WO2002018510A1

WO2002018510A1 - Hot-melt composition and modified aromatic petroleum resin for use therein

Info

Publication number: WO2002018510A1
Application number: PCT/JP2001/007359
Authority: WO
Inventors: Hitoshi Yanagishita
Original assignee: Nippon Petrochemicals Company, Limited
Priority date: 2000-08-29
Filing date: 2001-08-28
Publication date: 2002-03-07
Also published as: JP2002069408A

Abstract

A hot-melt composition which comprises specific amounts of: (a) an ethylene copolymer resin; (b) a modified aromatic petroleum resin with a specific weight-average molecular weight obtained by copolymerizing (1) a polymerizable ingredient contained in a fraction resulting from the thermal cracking of petroleum hydrocarbons having a specific boiling point range, a specific vinyltoluene content, and a specific indene content, (2) β-phellandrene or turpentine oil containing β-phellandrene, and (3) a phenol compound in a specific proportion with the aid of a Friedel-Crafts catalyst; and (c) a wax. The composition has excellent thermal stability and improved high-temperature bonding properties. It is usable in a hot-melt coating material, printing ink, adhesive, sealant, etc.

Description

Description Hot melt composition and modified aromatic petroleum resin used therefor

The present invention relates to a hot-melt composition and a modified aromatic petroleum resin used for the same, and more particularly to a hot-melt adhesive, for example, a hot-melt composition having improved heat stability and heat-resistant adhesiveness, and a hot-melt used for the same. The present invention relates to a modified aromatic petroleum resin for a composition. Background art

JP-A-55-65248 discloses a hot melt composition in which phenols and turpentine are combined in a specific pyrolysis oil fraction having a low indene content and a high vinyltoluene content. It has been proposed to incorporate a modified aromatic petroleum resin obtained by polymerization.

This modified aromatic petroleum resin has excellent compatibility with base resins such as ethylene monoacetate vinyl copolymer (hereinafter referred to as “EVA”), and is used in combination with EVA or the like. It is a petroleum resin suitable for an adhesive. However, this hot melt adhesive did not always have a sufficient practical adhesive strength in a region above a certain temperature.

For example, in a packaging operation in which various high-temperature liquids supplied from the manufacturing process are filled in appropriate containers such as cans and bottles, and then packed together in a cardboard box or the like, the heat of the contents is reduced by the packaging box. It is transmitted to. As described in the above-mentioned publication, generally, a hot-melt adhesive which exhibits an adhesive strength by solidification tends to have a reduced adhesive strength in a high-temperature environment. Therefore, since the contents must be left until the contents are sufficiently cooled and the temperature of the packaging box becomes sufficiently low, the production speed of the packaging is reduced by the amount of time for which the packaging is left. Therefore, it is desired to improve the heat resistance of various substrates, particularly paper substrates such as corrugated paper. In general, it is considered effective to increase the molecular weight of petroleum resin to improve heat resistance. However, a mere increase in molecular weight is not sufficient for adhesive properties, especially at low temperatures.

Replacement form (Rules Adhesion is likely to decrease.

The present invention provides a modified aromatic petroleum resin described in the above-mentioned publication, while maintaining good hot-melt adhesive properties, especially when used as a composition with EVA or the like, while maintaining its heat-resistant adhesive properties. It is an object of the present invention to provide a petroleum resin for a hot melt composition having improved heat stability. Disclosure of the invention

Hereinafter, the present invention will be described in detail.

The present inventors have conducted intensive studies on the above problems, and found that when polymerizing an aromatic petroleum resin, a pyrolyzed oil fraction containing a specific ratio of indene / vinyltoluene was used, and] 3 —It has been found that the above problem can be solved by selecting a phenandrene phenol compound.

That is, the first of the present invention is:

(a) 100 parts by weight of an ethylene copolymer resin,

(b) A modified aromatic petroleum resin having a weight average molecular weight in the range of 500 to 2000 obtained by copolymerizing the following (1) to (3) in the presence of a Friedel-Crafts type catalyst

50 ~: 1 50 parts by weight,

(1) The heat of petroleum hydrocarbons mainly consisting of components with a boiling point in the range of 140 to 220 ° C, with a toluene content of 10% or more and less than 60% and an indene content of 10-80%. 100 parts by weight of a polymerizable component of the pyrolyzed oil fraction obtained by cracking,

(2) | 3-Ferlandrene 3-40 parts by weight,

(3) Phenol compound:! ~ 15 parts by weight, and

(c) Wax 10 ~: L 00 parts by weight

The present invention relates to a hot melt composition comprising:

A second aspect of the present invention relates to the hot melt composition according to the first aspect of the present invention, wherein (1) the pyrolyzed oil fraction further has a conjugated diolefin content of 2.0% or less.

The third aspect of the present invention is that] 3-ferrandrene is 15 weight by weight. /. The first invention using (2-1) turpentine in an amount corresponding to 100 parts by weight of the polymerizable component of the pyrolyzed oil fraction and containing 3 to 40 parts by weight of 3-ferrandrene Hot Mel described G composition.

A fourth aspect of the present invention relates to the hot melt composition according to the third aspect, wherein (1) the content of conjugated diolefins in the pyrolysis oil fraction is 2.0% or less.

A fifth aspect of the present invention relates to the hot melt composition, which is the ethylene-based copolymer resin ethylene-butyl acetate copolymer according to the first or fourth aspect.

The sixth aspect of the present invention is (1) a pyrolyzed oil fraction obtained by pyrolysis of petroleum hydrocarbons, mainly composed of components having a boiling point in the range of 140 to 220 ° C. and having a toluene content of 10%. . /. More than 60. /. Less than 100 parts by weight of the polymerizable component, and (2)] 3-ferrandrene 3 to 40 parts by weight.

(3) F: a modified aromatic petroleum resin for a hot melt composition having a weight average molecular weight in the range of 500 to 2000, which is obtained by copolymerizing 1 to 15 parts by weight of an r-noll compound in the presence of a Friedel-Crafts type catalyst. .

Hereinafter, the present invention will be further described.

The (a) ethylene copolymer resin of the hot melt composition of the present invention may be a polar monomer copolymerizable with ethylene, for example, monocarboxylic acid butyl ester such as butyl acetate, acrylic acid, methacrylic acid and the like. (4) One or two or more copolymers of esters thereof with alcohols such as methanol and ethanol are exemplified. The content of the polar monomer component in the ethylene copolymer resin is 1 to 60% by weight, preferably 15 to 45% by weight. / ₀ is appropriate. The melt index (measured at 190 ° C, load 2.16 kg, for 10 minutes) used as a standard of molecular weight is preferably 10 to 1,000 g / l 0 minutes. More preferred examples of the ethylene-based copolymer resin include EVA and ethylene-ethyl acrylate copolymer. The (1) pyrolysis oil fraction of the (b) raw material of the modified aromatic petroleum resin used in the present invention is obtained by pyrolysis of petroleum hydrocarbons such as crude oil, kerosene oil, naphtha, butane, and It is a fraction mainly composed of components having a boiling point in the range of 140 to 220 ° C, and has a vinyltoluene content of 10%. /. More than 60. /. Less, preferably 10% or more and 55% or less, and an indene content of 10 to 80%, preferably 15 to 80%. Preferably, the conjugated diolefin content is 2.0% or less.

Usually, the pyrolysis oil fraction comprises a polymerizable component and a non-polymerizable component. The polymerizable component is a polymerizable unsaturated component included in the above boiling point range in the pyrolysis oil fraction, such as styrene, its alkyl derivative α-methylstyrene,] 3-methylstyrene, Vinyl / retoluene; indene; alkynole derivatives thereof; cyclopentadiene, methylcyclodicitadiene, dicyclopentadiene and alkyl derivatives thereof. These polymerizable components are usually present in the pyrolysis oil fraction at 10 to 90% by weight.

The non-polymerizable component is composed of the remaining components in the pyrolysis oil fraction, and is mainly a saturated hydrocarbon compound such as an alkyl benzene having 9 carbon atoms (C ₉ alkyl benzene). Make

Note that when the production of petroleum resins, viscosity adjustment, the content of the polymerizable components such as by addition of a saturated hydrocarbon compound such as c ₉ alkylbenzenes as separately by non-polymerizable components appropriate for other purposes,] 3 The polymerization can be adjusted by adjusting the amount of ferrandrene and, in some cases, J3-ferrandrene containing turpentine-phenol compound to 30 to 70% by weight based on the total amount of the turpentine.

Here, the vinyltoluene content (%) refers to the ratio of the content (wt%) of vinyltoluene to the amount of polymerizable components (wt./.) Of the components contained in the pyrolysis oil fraction. . The indene content (%) is the ratio of the total content (% by weight) of indene and its alkyl derivative to the amount of polymerizable components (% by weight) of the components contained in the pyrolysis oil fraction. Say. The conjugated diolefin content (%) refers to the total content (wt%) of pentagon and cyclopentene relative to the polymerizable component (wt%) of the components contained in the pyrolysis oil fraction. ). The total of the toluene content, the indene content and the conjugated diolefin content is 20% or more and 100% or more. /. Less than.

The content of each component can be analyzed by a conventional method using gas chromatography, and the content of each component is calculated from the results.

In the present invention, a fraction mainly composed of a component having a boiling point in the range of 140 to 220 ° C. is used as a pyrolysis oil fraction. Components having a boiling point of less than 140 ° C are not preferred because they contain a large amount of conjugated diolefins and non-conjugated diolefins, and the resulting resin has poor hue and heat stability. Also, if a component having a boiling point exceeding 220 ° C is used, Similarly, a resin having insufficient heat resistance and hue can be obtained, and the adhesiveness of a hot-melt adhesive becomes poor, which is not preferable.

Furthermore, it is important that the content of bürtoluene and indene be in the above-defined range specified in the present invention, and by doing so, the heat-resistant adhesiveness of the hot melt composition using the obtained resin can be improved.

The (1) pyrolyzed oil fraction preferably has a conjugated diolefin content of 2.0% or less. The conjugated diolefin content can be adjusted, for example, by distilling the pyrolysis oil fraction. In addition, if necessary, dicyclopentadiene of the pyrolysis oil fraction 蒸留 Dimethyl cyclopentadiene, etc., is pyrolyzed at a temperature lower than the thermal decomposition temperature of dicyclopentadiene, so that cyclopentadiene シ methylcyclopentane is not generated. The content of the conjugated diolefin can also be adjusted. If the content exceeds 2.0%, there is a concern that the hue and heat stability of the obtained resin are inferior.

The (1) pyrolysis oil fraction, which is a raw material of the present invention, mainly comprises a component having a boiling point in the range of 140 to 220 ° C of pyrolysis oil produced as a by-product during the pyrolysis of petroleum hydrocarbons. Thus, it can be easily obtained only by ordinary industrial distillation, and there is no need for precision distillation or multi-stage distillation. However, of course, it can also be obtained by appropriately performing such precision distillation and multi-stage distillation.

If the content of vinyltoluene and indene in the pyrolysis oil fraction is a predetermined ratio, it can be used as it is. Further, by distilling the pyrolysis oil fraction, fractions having different toluene toluene dendine contents can be separately adjusted, and the content can be adjusted by mixing these. The content can also be arbitrarily adjusted by separately preparing toluene and indene and mixing the same with the above pyrolyzed oil fraction. These unadjusted or adjusted fractions can be used alone or as a mixture of two or more. In this way, it is possible to prepare fractions having various contents. By using this fraction as a raw material, a resin having an arbitrary content can be produced, and the properties of the resin can be adjusted as needed. (B) The raw material of the modified aromatic petroleum resin of the present invention (2) —Fuelandrene is a monoterpene hydrocarbon. It is found in essential oils of grape, ginger oil, ginger oil, turpentine oil, Canadian balsam oil, etc. The abundance varies greatly depending on the type of plant and the place of production. ] 3-Frandrene can be obtained by further rectifying the fraction obtained by fractionating these essential oils as they are or after isomerizing them.

Industrially, it can be obtained by, for example, isomerizing and fractionating turpentine oil such as gum turpentine, wood turpentine, sulfate wood turpentine, and dry distilled turpentine by heat or the like. Also, as a method for synthesizing 3-ferrandrene, for example, a method is known in which p-mensen-11 is brominated, treated with alcoholic potassium hydroxide, and the resulting compound is rectified to obtain the compound. . ] -Ferandrene obtained by these methods can all be used in the present invention. In addition, a material obtained by a method other than these may be used.

The (2)] 3-flandren in the present invention is polymerized by using 3 to 40 parts by weight based on (1) 100 parts by weight of the polymerizable component of the pyrolysis oil fraction. If the amount is less than 3 parts by weight, the compatibility of the obtained resin with the base polymer becomes poor, while if it exceeds 40 parts by weight, the softening point of the resin decreases and the adhesiveness cannot be improved.

In the present invention, it is also possible to use turpentine oil having a content of (2-1) β-felandrene of 15% by weight or more in place of the above (2) j8-ferrandrene. Such turpentine oil is generally available and is cost effective because it does not require the purification of / 3-ferrandrene. In the case of turpentine having a content of 3-ferrandrene of less than 15% by weight, the compatibility of the obtained resin with the base polymer becomes poor.

(2-1) — Turpentine oil with a content of ferrandren of 15% by weight or more is fractionated by isomerizing turpentine oil such as gum turpentine, steam wood turpentine, sulfate wood turpentine, and carbonized turpentine with heat, etc. It can be manufactured by However, not all isomerized turpentine can be used because the content of 3-ferrandrene varies greatly depending on the type of turpentine and the manufacturing process. It is also possible to separately mix a predetermined amount of (2) / 3-ferrandrene with a known turpentine oil and adjust it to the above range before use.

Known turpentine oil is produced from volatile components of sap contained in softwoods. Industrially, it is mainly classified into those produced from four types: gum turpentine, steam pad turpentine, sulfur turpentine and carbonized pad turpentine. Among them, gum turpentine is obtained by distilling raw pine trees collected from wounds and scars on raw pine trees. Steam turpentine or wood turpentine is obtained by distilling the extract of unharvested pine stumps that have fallen off the bark and sapwood. Sulfate wood turpentine or sulfate turpentine is obtained by condensing the steam generated during the heating step of the papermaking kraft (sulfate) pulping process. The carbonized wood turpentine is produced from light distillates obtained by carbonizing (carbonizing) waste coniferous wood such as trees with high resin content and logging. What is commonly used is further distilled.

In the present invention, (3) 1 to 15 parts by weight of the phenol compound is further added to 100 parts by weight of the polymerizable component of the pyrolyzed oil fraction. Here, the phenol compound is an alkyl-substituted phenol such as phenol or cresol or xylenol. These can be used in combination. If the added funool compound is less than 1 part by weight, the compatibility of the obtained resin with the base polymer becomes poor, and if it exceeds 15 parts by weight, the softening point of the resin is lowered, and both improve the adhesiveness. Can not.

The polymerization of (b) the modified aromatic petroleum resin of the present invention may be carried out according to (1) 100 to 100 parts by weight of the pyrolysis oil fraction, (2)] 3- to 40 parts by weight of 3-ferrandrene or ) 15 _ weight of β_ferrandrene. /. The turpentine oil contained above and (3) 1 to 15 parts by weight of a phenol compound are added in the presence of 0.05 to 5.0% by weight of a Friedel-Crafts type catalyst. As the Friedel-Crafts type catalyst, aluminum chloride, boron trifluoride gas or a complex catalyst thereof using water, ethers, phenols, alcohols, etc., for example, boron trifluoride / phenolate is preferable. Although the amount of the phenol compound contained as the complex catalyst is usually small, the amount of the phenol compound is included in the amount of the phenol compound (3). Protonic acids such as sulfuric acid and hydrochloric acid, solid acids such as silica and alumina, and acidic ion exchange resins can also be used.

Although the polymerization temperature and the polymerization time are not particularly limited, for example, a temperature range of 120 to 80 ° C. The copolymerization can be carried out in the range of 0.1 to 10 hours. After the polymerization, the catalyst is neutralized and removed, and a modified aromatic petroleum resin having a weight average molecular weight of 500 to 2000 is obtained by distillation or the like as appropriate.

The mixing ratio of the (b) modified aromatic petroleum resin is in the range of 50 to 150 parts by weight per (a) 100 parts by weight of the ethylene copolymer resin. If the amount is less than 50 parts by weight, the initial adhesiveness, cold resistance and settability tend to decrease, and if it exceeds 150 parts by weight, the cohesive strength decreases and the adhesive strength also decreases.

As the wax (c), petroleum waxes such as paraffin wax and microcrystalline wax, natural wax, polyethylene wax, polypropylene wax, atactic polypropylene wax, and sasol wax are appropriately used according to the purpose. it can. This amount is (a) 100 to 100 parts by weight per 100 parts by weight of the styrene-based copolymer resin. If the amount is less than 100 parts by weight, the melt viscosity is high and the workability—the wettability to the substrate is reduced. If the amount is more than 100 parts by weight, the adhesive strength is reduced.

The hot melt composition of the present invention can be produced by mixing and melting the above (a) the ethylene copolymer resin, (b) the modified aromatic petroleum resin, and (c) the resin by an ordinary method.

The hot melt composition of the present invention can be used as a so-called hot melt type paint, printing ink, adhesive, sealant, and the like. A particularly preferred application is hot melt adhesives. Hot melt adhesives can be applied to various substrates such as paper, plastic, and metals such as aluminum. Particularly preferred substrates are cardboard and other paper substrates. It can also be used as a hot melt sealant for wood and bookbinding.

In addition, according to each application such as an adhesive and a sealant, a compounding agent known for each application, for example, a filler such as calcium carbonate, titanium oxide, talc or clay, a plasticizer, an organic or inorganic pigment, an antioxidant An appropriate amount of a polymerization inhibitor or the like can be added. BEST MODE FOR CARRYING OUT THE INVENTION Next, the present invention will be specifically described with reference to examples. The test methods in Examples and Comparative Examples are as follows.

(Test method)

(1) Weight average molecular weight

The weight average molecular weight of the petroleum resin is measured by GPC. The columns and analysis conditions are as follows.

Column: TSK—Gel G—4000 + 2000 Hs Analysis conditions: 38 ° C

Pressure 5.9MPa

Flow velocity 1.0 m 1 / min

Solvent Tetrahydrofuran (THF)

(2) Thermal stability test

50 g of the hot-melt adhesive obtained with the prescribed composition described below was placed in a 100 ml beaker, heated at 180 ° C for 72 hours, cooled and solidified, and visually observed for skinning and carbide formation. The determination is made based on the following criteria.

Here, the skinning is a gel that is generated on the surface of the hot melt adhesive by heat treatment, and the carbide is a black material that is generated in the hot melt adhesive under the beaker. Any of these causes is a very important item in the thermal stability test because it causes clogging of the hot melt adhesive discharge nozzle.

Evaluation: Leather upholstery: ◎ None, 〇 Slightly present, X many

Carbide: ◎ None, 有り Slightly present, X

(3) Heat resistance

A cardboard B flute (22 Og / m ² ) of ^two K liners with a width of 25 mm and a length of 100 mm was used as a test piece, and the hot-melt adhesive obtained with a prescribed composition described below was applied to the surface of the test piece. Apply at a right angle (width direction) to the flute, and bond the flute in parallel on the back surface of the same test piece material under the following bonding conditions.

Using this test piece, a shear creep test at a load of 1 kg and 60 ° C was performed, and the time at which the ruptured drop occurred at the joint of the adhesive test piece was measured. indicate. Bonding conditions: Adhesive application temperature 1 80 ° C

Adhesive application amount 3 g / m (0.05 g / 25 mm) Open time (solidification time of adhesive) 2 sec

Compression load 2 kg

Compression time 2 sec

(4) Low temperature adhesion

A corrugated cardboard B-flute (220 g Zm ² ) of K liner with a width of 50 mm and a length of 100 mm was used as a test piece. On the other hand, apply in parallel (width direction), and bond under the condition of (3) heat resistance adhesion so that the flutes cross the back surface of the test piece material.

When the joint of the adhesive test piece is broken in an L-shaped peeling mode at a predetermined low temperature, the state of rupture of the peeled surface of the test piece is determined according to the following determination conditions.

Evaluation: ◎ Material rupture, 〇 Most material rupture, △ Most interfacial fracture, X interfacial rupture

Example 1>

The pyrolysis oil fraction having the following composition and a boiling range of 140 to 220 ° C obtained by pyrolysis of petroleum was used as feedstock (a).

Polymerizable component 70.0 weight. /.

Total content of cyclopentadiene and methylcyclopentadiene

0.3% by weight Vinyl toluene content 30

'Induced ... Total conductor content 29 3% by weight Conjugated diolefin content 0 4%

Burtoluene content 43 0%

Inden content 41 9%

In 100 parts by weight of the polymerizable component of this raw material oil (a), the content of] -ferrandrene was 30% by weight and the content of limonene was 60% by weight / ⁰ . After adding 23 parts by weight of turpentine oil (tl) and 5 parts by weight of phenol, C ₉ alkylbenzene was further added to adjust the amount of the polymerizable component to 50% by weight (based on the total filling amount). Conversion Boron phenolate was added at 0.2% by weight and polymerized at 20 ° C. for 3 hours. The catalyst was neutralized with slaked lime, and then filtered. The unreacted oil and low-polymer were removed by distillation to obtain resin (A) having a weight average molecular weight of 1350.

100 parts by weight of resin (A) obtained, EVA (DuPont-Mitsui Polychemicals Co., Ltd.: trade name Evaflex # 21 0, a vinyl acetate content of 28 weight ^_0/0, Merutoi index 400 g / l 0 min 100 parts by weight, paraffin wax (Nippon Oil

(Mfg .: melting point: 155 F) 50 parts by weight were melt-mixed at about 180 ° C. by a conventional method to prepare a hot melt composition, which was tested for heat stability and low-temperature adhesion. <Example 2>

The pyrolyzed oil fraction having the following composition and a boiling range of 140 to 220 ° C obtained by the pyrolysis of petroleum was used as feedstock (b).

Polymerizable component 74.6% by weight Total content of cyclopentadiene and methylcyclopentadiene

1.4 weight. /. Vinyl toluene content 13.0% by weight Total content of indene and its alkyl derivative 50.2% by weight. / ₀ Conjugated diolephine content 1.9% Vinyltoluene content 17.4% Indene content 67.3% Polymerizable component of this stock oil (b) 100 parts by weight,] 3-Felandrene content But 30 weight ⁰ /. In 23 by weight part of the turpentine limonene content of 60 wt% (tl), was added to phenol 5 parts by weight, further added the total polymerizable components is 50 weight C ₉ alkylbenzenes. / ₀ , and polymerized under the same conditions as in Example 1 to obtain a resin B having a weight average molecular weight of 1,550.

Next, a hot melt composition was blended in the same manner as in Example 1, and the hot melt adhesive properties were tested on the hot melt composition.

Example 3>

The pyrolyzed oil fraction having the following composition and a boiling range of 140 to 220 ° C obtained by pyrolysis of petroleum was used as feedstock (c). Polymerizable component 58.9% by weight Total content of cyclopentadiene and methylcyclopentadiene

0.3% by weight Vinyl toluene content 28.7% by weight Total content of indene and its alkyl derivative 12.6% by weight Conjugated diolephine content 0.5%

Vinyl toluene content 49.0%

Linden content 21.4%

In 100 parts by weight of the polymerizable component of this raw material oil (c), 23 parts by weight of turpentine oil (t 2) having an 8-fufurandrene content of 40% by weight and a limonene content of 50% by weight After adding 5 parts by weight of phenol, C ₉ alkylbenzene was further added to bring the total polymerizable component to 50 parts by weight. /. The polymerization was carried out under the same conditions as in Example 1 to obtain a resin C having a weight average molecular weight of 1200.

Thereafter, a hot melt composition was prepared in the same manner as in Example 1, and the properties of the hot melt adhesive were tested.

The pyrolysis oil fraction having the following composition and a boiling range of 140 to 220 ° C obtained by pyrolysis of petroleum was used as feed oil (d).

Polymerizable components 5 7.

Total content of cyclopentadiene and methylcyclopentadiene

0 1% by weight Vinyl toluene content 3 11 1% by weight. /. Total content of indene and its alkyl derivative 58% by weight Conjugated diolefin content 0 2% Bull toluene content 5 45 5% Indene content 102% Polymerizable component of this feedstock oil (d) 100 parts by weight a, a- pinene content 9 0 wt%, 3- pinene content of 5 wt% a is commercially available turpentine oil (t 3) 2 3 parts by weight, was added to phenol 5 parts by weight, further added all polymerizing C ₉ alkylbenzenes 5 possible ingredients It was adjusted to be 0% by weight / o and polymerized under the same conditions as in Example 1 to obtain a resin D having a weight average molecular weight of 150.

C. After adding 23 parts by weight of the commercially available turpentine oil (t 3) of Comparative Example 1 and 5 parts by weight of phenol to 100 parts by weight of the feed oil fraction (c), C. Alkylbenzene was further added to adjust the polymerizable component to 50% by weight, and polymerization was carried out under the same conditions as in Example 1 to obtain a resin E having a weight average molecular weight of 110.

Next, a hot melt composition was prepared in the same manner as in Example 1, and the properties of the hot melt adhesive were tested.

Table 1 shows the test results of the adhesive properties and the thermal stability of the resin hot melt compositions in Examples 1 to 3 and Comparative Examples 1 and 2.

Example Comparative example

1 2 3 1 2 Change Feedstock (a) 100

(1)

Raw oil (b) 100

Stone cracked oil

Feedstock oil (c) 100 100 Oil component ―

Tree Raw oil (d) ― 100

Fat (2)] 3-Hue turpentine 11 23 23 —

Raw turpentine t 2 23

Charge Sales turpentine t 3 23 23

(3)

F: Ninoichi Fenomono 5 5 5 5 5

Odd! "Raw resin name A B C D E

1350 1550 1200 1050 1130 E Petroleum tree Molecular weight

Pair

V Fat Mixing ratio 100 100 100 100 100

Success

EVA compounding ratio 100 100 100 100 100

50 50 50 50 50 Lux

熱〇〇〇成定定成成成成成成成成成成成成成成成成成成成成成成成成成成成成成成成成成 5 成 5 成成成 5 成成 5 5 5 c ◎ ◎ ◎ ◎ ◎

5 ° C ◎ ◎ ◎ ◎ ◎ Property 0. C 〇〇 o 〇単位 Unit The compounding ratio is part by weight. Here, Comparative Example 1 uses a petroleum resin corresponding to Example 1 described in the above publication, and Comparative Example 2 uses Comparative Example 1 of the same publication. This is an example using a petroleum resin equivalent to the above.

As is clear from Table 1, the hot-melt composition according to the present invention has better adhesive properties to paper base materials such as corrugated pole paper, especially heat-resistant adhesives, compared to the hot-melt composition using a petroleum resin described in the above publication. In addition, it has excellent properties such as thermal stability and low-temperature adhesiveness. Industrial applicability

The hot melt composition of the present invention has excellent heat stability and improved heat resistance. The hot melt composition of the present invention can be used as a hot melt type paint, printing ink, adhesive or sealant as a specific application. For example, when a hot melt adhesive is used, a favorable effect is exhibited particularly when applied to a paper base material such as corrugated pole paper.

Furthermore, the modified aromatic petroleum resin of the present invention is a resin suitable for the above-mentioned hot melt application, particularly for a hot melt adhesive.

Claims

The scope of the claims

1. (a) 100 parts by weight of an ethylene copolymer resin,

50 ~: 1 50 parts by weight,

(1) Petroleum hydrocarbons with a boiling point in the range of 140 to 220 ° C and a vinyltoluene content of 10% to less than 60% and an indene content of 10 to 80% 100 parts by weight of a polymerizable component of a pyrolysis oil fraction obtained by pyrolysis,

(2) —Fuelandrene 3-40 parts by weight,

(3) 1 to 15 parts by weight of a phenolic compound, and

(c) Wax 10 to: 100 parts by weight.

2. The hot melt composition according to claim 1, wherein the content of conjugated diolefin in the (1) pyrolyzed oil fraction is 2.0% or less.

3. Includes 15% by weight or more of / 3--flandren and 100 parts by weight of the polymerizable component of the pyrolyzed oil fraction. 2-1) The hot melt composition according to claim 1, wherein turpent oil is used.

4. The hot melt composition according to claim 3, wherein (1) the content of conjugated diolefin in the pyrolysis oil fraction is 2.0% or less.

5. The hot melt composition according to claim 1, wherein the (a) ethylene-based copolymer resin is an ethylene monoacetate butyl copolymer.

6. (1) A pyrolysis oil fraction obtained by the pyrolysis of petroleum hydrocarbons, mainly consisting of components with a boiling point in the range of 140 to 220 ° C and a toluene content of 10% or more. . /. Less than 100% by weight of the polymerizable component.

(2)] 3-Ferrandrene 3-40 parts by weight

(3) Phenol compound 1 to 15 parts by weight

A modified aromatic petroleum resin for a hot melt composition having a weight average molecular weight in the range of 500 to 2,000, which is obtained by copolymerizing styrene in the presence of a Friedel Crafts type catalyst.