in the method for preparing a hot melt adhesive composition in Actual Series 1, Escorets 5300 (] which is a Shishihori family petroleum resin) was used.
- Except for the use, all preparations and performance evaluations of hot melt adhesives were carried out in the same manner as in Example 1. The melt viscosity of the composition was Vl 14.5 Pa, s. Evaluation result &:r,
'ije 1.

Implementation row 6 [Method for producing manoic anhydride-modified ethylene-ethyl acrylate compound] ff1KA-1 (manufactured by Mikata Polychemical Co., Ltd., Mikata ff1E
A.

A-704, KA27 direct weight% (9,3 molti), Meltoy/Dex 210 tons 4,6 o Metsu 7J-pass manoic anhydride 60t, 2,5- as organic peroxide
Dimethyl-2,5-bis(t-butylperoxy)hexa7-3 59- Mix uniformly under a metal atmosphere. This mixing 9IJ all diameter 30mm extruder total is 260
Extruded pellets were obtained at an a-plane temperature of .degree. This bellet t
All unreacted monomers were removed by washing with acetone. C+/
), l: maleic anhydride-modified ethynone-ethyl acrylate copolymerized wood (FMAH- [KA-1
The melt index was 90, and the graft ratio of anhydrous Malay/graft was 1.1.

[AIR Method for Hot Melt Adhesives Methodology Example 5 In the method for preparing a hot melt adhesive composition, unmodified pga-2 was substituted for MAR-f'KR-1.
(40 moles of ethylene, 60 moles of propylene, melt index 15) Preparation of an adhesive composition in the same manner as Example 5 except that the above MAH-RFiA-1 was used instead of ff1ffiA-1. and performance evaluation. The melt viscosity of the composition is 28
Pa and θ. Evaluation sub-results are shown in Table 1.

Example 7 In the method for preparing the hot melt adhesive composition of Example 5, the above MAH-P2K was used instead of unmodified KWA-1.
A-1 (KA 27 Weight Section 1M Worker 9 (1, MAHL, 1
%) The adhesion composition was evaluated in the same manner as in Example 5 except that sound was used and its performance was evaluated. Melt viscosity u of the composition
It was 23.0 Pa, s. Evaluation results μ are shown in Table 1.

Example 8.9 In the method for preparing the hot melt adhesive composition of Example 1, formulation 1 of 155F paraffin wax was mixed with 6450
Implemented 13'lJ in addition to changing to weight part and io melon part
In the same manner as described above, the adhesive was prepared, the proboscis was prepared, and the performance was evaluated. Melt viscosity of composition 8.0.47.
Q: Pa, s is not good enough. Evaluation results i''l-a Shown in 1 r0 Comparison 1ll (in the case where the direct-attached body components taJ and t are both unmodified) In the method for preparing the hot melt adhesive composition of Example 1, MAR-1 'gR-1 instead of non-f
Note PRiR-2 (ethylene-j, 6140 mol qb, /
/Robi V/Guryo 60 molti, melt index 15)
(The adhesive composition was processed and evaluated in the same manner as in Example 1 except for using i''. The adhesive composition had a viscosity of 17.5, Pa, and Evaluation results Table 1
Shown below.

Is the ethylene content of Comparative Example 2 (polymer component molecule a) 50 mole? In the method for preparing the hot melt adhesive composition of Example 6, unmodified gpR-x (
Including Echi V! 60 molti, clopyrene content 40 molti,
RA machining performance evaluation 1+lt1 of the adhesive composition was performed in the same manner as in Example 6 except that melt index 25) was used.
line! Yes. Melt viscosity of the composition V'L22.9 Pa,
I met with s. Evaluation results are shown in Table 1.

Comparative example 3 (directly combined main juice + b) 2 missing) implementation vAJl
In the method for preparing a hot melt adhesive composition, MAH-PfflR-1 is
An adhesive composition was prepared and performance evaluation 2 was carried out in the same manner as in Example 1 except that the total number of contributing parts was changed to 100. The melt viscosity of the composition i 55 Pa,s made the VC unsuitable for use in hot melt applicators. Sub-evaluation results μ are shown in Table 1.

Comparison row 4 (nail base component 1aJ k missing 48) In the method for preparing the hot melt adhesive composition of Example 1, MAH
-Unmodified zlnA-1il 0 without PFiR-1f
3. Preparation of an adhesive composition was performed in the same manner as in Example 1, except that the 0-fold ridge was used, and the performance was evaluated. It was OPa and θ.

Evaluation box 4: a Shown in Table 1.

Comparative Example 5 (Heavyweight component (when unmodified gVA is used) In the method for preparing the hot melt adhesive composition of Example 1, 2
and native EVA instead of native ff1fcA-1.
(Manufactured by Mikata Polychemical Co., Ltd., product name: Buff Knox 21
0, VA28it% (11.2 mol%), melt index 400, hereinafter abbreviated as jlCVA-1)? Preparation of the adhesive composition in the same manner as in Example 1 except for the use of Step 2 and Step 1.
Live performance review 11ifi Kingyo hatta. Bath melt viscosity of composition +3 (r
c9. It was I Pa,s. Evaluation 1 West results are shown in Table 1. It belongs to the previous invention, and its adhesive strength is comparable to that of the A4 invention, but the low-temperature flexibility is poor. and is inferior.

Comparative Example 6 (When the ethylene content of the heavy component ta was 50 mol%) In the method for preparing the hot melt adhesive composition of Example 1, MAR-mp was used instead of MAR-PEliR-1.
u-1 (Ethi V7 miya amount 60 molti, Gropi V7 included 1t4
Adhesive composition and performance evaluation were carried out in the same manner as in Example 1 except that kumquat was added (0% luthi, melt index 15, MAtiAtmigraft 2%). Melt viscosity of the composition Ill 18. It was OPa,s.

The evaluation results are shown in Table 1.

Comparative Example 7 (obtained in a back-door method using the manoic anhydride-modified ethylene-globin of Example 1 without using any tackifying fat) 7711A:1-PgR-
1100+1 copies and 1 unaltered! jVA-2 (VA28 j
Jii% (11,2 Moltino, Melt Index 15
) 70-weight part and J3) IT 2-type broken part and sodry play/
Then, the mixture was melt-kneaded using an extruded 4M (caliber: 3o-) metal to obtain a rectangular body component with a melt index of 190. This set IJX product 4/) Melt viscosity V'l 400 Pa, a
Atsushi. Performance using this? f number *6tx. Planned conclusion a table Bc is shown.

Comparative Example 8 (heavy body component molecule aJ, +1) is unmodified and Mal-PIR-1 is used in the method for preparing the hot melt adhesive composition of Example 1. native piR-2 instead of
Native E, Vk-1 instead of native FigA-1
The adhesive composition was prepared in the same manner as in Example 1 except that gold was used.
-4-manufacturing performance evaluation 11iIi was completed. The melting temperature of the composition is 15. Q Pa,s was. The evaluation results are shown in Table 1.

Comparison row 9 (when no tackifier resin is used) hot melt adhesive set IJy of Example 1, product preparation method VC,
In the same manner as in Example 1 except that no tackifying resin was used,
Preparation and performance evaluation of adhesive composition i++fi (r line 71
Tsulhi. The melt density of the composition was 20 Pa,s. Evaluation result 4: a Shown in Table 1.

Comparative Example 10 (when the tackifying resin is not used) MA) l-PIiiR-150 melon powder obtained by the method 2 of the ethynone maleic anhydride-glopine/conjugate combination of Example 1 and unmodified After drying the entire extruder with 50 heavy parts of ggA-i and 2 parts of BHr, the extruder was melted in a bath to obtain 95 parts of Meltoy/Dex.

The melt viscosity of this composition was 83 Pa.s. Evaluation results are shown in Table 1.

Comparative Example 11 (polymer component (aJ Zenkin missing, sword/tsudo association component (Riga EVA) In the method for preparing the hot melt adhesive composition of Example 1, lacking the polymer component + aJ', and polymer component +1
) J as unmodified gVA-1100 market failure part 1 (preparation and performance evaluation of adhesive composition in the same manner as in Example 1 except for the changes).Bath melt viscosity of the composition a1.7 Pa, s
There was ``'C.Review results are shown in Table 1.

(Space below) Example 10 In the method for preparing the hot melt adhesive composition of Example 2, preparation and performance evaluation 2 of M acid were carried out in the same manner as in Example 1 except that 155F paraffin wax T[1 was not used. . The melt viscosity of the composition was 14.0 Pa, s. The planning results are shown in Table 2.

Example 11 - In Example 10, MAR-PJCR-2 and ff1
KA-1's Goki Godo Kanayatani MAH-PER-275Ji
Am and performance evaluation of the composition was carried out in the same manner as in Example 8 except that the discharge part and ggA-i 25di part were changed.
It was. Melt viscosity of the composition 45. It was QPa-6.

The evaluation results are shown in Table 2.

Example 12 In Example 1O, MAH-IER-2 and EE:A
-1 before blending Kiyagaya MAH-PER-225 Naomobe, g
A composition was prepared and its performance was evaluated in the same manner as in Example 8, except that gA-i was changed to 75 parts by weight. The melt viscosity of the composition was 0.4 Pa, s. The evaluation results are shown in Table 2.

Comparative Example 12 (Polymer component molecule l)) @) Example 1
0, IUA-141-Used, MAH-PK
R-221o oExcluding the changer in the weight part e-work Alo
The composition was prepared and its performance was evaluated in the same manner as in 4) 12. Tangent 4, tI? Although the process was good, the bath melt viscosity of the composition was 70. OPa, g can be applied to hot applicators. Evaluation results are shown in Table 2.

Comparative Example 13 (Polymer DZ juice (aJ '2 lack type) implementation tlJ10 IIC O'Vh-C, MAH-PER-2
A composition was prepared in the same manner as in Example 1o, except that fp and KFi A-1 were changed to 100% gold and 100% gold. Melt viscosity D of the composition 6.69h,
It was e.

The evaluation results are shown in Table 2.

Examples 13 to 15 In Example 10, tackifying resin YSL/Jin PX1
The preparation of the composition and the performance evaluation were carried out in the same manner as in Example 10, except that the blended amount of 000 was changed to 25.50.1s o in the mold part. The melt viscosity of the composition is 4 each.
5.0.28.0.8. It was OPa,s. The planning results are shown in Table 2.

Comparative Example 14 (When polymer components lad and fuchi are both unmodified) In addition to using unmodified pgR-2'l in place of MAR-PhiR-2 in sister example 10, Example 1
The A-fiber and performance evaluations of the compositions were conducted in the same manner as in ゜. Melt viscosity of the composition: 30. It's OPa, s.

Evaluation results are shown in Table 2.

(This is white) Examples 16 to 18 In the method for preparing the hot melt adhesive composition of Example 10, terpene resin (YS Reg 7) was used as the tackifying resin.
f' Shaura Alcon P100) and aliphatic petroleum resin (Mikata Petrochemical Engineering Liang Shaura Hinotsu G1)
The composition was prepared in the same manner as in Example 10 except that 00
Ivy in Pa and s. The evaluation results are shown in Table 3.

Comparative Examples 15 to 18 (when a material other than time-setting was used as a tackifying finger) In accordance with the method for preparing the hot melt adhesive composition of Example 1O, Terbe/Resin (YS Registry) was used as the tackifying resin. yP
xLOOO) Instead of Kongo, Taniya Logi/g conductor (Super Ester A-75 manufactured by Arayo Kagaku Kogyo Co., Ltd.), aromatic petroleum tree BY1 (Petrology Y #too manufactured by Mikata Petrochemical Industry Co., Ltd.)
), styrene-based IIrtBvI (/~-Picolastic A-75 manufactured by Kyuns), and coumaron-i 7denheirou 8ji (1 iron coumaron 1 sealant V-1zo) 2 were used, but the composition was made in the same manner as in Example 10. 1SIiiJ# and performance evaluation llf[ik conducted. Depends on the melt viscosity of the composition.1. - 14.2.17.2.17.5.17.3 Pa, s.

The evaluation results are shown in Table 3.

(Hereinafter F margin) Example 19.20 In the method for preparing the hot melt adhesive composition of Leprosy Example 2, microcrystalline wax (Nippon Sei 9'Jt) was used instead of paraffin wax (Lubax 1266) with a softening point of 155F. a l'! Hi-MiQ1
The composition was prepared in the same manner as in Example 2, except that polyethylene wax (High Wax zxoP manufactured by Mikata Petrochemical Industry Co., Ltd.) was used.

Melt viscosity a-f of the composition: 17.5°19, 6, respectively
It was Pa, s. Evaluation results are shown in Table 4VC.

Example 21.22 Method for Preparing the Hot Melt Adhesive Composition of Example 2 ICj
i'', A, 155F paraffin wax and low-molecular broken polyglobylene wax (Viscol 660P manufactured by Sanyo Chemical Industries, Ltd.) as waxes, and a total of 40 parts, 10 parts of melon,
25.25 The preparation of the composition and the performance planning were carried out in the same manner as in Case 2 except for the formulation. The melt viscosities of the compositions were 25.3 and 45.2 Pa and s, respectively. Evaluation word *rc, 44VC is shown.

Actual Example 23 In the method for preparing the hot melt adhesive composition of Example 2, in place of the paraffin wax with a softening point of 155F, actic borigropinone (manufactured by Sumitomo Chemical Co., Ltd. 5x-1) was used.
io) The composition and preparation of the proboscis were carried out in the same manner as in Example 2, except for the preparation of the proboscis. The melt viscosity of the composition was approximately 40.2 Pa.s.

Table 4 shows the evaluation results.

(Margin below)

Claims (1)

[Scope of Claims] +11(4(-Low crystalline or non-crystalline ethylene-〇-olefin copolymer with an ethylene content of 20 to 50 molt, α-olefin content of t of 50 to 80 molt, a weight ratio of 25 to 75 and fbJ Ethylene-unsaturated carboxylic acid ester copolymer
Polymer component consisting of 75 to 25 polymers: 100 parts by weight (B) At least one tackifying resin selected from terpene resins, aliphatic petroleum resins, and alicyclic petroleum resins: 25 to 200 parts by weight In a hot melt adhesive composition consisting of parts, at least one of the polymer components is non-&! ! modified with an orocarboxylic acid or a derivative thereof, and the viscosity of the composition is 50
A hot melt adhesive composition characterized in that Pa,s (180°C) or less. f21tAJ (a) xchi V7 content 20~so mol%
, amorphous ethylene-α-olefin copolymer with an α-V fin content of 50 to 80 molt.
Ethylene-unsaturated carboxylic acid ester copolymer 7
Polymer component consisting of 5 to 25 polymers 100 parts (Bl terpene resin, 1 part aliphatic petroleum to at least one tackifier resin selected from alicyclic petroleum resins 25 to 200 parts) In a hot melt adhesive composition comprising a soft part 10J Works 75 or less, at least one of the polymer components is an unsaturated carboxylic acid or fc is modified with a derivative thereof, and the viscosity of the composition is so
A hot-melt adhesive composition characterized in that it has a temperature of 1 s o C or higher.