KR800000146B1 - Hot melt adhesive composition - Google Patents

Abstract

A by-product(b.p. 140-220≰C)of the steam cracking of naphtha was distd. and the distillate(contg. <2wt.%) indene and derivs.) was fractionated, giving a residue(contg.<=0.7wt.% cyclopentadiene and methylcyclopentadiene and methylcyclopentadiene and <3% conjugated dienes) which was polymd. in the presence of BF3 at 20≰C for 3hr. The polymer 40 parts were mixed with 40parts ethylene-vinylacetate copolymer, 20 parts paraffin wax at 180≰C to give a hot melt adhesive with good adhesion and heat resistance.

Description

Heat melt adhesive composition

The present invention relates to a heat-melt adhesive with improved adhesion and heat stability, and more particularly, polymerization of specific oils in cracked oil fractions obtained by pyrolysis of ethylene copolymers, waxes and resin components. A heat melt adhesive composition which is an aromatic hydrocarbon resin obtained by the present invention, and relates to an extremely good heat melt adhesive composition having improved adhesiveness, heat stability, and low temperature characteristics.

In recent years, the hot melt adhesive is 100% solid, has a number of advantages such as low risk of fire, shortened adhesive set time, ease of handling, and the like with the rapid spread of the applicator, It is used in a wide range of fields such as packaging and woodworking.

A hot melt adhesive is a solid adhesive at normal temperature, it melts with heat at the time of use, and it apply | coats to various base materials, solidifies by adhering and cooling, and expresses adhesive force. For this reason, a heat-melting adhesive must have excellent adhesiveness with respect to various base materials, and in order to obtain a product with a constant quality, it must be excellent in heat resistance stability, and it requires flexibility also at low temperature, depending on a use.

Currently, as the base polymer of these heat-melt adhesives, ethylene-based copolymers such as ethylene-vinyl acetate copolymer (EVA), ethylene-acrylate copolymer, polyethylene, thermoplastic rubber, polyamide, polyurethane, polyester, etc. A thermoplastic polymer is used, and various low molecular weight thermoplastic resins and various waxes are blended as tackifying resins and viscosity modifiers to improve adhesiveness and melt viscosity. As the base polymer, ethylene-based copolymers such as EVA and ethylene acrylate, which are inexpensive and excellent in flexibility and heat resistance, are widely used.

As the tackifying resin, natural resins such as rosin and telpen resins and various petroleum resins are used. Especially, rosin resins are widely used because of their excellent adhesion and flexibility at low temperatures, and because of their excellent heat stability. However, all of them are expensive because they are made from natural materials, and there are also problems with resources. In addition, various petroleum resins using inexpensive petroleum powders have been proposed and used as substitutes for rosin and telpen resins, but any of them are currently proposed to be comparable to rosin and telpen resins in terms of adhesiveness, heat stability, and low temperature characteristics Not.

The present invention relates to a heat-melt adhesive, which has excellent or superior performance as compared to a heat-melt adhesive made of rosin, telpen resin, etc., and contains extremely good heat containing a tackifying resin synthesized from a rich and inexpensive industrial raw material. It is an object to provide a melt adhesive. In other words, the present invention has a boiling point within the range of 140-220 ° C. in the decomposition oil component obtained by thermal decomposition of petroleum, in the heat-melt adhesive mainly composed of ethylene copolymer-adhesive resin-wax. The content of conjugated diolefin is 0.7 wt% or less, the content of conjugated diolefin is 3% or less, the total content of indene and its alkyl derivatives is 2 wt% or less, and the indene content is adjusted to 8% or less. It is an aromatic hydrocarbon resin obtained by adding a pretelcraft type catalyst in the range of 0.01-5 wt% with respect to raw material oil, and superposing | polymerizing at the temperature within the range of -30 degreeC to +60 degreeC, The heat-melting adhesive characterized by the above-mentioned. .

The composition of the present invention has excellent performance in all of adhesiveness, heat stability, low temperature characteristics, etc., compared to the heat-melt adhesive using a conventional petroleum resin, and comparable to or similar to natural resins such as rosin and telpen. It has extremely good performance that surpasses it.

As the ethylene-based copolymer of the present invention, one or two or more copolymers of ethylene, monocarboxylic acid vinyl ester and acrylic acid ester, and the content of the copolymer are 10-60 wt% (preferably 15-45 wt%). , Melt index (MI) of 0.1-1,000 (preferably 1-500).

Where the melt index is ASTM. According to D-1238, it refers to the gram number which flowed out at 190 degreeC and a load of 2,160g for 10 minutes.

The tackifying resin component of this invention is an aromatic hydrocarbon resin which is a polymer of the oil component which has a boiling point in the range of 140-220 degreeC among the decomposition oil components obtained by the thermal decomposition of petroleum.

In general, petroleum hydrocarbon resins are obtained by thermal decomposition of petroleum. It is obtained by polymerizing liquid decomposition oils at room temperature, but the boiling range is 20 ° -280 ° C, 20 ° -170 ° C, and 140 ° -280 ° C. When using a decomposition oil component having a boiling point range of 20 ° C. to 140 ° C. as a raw material, the resulting resin is a so-called non-aromatic hydrocarbon resin containing no aromatic nucleus. In this case, since a large amount of conjugated diolefins and non-conjugated diolefins are contained in the raw material oil, the resin has a high degree of unsaturation and poor color and heat resistance stability.

Resin obtained from the decomposition oil fraction having a boiling point of 140 ° -280 ° C as a raw material is an aromatic resin, and in this case, heat stability and color are not sufficient, and the adhesiveness in the case of a heat-melting adhesive is also low. do.

As a result of examining the characteristics of each component in the raw material oil in detail, the present inventors obtained a resin having good adhesion tablets and heat resistance stability from an oil component in which specific components in the raw material oil were strictly separated, and this was applied to the tackifying resin. Adoption of the present invention has led to the development of the present invention to obtain a heat-melt adhesive having extremely high performance.

The tackifying resin used in the present invention has a boiling point within the range of 140 ° -220 ° C in the cracked oil fraction obtained by thermal decomposition of petroleum oil, and the unsaturated compound contained therein is substantially styrene and its derivatives, indene and derivatives thereof. The starting oil is a conjugated diolefin content of 0.7 wt% or less, a conjugated diolefin content of 3% or less, a total content of indene and its alkyl derivatives of 2 wt% or less, and an indene content of 8% or less. It is an aromatic hydrocarbon resin prepared by superposing | polymerizing the oil fraction adjusted so that it may satisfy | fill the conditions to be satisfied using a pretel kraft type | mold catalyst, and removing an unreacted oil content and a low molecular weight polymerized product by evaporation or distillation.

Starting raw oil for obtaining the tackifying resin according to the present invention is petroleum, such as naphtha, kerosene or light oil, by thermal cracking, such as steam cracking, 1400- of the by-products obtained when producing ethylene, propylene, butenes and butadienes It is a decomposition oil component in the boiling point range of 220 degreeC.

As a result of analyzing each component of the decomposition oil of this boiling range according to the gas chromatograph method, as shown in Table 1, each component having the following boiling point was typically detected.

[Table 1] Components in Decomposed Oil of 140-220 ℃ Oil

Note 1) Some or all of the dicyclopentadiene may be depolymerized with cyclopentadiene by heating.

NOTE 2 Some of the undetected components include cyclopentadiene-methylcyclopentadiene codimer and methyl cyclopentadiene dimer.

Some or all of these may depolymerize to cyclopentadiene by heating, and these monomers can be analyzed by the said gas chromatograph method.

The sum total of styrene, its derivative (s), indene and its derivative (s) among the above components is made into a polymerizable component. In addition, when cyclopentadiene and methylcyclopentadiene generate | occur | produce by heating etc. as in Table 1 and said note 2, and it contains in raw material oil, these also add to a polymerizable component.

In order to obtain the resin according to the present invention, it is one of the necessary conditions to use a crude oil which is separated and adjusted so as to satisfy the following conditions in the oil having a boiling point within the range of 140-220 ° C in the cracked oil obtained from pyrolysis of petroleum. . Condition of raw material oil (Hereinafter, an oil having a boiling point within the range of 140-220 ° C. among the cracked oil components obtained by pyrolysis of petroleum is referred to as “starting raw oil” and an oil satisfying the following conditions is referred to as “raw oil”).

(A) The total content of cyclopentadiene and methylcyclopentadiene in the raw material oil separated from the starting raw material oil, that is, the conjugated diolefin content is 0.7 wt% or less, and the conjugated diolefin content defined in the formula (1) 3% or less.

Note 1) The conjugated diolefin content means the total content of cyclopentadiene and methylcyclopentadiene.

(B) The total content of indene and its alkyl derivatives in the crude oil separated from the starting crude oil is 2 w% or less, and the indene content defined in formula (2) is 8% or less.

Each component of starting oil and raw oil are analyzed by the gas chromatograph method under the following conditions.

(i) Styrene, arylbenzenes, 1,3,5-trimethylbenzene and 0-ethyltoluene consisted of celite (Celite, Johns Manville Corp.) containing 20 wt% of Apeis Lgrease (produced by Associated Electrical Industries Ltd). Product) and filled into a column of 3 m in length and analyzed under conditions of 60 cc / min of helium flow rate at 100 ° C.

(ii) Each component other than the components shown in (i) is filled with a 3m-long column containing 20 wt% of polyethylene glycol 4,000, and analyzed under conditions of 60 cc / min of helium flow rate at 125 ° C.

The total amount of styrene, its alkyl derivative, indene and methylcyclopentadiene content analyzed by the above method is made into a polymerizable component.

The manufacturing method of the tackifying resin in this invention is described in patent claim 1 of US Pat. No. 3,778,421, and the above-mentioned patent is referred for the manufacturing method.

In the method for producing a resin according to the present invention, 4 items are: 0.7 wt% of conjugated diolefin content, 3% of conjugated diolefin content, 2% by weight of indene and its alkyl derivatives, and 8% of indene content, which are the limiting limits of raw material oil. The color and heat stability of the resin obtained by polymerizing under the above polymerization conditions using a raw material exceeding this limit in any of the items is poor, in particular, when the coloration becomes severe and the heat-melting adhesive is used. The resistance and heat stability become poor, and the performance as an adhesive is insufficient.

As the waxes, petroleum waxes such as paraffin wax, agate crystal wax, natural wax, polyethylene wax, polypropylene wax, atactic polypropylene wax and the like can be applied according to the purpose.

In the heat-melt adhesive of the present invention, the resin is used as a tackifying resin component and mixed with the ethylene copolymer and the wax, but the mixing ratio of the resin component and the ethylene copolymer and the wax is selected in a wide range. Can be. For example, paper, plastic film, aluminum foil and other packaging adhesives can be applied by various coating methods such as roll-coating, gravure-coating, tape-coating, etc. Can also be used. In general, for the purpose of blending, 20 to 300 parts by weight of the tackifier and 10 to 400 parts by weight of wax are preferably added to 100 parts by weight of the ethylene copolymer.

In addition, when a relatively strong adhesive force is required, such as for woodworking and bookbinding, or a mixture containing many ethylene-based copolymers or a mixture mainly composed of an ethylene-based copolymer and the above-mentioned resin, it is rich in rigidity and flexibility and has high adhesiveness. It is possible to prepare a heat-melt adhesive having a composition.

As blending in this case, it is applicable in the range of 20-200 weight part of said tackifying resin and 10-100 weight part of waxes with respect to 100 weight part of ethylene-type copolymers.

Examples will be illustrated below to specifically clarify the contents of the present invention, but these are examples, and the present invention is not limited to the present embodiment unless it contradicts the spirit thereof.

Example 1

First, the tackifier resin component used in the present invention is prepared as follows, for example.

The cracked oil fraction F in the boiling point range of 140 ° -220 ° C, which is a byproduct of steam cracking of naphtha, has the following composition as a result of gas chromatography analysis.

Polymerizable component (wt%) 49.0

Total content of cyclopentadiene and methylcyclopentadiene (wt%) 1.6

Total content of indene and its alkyl derivatives (wt%) 8.4

Dicyclopentadiene Content (wt%) 0.4

Conjugated Diolefin Content (%) 4.0

Inden Content (%) 18.5

This cracked oil fraction F is used as a starting raw material oil and charged to the rectification column A-1 shown in Table 2 via a heater, and the total content of indene and its alkyl derivatives, which are one of the conditions for regulation of the raw material oil of the present invention, in the column top is 2 The operating conditions of an oil refinery tower are set so that the oil content of% or less and an indene content of 8% or less is obtained.

The conditions are shown in Table 2.

[Table 2] Operation Conditions in Oil Refinery

Subsequently, the oil flowing out from the column A-1 is charged into the rectification column C-1 shown in Table 2, and the total content of cyclopentadiene and methylcyclopentadiene is 0.7 wt% or less under the operating conditions shown in Table 2, and the conjugated di The raw material oil which satisfy | fills the raw material oil regulation of this invention that an olefin content rate is 3% or less is obtained by C-1 tower column top. The conjugated diolefins flow out of the column C-1.

This operation gave 58 parts of the raw material oil of the present invention with 100 parts by weight of the starting raw material oil. Moreover, the composition of this raw material oil is as follows.

Polymerizable Content (wt%) 42.60

Total cyclopentadiene and ethylcyclopentadiene (wt%) 0.40

Total content of indene and its alkyl derivatives (wt%) 1.00

Conjugated Diolefin Content (%) 0.84

Indene Content (%) 2.51

0.5 wt% of the boron trifluoride phenol complex compound catalyst was added to the crude oil thus obtained, polymerized at 20 DEG C for 3 hours, removed with caustic soda aqueous solution, washed with water, and distilled to remove unreacted oil and low polymer. 1-A was obtained.

The softening point (circulation method) of Resin 1-A was 95 degreeC, and the cancellation value (according to ASTMD-1,158-57T) was 7, color 1- (Gardner color number based on ASTMD-1,544-58T).

40 parts by weight of the resin 1-A thus obtained, 40 parts by weight of an ethylene-vinyl acetate copolymer (Mitsui Poly Chemicals Co., Ltd .: Everflex # 220, vinyl acetate content 28% MI150), paraffin wax (manufactured by Japan Petroleum Co., Ltd .; Melting | fusing point 145 degreeF) 20 weight part was melt-mixed at about 180 degreeC, and the thermomelt adhesive was prepared.

Example 2

Boron trifluoride phenol complex catalyst was carried out at 1.0wt%, polymerization temperature 40 ° C., and others were polymerized in the same manner as in Example 1 to obtain a resin 2-A having a softening point of 80 ° C., cancellation of 14 and color ¹⁺ , and Example 1 A thermal melt adhesive was obtained in the same manner as described above.

Example 3

Boron trifluoride phenol complex catalyst subjected to 0.5wt%, the polymerization temperature is 15 ℃ other and polymerized in the same manner as in Example 1, the softening point 105.C, canceled 7, color 1 ^- to obtain a resin A-3 of Example The heat-melt adhesive was obtained in the same manner as 1.

Example 4-11

The heat-melt adhesive was obtained like Example 1 with the compounding system shown in Table 3.

Comparative Example 1-2

While starting polymer oil F in Example 1 was polymerized as it was under the same conditions as in Example 1, polymerization was carried out under the same conditions as in Example 1 except that starting raw material oil F and a polymerization temperature of 60 ° C. were separately used, and each softening point was 120. C, 80 degreeC, cancellation | fever obtained 18,25 and resin F-1 and F-2 of the color 4,5.

Also about resin F-1 and F-2, the heat-melt adhesive was obtained by the same method as Example 1, and it was set as the adhesive agent of Comparative Examples 1 and 2, respectively.

[Comparative Example 3-7]

As a resin of Table-4 and a compounding system, it carried out similarly to Example 1, and obtained the heat-melt adhesive agent as the adhesive agent of the comparative example 3-7, respectively.

The test of each item mentioned later about the heat melt adhesive prepared by each said Example and the comparative example was done.

The results are shown in Tables 3 and 4.

In Tables 3 and 4, it is evident that the heat-melt adhesive composition according to the present invention is excellent in both low temperature and color as well as adhesion.

In addition, the softening point of the resin used in the present invention is selected in a wide range of 50-125 ℃ depending on the application, but if the softening point is lower than this range, the softening point of the heat-melting adhesive is lowered, the heat resistance is worse, and if it is higher, the compatibility decrease The adhesiveness is also lowered, preferably in the range of 60 ° -120 ° C.

In addition, the copolymer component content of ethylene-based copolymers such as EVA used in the heat-melt adhesive composition of the present invention is too small, the compatibility is lowered, and the adhesion is poor, so the copolymer component content is 10-60wt%, preferably 15 -45 wt% is suitable.

As the wax component, petroleum waxes such as paraffin wax and microcrystalline wax having a melting point of 50 ° C-93.3 ° C (110 ° F-200 ° F) and natural waxes such as carnauba can be used. As also indicated, when the low molecular weight by-product wax produced by PE production and various synthetic waxes are used, a particularly heat-melting adhesive composition having a high softening point and excellent adhesive properties is obtained.

Test method

(1) Softening point (circulation method)

According to JISK-2,531.

(2) melt viscosity

-According to Brookfield viscometer.

(3) adhesion

(A) Base material: aluminum

The adhesive layer was pressed at 180 ° C for 3 minutes so that the adhesive layer became 0.2mm between 0.1mm aluminum stages, and was left at 20 ± 1 ° C and 60% humidity for 2.4 hours, followed by T-type peeling with a Tensile tensile tester (peel rate 150mm / min). Done.

(B) Base material: polyester

It applied to the polyester film (38 micrometers in thickness) with the applicator so that an adhesive bond layer might be 0.1 mm, and the adhesive force was calculated | required as 1.0 second hot rod and (A) at 2 kg / cm <3> at 120 degreeC.

(4) low temperature characteristics

A test piece of 100 (length) x 10 (width) x 2 (thickness) mm of the heat-melt adhesive was prepared and judged whether or not it was bent along the axis of the 3 mm mandrel with a JISK-5,400 bending tester at -10 ° C.

(Circle): It does not bend. X: Folds.

(5) color evaluation

The color of the heat-melt adhesive solidified after blending was determined by the criteria indicated below.

White: ◎, Pale yellow: ○, Yellow: △, Brown: ×

TABLE 3

* -1 Japan Petroleum Co., Ltd. melting point 64 ℃ (145。F)

* -2 Japan Petroleum Co., Ltd. melting point 82.2 ° C (180 ° F)

* -3 Low molecular weight polyethylene wax softening point made by Nippon Petrochemical Co., Ltd. 91 ℃

TABLE 4

Claims (1)

It has a boiling point within the range of 140-220 ° C. in the decomposition oil obtained from thermal decomposition of petroleum, the content of conjugated diolefin is 0.7 wt% or less, the content of conjugated diolefin is 3% or less, and the total content of indene and its alkyl derivatives. Using 2 wt% or less of an oil adjusted to a condition of indene content of 8% or less as a raw material, a Friedel Craft catalyst is added within the range of 0.01-5 wt% with respect to the raw material oil, and within a range of -30 ° C to + 60 ° C. A heat-soluble adhesive composition comprising an aromatic hydrocarbon resin obtained by polymerization at a temperature as an essential component such as an ethylene copolymer and a wax.