JP2002069408A - Hot melt composition and modified aromatic petroleum resin used for hot melt component - Google Patents

Abstract

PROBLEM TO BE SOLVED: To develop a hot melt component which has a superior thermal stability and an improved heat-resistant tackiness in using for hot-melt type paint, printing ink, adhesives or sealant. SOLUTION: The hot melt component is constituted of; (a) an ethylene-based copolymer resin, (b) (1) components, capable of being polymerized, of pyrolysis oil fraction that can be secured by thermal decomposition of a petroleum hydrocarbon having vinyltoluene content rate and indene content rate, mainly to be the components of its boiling point ranging from 140 deg.C to 220 deg.C; (2) a phellandorene or a turpentine oil containing a β-phelladorene; and (3) a modified aromatic petroleum resin of weight average molecular weight ranging from 500 to 2,000 secured by copolymerizing phenol compounds by using Friedel-Craft' s catalyst, and (c) a wax.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hot melt composition and a modified aromatic petroleum resin for use in the hot melt composition, and more particularly to a hot melt adhesive having improved heat stability and heat resistance. The present invention relates to a hot melt composition and a modified aromatic petroleum resin for the hot melt composition used therein.

[0002]

2. Description of the Related Art As a hot melt composition, Japanese Patent Application Laid-Open No.
JP-A-5-65248 proposes to blend a modified aromatic petroleum resin obtained by copolymerizing phenols and turpentine with a specific pyrolysis oil fraction having a low indene content and a high vinyltoluene content. Have been.

[0003] The modified aromatic petroleum resin has excellent compatibility with a base resin such as an ethylene-vinyl acetate copolymer (hereinafter referred to as "EVA"), and is used in combination with EVA or the like. It is a petroleum resin suitable for a melt adhesive. However, this hot-melt adhesive does not always have a sufficient practical adhesive strength in a region above a certain temperature.

[0004] For example, in a packaging operation in which various high-temperature liquids supplied from a manufacturing process are filled in an appropriate container such as a can or a bottle, and these are collectively packed in a cardboard box or the like, the heat of the contents is reduced. It is transmitted to the packaging box. As described in the above publication, a hot-melt adhesive which generally 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 of the leaving. Therefore, it is desired to improve the heat resistance of various substrates, especially paper substrates such as corrugated paper. To improve heat resistance,
Generally, it is considered effective to increase the molecular weight of the petroleum resin. However, a mere increase in molecular weight tends to cause a decrease in adhesive properties, particularly low-temperature adhesiveness.

[0005]

DISCLOSURE OF THE INVENTION The present invention relates to a hot-melt adhesive having good modified low-temperature adhesiveness when a modified aromatic petroleum resin described in the above-mentioned publication has a composition with EVA or the like. It is an object of the present invention to provide a petroleum resin for a hot melt composition having improved heat resistance and heat stability while maintaining the same.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies on the above problems, and as a result, when polymerizing an aromatic petroleum resin, a pyrolysis oil containing a specific ratio of indene or vinyltoluene. It has been found that the above problem can be solved by using a fraction and selecting β-phenlandrene and a phenol compound.

That is, a first aspect of the present invention is that (a) 100 parts by weight of an ethylene copolymer resin, and (b) the following (1) to (3) are copolymerized in the presence of a Friedel-Crafts type catalyst. 50 to 150 parts by weight of a modified aromatic petroleum resin having a weight average molecular weight of 500 to 2,000, and (1) a component having a boiling point of 140 to 220 ° C. and a vinyltoluene content of 10% or more. 100 parts by weight of a polymerizable component of a pyrolyzed oil fraction obtained by pyrolysis of petroleum hydrocarbons having an indene content of less than 60% and an indene content of 10 to 80%, (2) 3 to 40 parts by weight of β-ferrandrene (3) a hot melt composition comprising 1 to 15 parts by weight of a phenol compound and (c) 10 to 100 parts by weight of a wax.

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.

A third aspect of the present invention is to provide a thermal cracking oil fraction containing (2-1) turpentine oil containing not less than 15% by weight of β-felandrene instead of (2) β-felandrene as β-phelandrene. 3 parts per 100 parts by weight of the polymerizable component
It relates to a hot melt composition using an amount corresponding to ４０40 parts by weight.

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

A fifth aspect of the present invention relates to a hot melt composition wherein the ethylene copolymer resin in the first or fourth aspect is an ethylene-vinyl acetate copolymer.

A sixth aspect of the present invention is (1) a pyrolysis oil fraction obtained by pyrolysis of petroleum hydrocarbons, which has a boiling point of 140.
To 220 ° C., the content of vinyltoluene is 10% or more and less than 60%, and the content of indene is 10% or more.
To 80% by weight, and 100 parts by weight of the polymerizable component, (2) 3 to 40 parts by weight of β-ferrandrene and (3) 1 to 15 parts by weight of a phenol compound in the presence of a Friedel-Crafts type catalyst. The present invention relates to a modified aromatic petroleum resin for a hot melt composition having a weight average molecular weight in the range of 500 to 2,000 obtained by polymerization.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be further described.
Examples of the (a) ethylene copolymer resin of the hot melt composition of the present invention include polar monomers copolymerizable with ethylene, for example, vinyl monocarboxylates such as vinyl acetate, acrylic acid, methacrylic acid and the like. One or more copolymers of esters with alcohols such as methanol and ethanol are exemplified. The content of the polar monomer component in the ethylene copolymer resin is suitably 1 to 60% by weight, preferably 15 to 45% by weight. The melt index (measured at 190 ° C. under a load of 2.16 Kg for 10 minutes) used as a measure of the molecular weight is preferably from 10 to 1000 g / 10 minutes. EV is a preferred example of an ethylene copolymer resin.
A, ethylene-ethyl acrylate copolymer and the like.

The (1) pyrolyzed 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 and butane. And a fraction mainly composed of components having a boiling point in the range of 140 to 220 ° C. and having a vinyltoluene content of 10
% To less than 60%, preferably 10% to 55%,
Indene content of 10-80%, preferably 15-80
%. 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 among the components included in the above boiling point range in the pyrolysis oil fraction, for example, styrene, its alkyl derivatives α-methylstyrene and β-methylstyrene, vinyl Toluene; indene; alkyl derivatives thereof; cyclopentadiene, methylcyclopentadiene, dicyclopentadiene and alkyl derivatives thereof. These polymerizable components are usually present in the pyrolysis oil fraction in an amount of 10 to 90% by weight. The non-polymerizable component is composed of the remaining components in the pyrolysis oil fraction, and contains an alkylbenzene having 9 carbon atoms (C
₉ ), mainly a saturated hydrocarbon compound such as ( _9- alkylbenzene), and functions mainly as a solvent in the present invention.

In the production of a petroleum resin, the content of the polymerizable component is adjusted by adding a saturated hydrocarbon compound such as C ₉ alkylbenzene as a non-polymerizable component as needed for viscosity adjustment and other purposes. 3 to the total penetration amount including β-felandrene and, in some cases, turpentine oil and phenol compound containing β-felandrene.
The polymerization can be adjusted by adjusting the amount to 0 to 70% by weight.

Here, the vinyl toluene content (%) is
It refers to the ratio of the content (wt%) of vinyl toluene to the amount of polymerizable components (wt%) of the components contained in the pyrolysis oil fraction. The indene content (%) refers to the ratio of the total content (% by weight) of indene and its alkyl derivative to the amount of polymerizable components (% by weight) among the components contained in the pyrolysis oil fraction. In addition, the conjugated diolefin content (%) refers to the total content (% by weight) of cyclopentadiene and methylcyclopentadiene with respect to the amount of polymerizable components (% by weight) among the components contained in the pyrolysis oil fraction. Refers to the ratio. The total of the vinyl toluene content, the indene content, and the conjugated diolefin content is 20% or more and less than 100%.

The content of each component can be analyzed by gas chromatography according to a conventional method, and the respective contents are calculated from the results. In the present invention,
A raw material is a fraction mainly composed of components having a boiling point in the range of 140 to 220 ° C. 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. In addition, when a component having a boiling point exceeding 220 ° C. is used, a resin having a heat resistance and a hue that is not sufficient is obtained, and the adhesiveness when a hot melt adhesive is formed is also unfavorable. .

Further, it is important that the contents of vinyltoluene and indene be within the above-specified ranges specified in the present invention, whereby the heat-resistant adhesiveness of the hot melt composition using the obtained resin is improved. be able to.

The (1) pyrolysis 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. Also, if necessary,
Distilled below the pyrolysis temperature of dicyclopentadiene to adjust the conjugated diolefin content so that dicyclopentadiene and dimethylcyclopentadiene etc. of the pyrolysis oil fraction do not pyrolyze to produce cyclopentadiene or methylcyclopentadiene You can also. If the content exceeds 2.0%, there is a concern that the resulting resin has poor color tone and heat stability.

The (1) pyrolysis oil fraction, which is a raw material of the present invention, mainly comprises a pyrolysis oil by-produced during the pyrolysis of petroleum hydrocarbons, having a boiling point in the range of 140 to 220 ° C. Thus, it can be easily obtained only by ordinary industrial distillation, and there is no need to perform precision distillation or multi-stage distillation. However, of course, it can also be obtained by appropriately performing such precision distillation and multistage 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, the fractions having different contents of vinyltoluene and indene can be separately adjusted by distilling the pyrolysis oil fraction, and the contents can be adjusted by mixing these. The content can also be adjusted arbitrarily by separately preparing vinyltoluene or indene and mixing it with the pyrolysis 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 necessary.

(B) β-Phellandrene, which is a raw material of the modified aromatic petroleum resin of the present invention, is a monoterpene hydrocarbon. It is found in ginger oil, ginger oil, turpentine oil, Canadian balsam oil, and others. The abundance varies greatly depending on the type of plant and the place of production. β-Phellandrene can be obtained by further rectifying a fraction obtained by fractionating these essential oils as they are or after isomerizing them. Industrially, for example, it can be obtained by isomerizing and fractionating turpentine oil such as gum turpentine, wood turpentine, sulfate wood turpentine, and carbonized wood turpentine by heat or the like. As a method for synthesizing β-phenlandrene, for example, a method is known in which p-menthene-1 is brominated, treated with alcoholic potassium hydroxide, and the obtained compound is rectified to obtain the compound. The β-ferrandrene obtained by these methods can all be used in the present invention. Further, a material obtained by a method other than these may be used.

In the present invention, (2) β-phelandrene is used in an amount of 3 to 40 parts by weight based on 100 parts by weight of the polymerizable component of the (1) pyrolyzed oil fraction. If the amount is less than 3 parts by weight, the compatibility of the obtained resin with the base polymer is deteriorated. On the other hand, if the amount is more than 40 parts by weight, the softening point of the resin is lowered 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-pherandrene of 15% by weight or more instead of the above (2) β-pherandrene. Such turpentine oil is generally available and is cost effective because it does not require the purification of β-phelandrene. In the case of turpentine having a content of β-phelandrene of less than 15% by weight, the compatibility of the obtained resin with the base polymer becomes poor.

The above-mentioned (2-1) turpentine oil having a β-ferrandrene content of 15% by weight or more isomerizes turpentine oil such as gum turpentine, steam wood turpentine, sulfate wood turpentine or carbonized wood turpentine by heat or the like. It can be produced by fractionation. However, not all isomerized turpentine oils can be used because the content of β-ferrandrene varies greatly depending on the type of turpentine oil and the production process. It is also possible to separately blend (2) β-phenlandrene in a predetermined amount with a known turpentine oil and adjust it to the above range before use.

Known turpentine oils are produced from volatile components of sap contained in conifers, and are industrially mainly produced from gum turpentine, steam wood turpentine, sulfate wood turpentine and carbonized wood turpentine. Are classified into Of these, gum turpentine is obtained by distilling raw pine tar collected from wounds and scars on raw pine trees. Steam turpentine or wood turpentine is obtained by distilling the extract of unharvested pine stumps from which the bark and sapwood rot and fall off. Sulfate wood turpentine or sulfate turpentine is also obtained by condensing the steam generated in the heating step of the paper kraft (sulfate) pulping process. A carbonized wood turpentine is produced from light distillates obtained by carbonizing (carbonizing) waste coniferous wood such as trees and cut trees containing a large amount of resin. 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 pyrolysis oil fraction. Here, the phenol compound is phenol and an alkyl-substituted phenol such as cresol and xylenol. These can be used in combination. 1 phenol compound added
If the amount is less than 15 parts by weight, the compatibility of the obtained resin with the base polymer becomes poor. On the other hand, if the amount exceeds 15 parts by weight, the softening point of the resin decreases, and neither can improve the adhesiveness.

In the polymerization of the modified aromatic petroleum resin (b) of the present invention, (2) 3 to 40 parts by weight of β-ferrandrene or (2-
1) Turpentine oil containing 15% by weight of β-pherandrene; (3) 1 to 15 parts by weight of a phenol compound in 0.05%
It is carried out in the presence of .about.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 using water, ethers, phenols, alcohols or the like, 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). Proton 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, 0.1 to -20 to 80 ° C.
The copolymerization can be carried out in a range of from 10 hours to 10 hours. After polymerization,
The catalyst is neutralized and removed, and a modified aromatic petroleum resin having a weight average molecular weight of 500 to 2,000 is obtained as appropriate by distillation or the like.

The blending ratio of the (b) modified aromatic petroleum resin is as follows: (a) 100 parts by weight of the ethylene copolymer resin,
It is in the range of 50 to 150 parts by weight. If the amount is less than 50 parts by weight, the initial adhesiveness, cold resistance, and settability are liable to decrease.
When the amount is more than the weight part, the adhesive strength is apt to decrease with the decrease of the cohesive force.

As the wax (c), petroleum waxes such as paraffin wax and microcrystalline wax, natural waxes, polyethylene wax, polypropylene wax, atactic polypropylene wax, sasol wax and the like can be appropriately used according to the purpose. . This amount is calculated based on (a) 100 weight of ethylene copolymer resin.
It is 10 to 100 parts by weight per part by weight. If the amount is less than 10 parts by weight, the melt viscosity is high, and the workability and wettability to the substrate are reduced. If the amount is more than 100 parts by weight, the adhesive strength is reduced.

(A) the ethylene copolymer resin, (b)
The hot melt composition of the present invention can be produced by mixing and melting the modified aromatic hydrocarbon and the wax (c) 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 or the like. A particularly preferred application is a hot melt adhesive. The hot melt adhesive can be applied to various substrates such as paper, plastic, and metals such as aluminum. Particularly preferred substrates are cardboard and other paper substrates. As a hot melt sealant, it can be used for woodworking, bookbinding and the like. In addition, according to each use such as an adhesive and a sealant, a compounding agent known for each use, for example, a filler such as calcium carbonate, titanium oxide, talc or clay, a plasticizer, an organic or inorganic pigment, an antioxidant And an appropriate amount of a polymerization inhibitor and the like.

[0033]

Next, the present invention will be described specifically with reference to examples. In addition, the test method in an Example and a comparative example is as follows. (Test method) (1) Weight average molecular weight The weight average molecular weight of a petroleum resin is measured by GPC. The columns and analysis conditions are as follows. Column: TSK-Gel G-4000 + 2000Hs Analysis conditions: Temperature 38 ° C. Pressure 5.9 MPa Flow rate 1.0 ml / 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. Is determined based on the following criteria. Here, the skinning is a gelled substance generated on the surface of the hot melt adhesive by heat treatment, and the carbide is a black substance generated in the hot melt adhesive at the lower part of the beaker. Both occurrences are very important items in the thermal stability test because they cause clogging of the discharge nozzle of the hot melt adhesive. Evaluation: Skinning: ◎ None, ○ Slightly present, × Many Carbide: ◎ None, ○ Slightly present, × Many

(3) Heat-resistant adhesiveness Two corrugated cardboard B flutes (220 g / m ² ) of 25 mm in width and 100 mm in length were used as test pieces, and the hot melt adhesive obtained in a prescribed composition described later was tested. Apply to the surface of the piece at right angles to the flute (width direction)
Under the following bonding conditions, the same test piece material is adhered so that the flutes are parallel on the back surface. Using this test piece, a shear creep test at a load of 1 kg and 60 ° C. is performed, and the time at which the joint of the adhesive test piece is broken and dropped is measured, and is expressed in terms of heat resistance (hour) (hr). Adhesion condition: 180 ° C of adhesive application temperature Adhesive application amount 3 g / m (0.075 g / 25 mm) Open time (solidification time of adhesive) 2 sec Pressing load 2 kg Pressing time 2 sec

(4) Low temperature adhesiveness Step ball B of a K liner having a width of 50 mm and a length of 100 mm
Full - DOO and (220 g / m ²⁾ The test piece, on the surface of the obtained hot-melt adhesive test piece with a predetermined formulation to be described later, subjected coated in parallel to the flute (width direction), the (3 ) Under the conditions of heat-resistant adhesiveness, the test piece material is stuck so that the flutes cross on the back surface. The destruction state of the peeled surface of the test piece when the joint of the adhesive test piece is broken in an L-shaped peeling mode at a predetermined low temperature is determined according to the following determination conditions. Evaluation: ◎ Material destruction, ○ Most material destruction, △ Most interfacial destruction, × Interfacial destruction

Example 1 A pyrolysis oil fraction having the following composition and having a boiling range of 140 to 220 ° C. and obtained by pyrolysis of petroleum was used as a feed oil (a). Polymerizable component 70.0% by weight Total content of cyclopentadiene and methylcyclopentadiene 0.3% by weight Vinyl toluene content 30.1% by weight Total content of indene and its alkyl derivative 29.3% by weight Containing conjugated diolefin Rate 0.4% vinyl toluene content 43.0% indene content 41.9%

Turpentine (t1) 23 having a β-pherandrene content of 30% by weight and a limonene content of 60% by weight was added to 100 parts by weight of the polymerizable component of the stock oil (a).
Parts, after addition of phenol 5 parts by weight, adjusted to the polymerizable components further added to C ₉ alkylbenzenes of 50 wt% (based on the total imposition volume), three Hutu boron phenolate 0.2 % By weight and polymerized at 20 ° C. for 3 hours. The catalyst was neutralized with slaked lime and filtered to remove unreacted oil and low polymer by distillation.
50 resins (A) were obtained.

100 parts by weight of the obtained resin (A), EV
A (manufactured by Du Pont-Mitsui Polychemicals Co., Ltd .: trade name Evaflex # 210, vinyl acetate content 28% by weight,
Melt index 400 g / 10 min) 100 parts by weight, paraffin wax (manufactured by Nippon Oil Co., Ltd .: melting point 15)
5 ° 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) A pyrolysis oil fraction having the following composition and having a boiling range of 140 to 220 ° C and obtained by pyrolysis of petroleum was used as a feed oil (b). Polymerizable component 74.6% by weight Total content of cyclopentadiene and methylcyclopentadiene 1.4% by weight Vinyl toluene content 13.0% by weight Total content of indene and its alkyl derivative 50.2% by weight Containing conjugated diolefin 1.9% Vinyl toluene content 17.4% Indene content 67.3%

In 100 parts by weight of the polymerizable component of the stock oil (b), 2 parts of turpentine (t1) having a β-pherandrene content of 30% by weight and a limonene content of 60% by weight were used.
After adding 3 parts by weight and 5 parts by weight of phenol, C ₉ alkylbenzene was further added to make the total polymerizable component 50% by weight.
The polymerization was performed under the same conditions as in Example 1 to obtain a resin B having a weight average molecular weight of 1550. Then
A hot melt composition was compounded in the same manner as in Example 1, and the hot melt adhesive properties were tested on this.

Example 3 A pyrolyzed oil fraction having the following composition and having a boiling range of 140 to 220 ° C. and obtained by pyrolysis of petroleum was used as a feed oil (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 Containing conjugated diolefin 0.5% Vinyl toluene content 49.0% Indene content 21.4%

In 100 parts by weight of the polymerizable component of the starting oil (c), turpentine (t2) containing 40% by weight of β-pherandrene and 50% by weight of limonene was added
After adding 3 parts by weight and 5 parts by weight of phenol, C ₉ alkylbenzene was further added to make the total polymerizable component 50% 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.

Comparative Example 1 A pyrolysis oil fraction having the following composition and having a boiling range of 140 to 220 ° C. and obtained by pyrolysis of petroleum was used as a feed oil (d). Polymerizable component 57.1% by weight Total content of cyclopentadiene and methylcyclopentadiene 0.1% by weight Vinyl toluene content 31.1% by weight Total content of indene and its alkyl derivative 5.8% by weight Containing conjugated diolefin 0.2% Vinyl toluene content 54.5% Indene content 10.2%

To 100 parts by weight of the polymerizable component of the feedstock oil (d), an α-pinene content of 90% by weight and a β-pinene content of 5% were added.
Commercially available turpentine by weight% (t3) 23 parts by weight, after addition of phenol, 5 parts by weight of the total polymerizable components further added to C ₉ alkylbenzenes are prepared so that 50 wt%, Example 1 under the same conditions To obtain resin D having a weight average molecular weight of 1050. 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.

Comparative Example 2 The feed oil fraction (c) 100
With respect to parts by weight, the commercially available turpentine (t3) 23 of Comparative Example 1
After adding 5 parts by weight of phenol and 5 parts by weight of phenol, C ₉ alkylbenzene was further added to adjust the polymerizable component to 50% by weight. Polymerization was carried out under the same conditions as in Example 1 to obtain a resin having a weight average molecular weight of 1130. E was obtained. Next, a hot melt composition was prepared in the same manner as in Example 1, and the hot melt adhesive properties were tested.

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

[Table 1]

Here, Comparative Example 1 used a petroleum resin corresponding to Example 1 described in the above publication, and Comparative Example 2 used
This is an example using a petroleum resin corresponding to Comparative Example 1 of the above publication. As is evident from Table 1, the hot melt composition according to the present invention is superior to the hot melt composition using the petroleum resin described in the above-mentioned publication in adhesive properties to paper base materials such as corrugated paper, especially excellent heat resistance. On the other hand, it has excellent performance such as thermal stability and low-temperature adhesiveness.

[0049]

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 substrate such as corrugated 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 (6)

[Claims] (1) 100 parts by weight of an ethylene copolymer resin, (b) a weight average molecular weight of 500 to 500 obtained by copolymerizing the following (1) to (3) in the presence of a Friedel-Crafts type catalyst. 50 to 150 parts by weight of a modified aromatic petroleum resin in the range of 2,000, (1) Mainly components having a boiling point in the range of 140 to 220 ° C, vinyl toluene content of 10% or more and less than 60%, indene content 100 parts by weight of a polymerizable component of a pyrolyzed oil fraction obtained by pyrolysis of petroleum hydrocarbons having a content of 10 to 80%, (2) 3 to 40 parts by weight of β-ferrandrene, (3) phenol compound 1 To 15 parts by weight, and (c) 10 to 100 parts by weight of a hot melt composition. 2. The hot melt composition according to claim 1, wherein the content of the conjugated diolefin in the (1) pyrolyzed oil fraction is 2.0% or less. 3. The turpentine oil according to claim 1, wherein (2-1) turpentine oil containing 15% by weight or more of β-felandrene instead of β-felandrene is used as β-phelandrene.
3-4 based on 100 parts by weight of polymerizable component of pyrolysis oil fraction
A hot melt composition using an amount corresponding to 0 parts by weight. 4. The hot melt composition according to claim 3, wherein (1) the content of the 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 copolymer resin is an ethylene-vinyl acetate copolymer. (1) A pyrolysis 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 vinyltoluene content of 10% to 60%. %, The indene content is 10-80%,
A weight average obtained by copolymerizing (2) 3 to 40 parts by weight of β-ferrandrene and (3) 1 to 15 parts by weight of a phenol compound in the presence of a Friedel-Crafts type catalyst with respect to 100 parts by weight of the polymerizable component. A modified aromatic petroleum resin for a hot melt composition having a molecular weight of 500 to 2,000.