KR20040108562A - Aromatic petroleum resin for hot-melt adhesive, aromatic petroleum resin composition for hot-melt adhesive and hot-melt adhesive composition - Google Patents

Abstract

PURPOSE: Provided are an aromatic petroleum resin for hot melt adhesive, aromatic petroleum resin composition for hot melt adhesive, and hot melt adhesive using the same which has excellent heating stability, heat resistance and high-temperature adhesion. CONSTITUTION: The aromatic petroleum resin has the following characteristics based on proton NMR spectrum: (1) the area proportion of aromatic hydrogen atoms is 39-43%; (2) the area proportion of olefinic double bond-based hydrogen atoms is 0.7% or less; and (3) the area proportion of hydrogen atoms derived from hydroxyl groups is 0.5% or less, and the molecular weight distribution (Mw/Mn) is 1.75 or less. Particularly, the aromatic petroleum resin has a hydroxyl number of 5 mg KOH/g or less. The aromatic petroleum resin composition comprises 100 parts by weight of the above aromatic petroleum resin and 0.03-2 parts by weight of a hindered amine compound.

Description

Aromatic Petroleum Resin for Hot Melt Adhesive, Aromatic Petroleum Resin Composition for Hot Melt Adhesive, and Hot Melt Adhesive Composition {AROMATIC PETROLEUM RESIN FOR HOT-MELT ADHESIVE

The present invention relates to an aromatic petroleum resin for a hot melt adhesive, an aromatic petroleum resin composition for a hot melt adhesive, and a hot melt adhesive composition having excellent heat stability and heat adhesive resistance using the same.

In a hot melt adhesive, it is a thermoplastic resin used as a main component, and it is called polyolefin type, polyester type, or polyamide type hot melt adhesive according to the kind of this thermoplastic resin. Moreover, the hot-melt adhesive agent which has a thermoplastic elastomer which uses styrene block copolymers, such as a styrene butadiene copolymer (SBS) or a styrene isoprene copolymer (SIS) as a main component, is also known. Among them, a polyolefin-based hot melt adhesive, in particular an ethylene-vinyl acetate copolymer (hereinafter referred to as EVA), a hot melt adhesive blended with a tackifying resin and a wax is inexpensive, and the vinyl acetate content, molecular weight, and blending of EVA, which are main components, are inexpensive. It is widely used in the field of packaging use, bookbinding use, plywood, woodworking adhesive use, etc., since it is possible to prepare a hot melt adhesive applicable to a wide range of applications by changing the prescription. Until now, the hot melt adhesive suitable for various uses has been researched by optimizing the kind and compounding ratio of EVA, tackifying resin, wax, etc. which are used for compounding.

In EVA-based hot melt adhesives using aromatic petroleum resins as tackifying resins, a problem that has been pointed out conventionally is deterioration of heating stability and heat adhesive resistance. Deterioration of the heat stability causes a problem in that the tackifying resin is oxidatively deteriorated to become a carbonized / insoluble component, causing "skinning" to be separated from the surface, which causes problems such as clogging of the nozzle of the hot melt adhesive applicator. In addition, the lowering of the heat-adhesive resistance causes troubles such as opening due to softening of the adhesive layer when storing articles such as cardboard packages adhered in summer, in the warehouse.

As a means to solve the said problem, the examination which optimizes the kind, quantity, etc. of the vinyl acetate amount, tackifying resin, and wax of EVA which are used for a hot melt composition conventionally has been performed.

For example, 50-200 weight part of tackifying resin containing an aromatic component, and 2-100 weight part of paraffin wax are contained with respect to 100 weight part of EVA which content vinyl acetate is 30 weight% or more, The hot-melt adhesive composition characterized by the above-mentioned. Is disclosed (for example, refer patent document 1). However, no examination to optimize the tackifying resin has been conducted.

As a study from a tackifying resin, it is a hot melt adhesive composition, for example, (1) The polymerizable component of the pyrolysis oil distillate obtained by the thermal decomposition of petroleum hydrocarbons which have a specific boiling range, vinyltoluene content rate, and indene content rate, ( 2) It is proposed to use a modified aromatic petroleum resin copolymerized with a specific terebin oil and (3) phenolic compound using a Friedel-Crafts type catalyst as a specific ratio (for example, See Patent Documents 2 to 4). However, it is uneconomical because it uses terebin oil which is expensive compared to the pyrolysis oil distillate.

Moreover, the method of mix | blending a hindered compound with petroleum resin and improving heating stability is proposed (for example, refer patent document 5). However, simply adding a hindered amine compound to commercially available petroleum resins had insufficient effect of improving heating stability.

On the other hand, the method of improving heating stability using the hydrogenated aromatic petroleum resin (henceforth a water petroleum resin) as a tackifying resin is known (for example, refer patent document 6). However, since this resin is produced by further hydrogenating aromatic petroleum resins, it is expensive to use water-adding equipment and water-adding raw materials (hydrogen, solvent, catalyst) as compared with petroleum resins without water.

[Patent Document 1] Japanese Patent Application Laid-Open No. 2001-59078 (Page 1)

[Patent Document 2] Japanese Patent Publication No. 2002-69408 (Page 1)

[Patent Document 3] Japanese Patent Application Laid-Open No. 9-316294 (Page 1)

[Patent Document 4] Japanese Patent Application Laid-open No. 55-65248 (Page 1)

[Patent Document 5] Japanese Patent Publication No. Hei 3-35335 (Page 1)

[Patent Document 6] Japanese Patent Application Laid-Open No. 2000-103820 (Page 1)

An object of the present invention is to provide an aromatic petroleum resin for a hot melt adhesive, an aromatic petroleum resin composition for a hot melt adhesive, and a hot melt adhesive excellent in heat stability and heat adhesive resistance using the same.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, it discovered that the heat stability and heat resistance of a hot melt adhesive composition can be improved by optimizing the composition, molecular weight distribution, etc. of the aromatic petroleum resin for hot melt adhesives used for a hot melt adhesive composition. The present invention has been completed.

That is, in the present invention, in the Floton NMR spectrum, (1) aromatic hydrogen area ratio is 39 to 43%, (2) olefinic double bond hydrogen area ratio is 0.7% or less, and (3) hydroxyl group-derived hydrogen area ratio is The present invention relates to an aromatic petroleum resin for hot melt adhesive, an aromatic petroleum resin composition for hot melt adhesive, and a hot melt adhesive composition using the same, characterized by 0.5% or less and a molecular weight distribution (Mw / Mn) of 1.75 or less.

First, the aromatic petroleum resin for hot melt adhesive of this invention is demonstrated.

As for the composition of the aromatic petroleum resin for hot melt adhesives of this invention, it is necessary for the area percentage of the spectrum observed when Floton NMR is measured to satisfy the conditions (1)-(3).

Namely, the area ratio of aromatic hydrogens observed at (1) 7.0 to 8.0 ppm is 39 to 43%, and (2) the area ratio of olefinic double bond hydrogens observed at 5.0 to 6.0 ppm is 0.7% or less, (3 The area ratio of hydroxyl-derived hydrogen observed at 3.5 to 5.0 ppm is less than 0.5%.

(1) When the area ratio of aromatic hydrogen falls outside the above range (less than 39% or more than 43%), compatibility with the ethylene / unsaturated ester copolymer used in the hot melt adhesive composition of the present invention is lowered, It leads to deterioration of thermal stability and heat adhesiveness. In addition, both the olefinic double bond hydrogen of (2) and the hydroxyl group-derived hydrogen of (3) are susceptible to oxidative degradation, and when the area percentage of each exceeds the above range (i.e., of the olefinic double bond hydrogen) When the area ratio exceeds 0.7%, when the area ratio of hydroxyl-derived hydrogen exceeds 0.5), thermal stability is lowered, which is not preferable.

The molecular weight distribution (Mw / Mn) of the aromatic petroleum resin for hot melt adhesive of the present invention needs to be 1.75 or less. When the molecular weight distribution (Mw / Mn) of the aromatic petroleum resin for hot melt adhesive exceeds 1.75, the heat adhesive resistance of the hot melt adhesive is reduced. In addition, Mw represents a weight average molecular weight and Mn represents a number average molecular weight.

In addition, the pure acid value of the aromatic petroleum resin for hot melt adhesive of the present invention is preferably 5 mg-KOH / g or less from the viewpoint of heating stability.

If the aromatic petroleum resin for hot melt adhesive of the present invention satisfies the above conditions, other physical properties are not particularly limited, but the softening point is preferably 50 to 200 ° C and 500 to 3000 Mw.

The aromatic petroleum resin for hot melt adhesive of the present invention is a distillate having a boiling point in the range of 140 to 280 ° C, for example, styrene, and an alkyl derivative thereof, among the decomposition oils obtained by pyrolysis of petroleum as its raw material oil. A polymerizable component such as styrene, β-methylstyrene, vinyltoluene, indene and alkyl derivatives thereof, dicyclopentadiene and derivatives thereof is homopolymerized or copolymerized. It is usually prepared after the polymerization, also by decomposition of the catalyst with alkali, followed by removal of the unreacted oil and the low polymer.

The aromatic petroleum resin for a hot melt adhesive of the present invention can be obtained by preferably selecting a polymerizable component composition and polymerization conditions (catalyst, polymerization temperature, molecular weight adjusting method, etc.).

The polymerizable component composition preferably has an indene content of 30 to 70%, more preferably 40 to 60%, and a dicyclopentadiene content of preferably less than 5%. Here, indene content rate shows the weight% of the sum total of indene and its alkyl derivative with respect to a polymerizable component, and dicyclopentadiene content rate shows the weight% of the sum of dicyclopentadiene and its alkyl derivative with respect to a polymerizable component. . Adjustment of such a polymerizable component composition is achieved by refine | purifying pyrolysis oil by distillation. In addition, the composition and the said content rate of a polymerizable component can be analyzed and measured by a well-known gas chromatograph method.

As the polymerization catalyst, a known Friedelkratz catalyst can be used. For example, aluminum trichloride, aluminum tribromide, boron trifluoride, its complex, etc. are illustrated. Among them, a complex of a gas of boron trifluoride or boron trifluoride and water, ethers, phenols, alcohols, organic acids and the like is preferable, and a phenol complex of boron trifluoride is particularly preferable since the post-polymerization post-treatment is easy. The amount of the catalyst is not particularly limited, but is preferably 0.1 to 2.0% by weight based on the raw material oil.

Polymerization temperature becomes like this. Preferably it is 50-90 degreeC, More preferably, it is the range of 60-80 degreeC. When the polymerization temperature is less than 50 ° C, the molecular weight increases, so that the compatibility with the ethylene-unsaturated ester copolymer decreases, and when the temperature exceeds 90 ° C, the color of the prepared petroleum resin deteriorates, which is not preferable. Moreover, although polymerization time is not specifically limited, 0.1-10 hours are preferable.

A molecular weight adjustment method is mainly performed by control of polymerization temperature, and a molecular weight regulator is not used. The reason for not using a molecular weight regulator is, for example, a molecular weight regulator generally exemplified by phenol or alkyl-substituted phenols such as cresol, xylenol, p-tert-butylphenol and nonylphenol is easily oxidized by oxygen. This is because the heating stability of the petroleum resin is lowered.

Next, the aromatic petroleum resin composition for a hot melt adhesive of the present invention will be described in detail.

In the aromatic petroleum resin composition for hot melt adhesive of the present invention, the hindered amine compound is preferably added in an amount of 0.03 to 2 parts by weight, and more preferably 0.03 to 0.5 part by weight based on 100 parts by weight of the aromatic petroleum resin for hot melt adhesive. It is done.

Here, when the compounding quantity of a hindered amine compound is less than 0.03 weight part, the heat stability of the aromatic petroleum resin composition obtained is inferior, and it is unpreferable. On the other hand, when the compounding quantity of a hindered amine compound exceeds 2 weight part, the improvement of the heating stability of the aromatic petroleum resin composition obtained is not seen, and it is unpreferable.

As a hindered amine compound used by this invention, if it is a compound belonging to the category called a hindered amine compound, it can be used without a restriction | limiting, Especially since the aromatic petroleum resin composition for hot melt adhesives excellent in heat stability is obtained, It is preferable that it is a compound which has a 2,2,6,6- tetraalkyl-4- piperidyl group represented by general formula.

Here, R1-R4 in general formula is a C1-C4 alkyl group, R5 is hydrogen or a C1-C8 alkyl group or alkoxy group which may have a substituent. R1 to R4 may be the same as or different from each other. Specific examples thereof include a methyl group and an ethyl group, but a methyl group is preferable. As a specific example of R <5>, hydrogen, a methyl group, an octyl group, etc. are mentioned, Hydrogen and a methyl group are preferable.

It is known that the hindered amine compound represented by general formula has a molecular weight of 400-4000, and it is marketed as a hindered amine light stabilizer (HALS). Specific commercially available products include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis (1,2, manufactured by Chiba Specialty Chemicals Co., Ltd. and Asahi Denka Kogyo Co., Ltd.). 2,6,6-pentamethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxyl , Tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, poly [{6- (1,1,3, 3-tetramethylbutyl) amino-1,3,5-triadine-2,4-diyl} {2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2, 2,6,6-tetramethyl-4-piperidyl) imino}] and the like.

The manufacturing method of the aromatic petroleum resin composition for hot melt adhesives of this invention can use any method as long as it can mix | blend 0.03-2 weight part of hindered amine compounds with respect to 100 weight part of aromatic petroleum resins for hot melt adhesives. In general, aromatic petroleum resins are easily oxidized even under normal temperature to form peroxides, and heat-melting aromatic petroleum resins that have been stored for a long period of time readily causes decomposition of the formed peroxides to cause peeling, heating complexes, and gelation. Therefore, in order to obtain aromatic petroleum resin for hot melt adhesive which is more excellent in heat resistance and heating stability, aromatic petroleum for hot melt adhesive in the molten state immediately after distilling off the coexisting solvent or low molecular compound after completion of polymerization reaction of aromatic petroleum resin for hot melt adhesive The method of mix | blending the melted hindered compound with resin is preferable. In addition, the oxygen concentration in the blender at the time of the blending is preferably 1000 ppm or less, more preferably 100 ppm or less, particularly preferably 10 ppm or less, and oxidation of the aromatic petroleum resin for hot melt adhesive in the molten state during blending, in particular by oxygen It is preferable because oxidation can be prevented.

Moreover, the aromatic petroleum resin composition for hot melt adhesives of this invention is an additive normally mix | blended with a resin composition, as long as it does not deviate from the objective of this invention, For example, a phenolic antioxidant, phosphorus antioxidant, and sulfur type An antioxidant, a lactone antioxidant, a ultraviolet absorber, a pigment, calcium carbonate, glass beads, etc. may be mix | blended.

Next, the hot melt adhesive composition of the present invention will be described in detail.

The ethylene-unsaturated ester copolymer used in the hot melt adhesive composition of the present invention is not particularly limited, but examples of the unsaturated ester include vinyl acetate (VAc), monocarboxylic acid vinyl ester, acrylic acid ester and the like. Especially, the ethylene vinyl acetate copolymer (henceforth EVA) is preferable at the point of the flexibility of an adhesive agent. Moreover, EVA which contains 20-50 weight% of VAc from an adhesive point, and whose melt index (henceforth MI) is 10-2000g / 10min is preferable. Here, MI means the number of grams (g / 10 minutes) leaked per unit time when measured under conditions of a temperature of 190 ° C., a load of 2160 g, and 10 minutes in accordance with ASTM D-1238-89.

The aromatic petroleum resin for hot melt adhesive and / or the aromatic petroleum resin composition for hot melt adhesive used for tackifying resin in the hot melt adhesive composition of this invention may be used independently, and may use two or more types together.

The blending ratio of the ethylene-unsaturated ester copolymer and the aromatic petroleum resin composition for hot melt adhesives and / or the aromatic petroleum resin composition for hot melt adhesives is not particularly limited as long as it satisfies the properties required as the hot melt adhesive, and can be widely changed. However, the preferred blending ratio is preferably 50 to 150 parts by weight of aromatic petroleum resin for hot melt adhesive and / or aromatic petroleum resin composition for hot melt adhesive with respect to 100 parts by weight of ethylene / unsaturated ester copolymer. 120 parts by weight. When such a compounding ratio deviates from the said range (50-150 weight part), the adhesiveness of a hot melt adhesive composition falls and it is not suitable for practical use.

Examples of the wax used in the hot melt adhesive composition of the present invention include synthetic waxes such as petroleum wax such as paraffin wax and microcrystalline wax, polyethylene wax, Fischer-Tropsch wax, polypropylene wax, and atactic polypropylene. Natural waxes such as wax, wax, carnava wax and yellow wax and the like, and are used alone or as a mixture.

In the hot melt adhesive composition according to the present invention, the blending ratio of the wax is preferably 10 to 100 parts by weight, more preferably 10 to 50 parts by weight based on 100 parts by weight of the ethylene-unsaturated ester copolymer. It is not preferable that the compounding amount of the wax exceeds the above range (10 to 100 parts by weight) because it causes a decrease in the adhesive strength of the hot melt adhesive composition.

The viscosity of the hot melt adhesive composition varies depending on the purpose of use, but the viscosity adjustment depends on the compound, that is, the molecular weight of the ethylene / unsaturated ester copolymer, the viscosity of the tackifying resin, the viscosity of the wax, and the blending ratio of these compounds also changes. do. Therefore, it is necessary to optimize the blending ratio according to the purpose. Usually, it is preferable that melt viscosity in 180 degreeC is 100-10000 mPa * s.

The hot melt adhesive composition of the present invention may be blended with various stabilizers including oils, plasticizers, inorganic fillers, etc., if necessary, including pigments, dyes and antioxidants. The hot melt adhesive composition of the present invention can be produced by a known method, that is, by mixing each compounding component under melting. Although the melting temperature in this manufacturing method is not specifically limited, There is no problem in particular unless it is the extremely low temperature at which melt stirring becomes difficult, or the low temperature at which a compound does not melt or flow. On the other hand, at high temperature, depending on the decomposition of the ethylene-unsaturated ester copolymer or the tackifying resin, it may be colored, which is not preferable. Considering these things, 160-230 degreeC is preferable, More preferably, it is 180-200 degreeC. Mixing can be performed using a well-known method, such as an extruder, an open roll mill, a Bumbury mixer, a kneader, a kneader ruder, a melt mixing tank, etc.

The hot melt adhesive composition of the present invention can be used for conventionally used applications, namely, for bonding wood, cloth, thermoplastic resin, thermoplastic elastomer, rubber, etc., such as paper, polyester film, metal, and plywood.

Although the adhesion method is not specifically limited, It is possible to use the conventionally well-known apparatus for hot melt adhesives, A nozzle type hot melt applicator, a spray type hot melt applicator, a flat nozzle type hot melt applicator, a roll type coater, an extrusion type coater, etc. are illustrated.

EXAMPLE

Hereinafter, although an Example demonstrates this invention, this invention is not limited at all by these Examples. In addition, the preparation, analysis, and test method of the raw material resin, a compound, and a composition which were used in the Example and the comparative example are as follows.

1. Raw material

(1) EVA

Tosoh Co., Ltd. product, ultracene 0B53C (vinyl acetate content = 28 weight%, MI = 400 g / 10 minutes)

Tosoh Co., Ltd. product, ultracene 0B54A-3 (vinyl acetate content = 33 weight%, MI = 400 g / 10 minutes)

(2) Aromatic petroleum resin for hot melt adhesive: It manufactured by the conditions of Examples 1-3 and Comparative Examples 1-3.

(3) Aromatic petroleum resin composition for hot melt adhesive: It manufactured by the conditions described in Examples 4-7 and Comparative Examples 4-5.

(4) Wax: Paraffin wax (Nippon Sero Corporation, paraffin wax 155F), Fisher-Tropsk Wax (Schumannsazol company, Paraprint H1)

(5) Antioxidant: Phenolic antioxidant (product of Chiba Specialty Chemicals, Irganox1010)

(6) Hindered amine compound: Adecaster light stabilizer LA-77 (Asa Hiden Kagogyo Co., Bis (2, 2, 6, 6- tetramethyl-4- piperidyl) sebacate)

2. Preparation method of hot melt adhesive composition

It described in the Example.

3. Analysis method

(1) Content of each component of raw material oil: It analyzed using the well-known gas chromatograph method.

(2) Weight average molecular weight: Polystyrene was used as a standard, and was measured by gel permeation chromatography.

(3) Floton NMR (nuclear magnetic resonance spectrum): The aromatic petroleum resin for hot melt adhesive was dissolved in chloroform-d (manufactured by Wako Pure Chemical Industries, Ltd.) and measured by a conventional NMR measurement method. About the obtained spectrum, area ratio was calculated | required based on the following formula.

Area ratio (%) = (each peak area) / (total total peak area) x 100

In addition, each peak is as follows.

Aromatic Hydrogen Peak: 7.0 to 8.0 ppm

Olefinic double bond hydrogen peak: 5.0 to 6.0 ppm

Hydroxide-derived hydrogen peak: 3.5 to 5.0 ppm

(4) The hydroxyl value: It measured by the method based on JISK-0070 (1966).

(5) Softening point: It measured by the method based on JISK-2531 (1960) (circulation method).

4. Test Method

(1) Test method of heat resistance adhesion: heat creep test

In accordance with JAI-7 (Japan Association of Adhesion and Industry Association), two sheets of cardboard (K liner) cut to 50 mm x 150 mm are used as the adherend, and the coating temperature is 180 ° C and the coating speed is 7.5 m using a hot melt open time tester. Hot-melt adhesive composition is applied to one side of one adherend under conditions of 50 mm × 100 mm and coating amount (adhesive area) of 50 mm × 100 mm / minute, and the other adherend is bonded after 2 seconds of open time. 2 kg of press load was allowed to cool to prepare an adhesion test piece. Subsequently, after cutting the said adhesive test piece to 25 mm x 150 mm, when the load of 300 g / 25 mm is fixed to the one end by the method of T-type peeling, it is left to stand in 55 degreeC oven, and the load falls. The time until minutes was measured. The longer the time is, the better the heat resistant adhesiveness is.

(2) Test method of heating stability: heating deterioration test

50 g of the hot melt adhesive obtained in the method for preparing the 2. hot melt adhesive composition described above was put in a gear oven at 180 ° C., and the sample surface was observed every 24 hours. Deterioration time was defined as the time when thermal deterioration products such as gels and carbides were first discovered. The longer the time, the better the heat stability.

Manufacture of Aromatic Petroleum Resins for Hot Melt Adhesives

Example 1

Friedel 100 parts by weight of distillate (polymerizable content: vinyltoluene 41%, indene 40%, styrene 17%, dicyclopentadiene 1%) having a boiling point range of 140 to 280 ° C obtained by pyrolysis of petroleum. 1.0 wt% of boron trifluoride complex (Sterracemipa boron trifluoride) was added as a kraft-type catalyst and polymerized at 75 ° C. for 2 hours, followed by removing the catalyst with an aqueous solution of caustic soda. The oily unreacted oil was distilled off and the aromatic petroleum resin (A) for hot melt adhesives was obtained. The physical properties (softening point, molecular weight distribution, Floton NMR measurement results, and hydroxyl value) of this resin (A) are shown in Table 1.

Example 2

The distillation fraction in which the boiling point range obtained by pyrolysis of petroleum is in the range of 140-280 degreeC is made into (polymerizable content: vinyl toluene 29%, indene 41%, styrene 27%, dicyclopentadiene 4%), and superposition | polymerization temperature Aromatic petroleum resin (B) for hot melt adhesive was prepared under the same conditions as in Example 1 except that the temperature was 90 ° C. Table 1 shows the physical properties (softening point, molecular weight distribution, Floton NMR measurement results, and hydroxyl value) of this resin (B).

Example 3

The distillation fraction in which the boiling point range obtained by pyrolysis of petroleum is 140-280 degreeC is made into (polymerization possibility content: 42% of vinyltoluene, 46% of indenes, 12% of styrene, 1% of dicyclopentadiene), and superposition | polymerization temperature Aromatic petroleum resin (C) for hot melt adhesive was prepared under the same conditions as in Example 1 except that the temperature was 60 ° C. The physical properties (softening point, molecular weight distribution, Floton NMR measurement results, and hydroxyl value) of this resin (C) are shown in Table 1.

Comparative Example 1

Distillate having a boiling point range of 140 to 280 ° C obtained by pyrolysis of petroleum is (polymerizable content: 53% vinyltoluene, 38% indene, 4% styrene, 5% dicyclopentadiene) and trifluoride An aromatic petroleum resin (D) for hot melt adhesive was prepared under the same conditions as in Example 1 except that 1.0 wt% of a boron ether complex (Sterracemipa boron trifluoride ethyl ether) was added and the polymerization temperature was 60 ° C. It prepared. The physical properties (softening point, molecular weight distribution, Floton NMR measurement results, and hydroxyl value) of this resin (D) are shown in Table 1.

Comparative Example 2

Phenol 2 in 100 parts by weight of distillate (polymerizable content: 39% vinyltoluene, 43% indene, 11% styrene, 8% dicyclopentadiene) having a boiling point range of 140 to 280 ° C obtained by pyrolysis of petroleum. After adding parts by weight, the polymerizable component was prepared to be 50%, and the aromatic petroleum resin (E) for hot melt adhesive was prepared under the same conditions as in Example 3 except that the polymerization temperature was 40 ° C. The physical properties (softening point, molecular weight distribution, Floton NMR measurement results, and hydroxyl value) of this resin (E) are shown in Table 1.

Comparative Example 3

According to Japanese Patent Application Laid-open No. 55-65248 in Patent Document 4, a distillate having a boiling point range of 140 to 280 ° C obtained by pyrolysis of petroleum (polymerization possibility: 41% vinyltoluene, 40% indene, styrene After adding 23 parts by weight of commercially available terevin oil (manufactured by Wako Pure Chemical Industries, Ltd.) and 5 parts by weight of phenol, a diene of 7 (cg / g) was added to 100 parts by weight of 17% and dicyclopentadiene 1%). Prepare the potential component to 50%, add 1.0 wt% of boron trifluoride complex (Sterracemipa Co., Ltd. boron trifluoride), polymerize at 20 ° C for 3 hours, and then remove the catalyst with an aqueous solution of caustic soda. The oil-free unreacted oil was distilled off and the aromatic petroleum resin (F) for hot melt adhesives was obtained. The physical properties of the resin (F) (softening point, molecular weight distribution, Floton NMR measurement results, and hydroxyl value) are shown in Table 1.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Resin A Resin B Resin C Resin D Resin E Resin F Softening point (℃) Molecular weight Mn Molecular weight MwMw / Mn Hydroxide (mg-KOH / g) 120 116 119 830 770 8 501 350 1240 14801.63 1.61 1.744 0 0 120 120 123 770 840 7301 580 1500 12502.05 1.79 1.710 10 15 Area ratio of Floton NMR spectrum (%) Aromatic hydrogen olefin double bond hydrogen hydroxyl group derived hydrogen 41.08 42.12 39.440.02 0.64 0.180.45 0.27 0 37.18 38.89 36.30.77 1.15 1.470 0.87 0.76

The aromatic petroleum resins (D, E, F) for hot melt adhesives obtained in Comparative Examples 1 to 3 had an aromatic hydrogen area ratio of 39 to 43% and an olefinic double bond hydrogen area ratio of 0.7% or less, The hydrogen area ratio was 0.5% or less, the molecular weight distribution (Mw / Mn) was 1.75 or less, and the hydroxyl value did not satisfy all or either of the items of 5 mg-KOH / g or less.

Manufacture of Aromatic Petroleum Resin Compositions for Pyrolysis Adhesives

Example 4

0.1 parts by weight of a hindered amine compound (manufactured by Asahi Denka Kogyo, trade name Adecasterb Light Stabilizer LA-77) with respect to 100 parts by weight of the resin (A) immediately after the manufacture under a nitrogen stream having an oxygen concentration of 2 ppm at 100 캜, and a stirring rotation speed. It mix | blended on the conditions of 300 rpm, and obtained the aromatic petroleum resin composition (G) for hot melt adhesives. The compounding ratio of resin composition (G) is shown in Table 2.

Example 5

The hindered amine compound was mix | blended with resin (B) by the method similar to Example 4, and the aromatic petroleum resin composition (H) for hot melt adhesives was obtained. The compounding ratio of the resin composition (H) is shown in Table 2.

Example 6

The hindered amine compound was mix | blended with resin (C) in the same way as Example 4, and the aromatic petroleum resin composition (I) for hot melt adhesives was obtained. The compounding ratio of resin composition (I) is shown in Table 2.

Example 7

0.02 parts by weight of a hindered amine compound (manufactured by Asahi Denka Kogyo, trade name Adecasterb Light Stabilizer LA-77) with respect to 100 parts by weight of the resin (A) immediately after production under a nitrogen stream having an oxygen concentration of 2 ppm at 100 ° C., with a stirring rotation speed. It mix | blended on the conditions of 300 rpm, and obtained the aromatic petroleum resin composition (J) for hot melt adhesives. The compounding ratio of the resin composition (J) is shown in Table 2.

Comparative Example 4

In the same manner as in Example 4, the hindered amine compound was blended with the resin (D) to obtain an aromatic petroleum resin composition (K) for a hot melt adhesive. The compounding ratio of the resin composition (K) is shown in Table 2.

Comparative Example 5

In the same manner as in Example 4, the hindered amine compound was blended with the resin (E) to obtain an aromatic petroleum resin composition (L) for a hot melt adhesive. The compounding ratio of the resin composition (L) is shown in Table 2.

Example 4 Example 5 Example 6 Example 7 Comparative Example 4 Comparative Example 5 Composition G Composition H Composition I Composition J Composition K Composition L Hindered amine compound (weight part) 0.1 0.1 0.1 0.02 0.1 0.1 Aromatic Petroleum Resin (parts by weight) A B C100 100 100 A100 D E100 100

`` Production of Hot Melt Adhesive Composition ''

Example 8

100 parts by weight of EVA (DOSOU CO., LTD., Ultracene 0B53C), 100 parts by weight of aromatic petroleum resin (A) for hot melt adhesive prepared in Preparation Example 1, 25 parts by weight of paraffin wax 155F, 25 parts by weight of paraprint H1, antioxidant 0.8 The weight part was placed in a 500 ml Teflon (registered trademark) beaker, the contents were completely melted in an oven warmed at 180 ° C, sufficiently stirred and mixed, and cooled to prepare a hot melt adhesive composition. Table 3 shows the results of the heat-resistant creep test and heat deterioration test of the hot melt adhesive composition.

Examples 9-10, Comparative Examples 6-8

A hot melt adhesive composition was prepared in the same manner as in Example 8 except that the blend composition of EVA, a petroleum resin, a wax, and an antioxidant as a raw material of the hot melt adhesive composition was changed as shown in Table 3. The results of the heat creep test and heat deterioration test are shown in Table 3.

In addition, the hot melt adhesive compositions of Examples 8 to 10 had long heat deterioration time and heat creep time, and were excellent in heat stability and heat adhesive resistance. However, in Comparative Examples 6 to 8, both the heat deterioration time and the heat creep time were short, and the heat stability and heat adhesive resistance were deteriorated.

Examples 11-14, Comparative Examples 9-12

A hot melt adhesive composition was prepared in the same manner as in Example 8 except that the blend composition of EVA, a petroleum resin, a wax, and an antioxidant as a raw material of the hot melt adhesive composition was changed as shown in Table 4. The results of the heat creep test and heat deterioration test are shown in Table 4.

Further, the hot melt adhesive compositions of Examples 11 to 14 had a good balance of heat deterioration time and heat creep time, and were excellent in heat stability and heat adhesive resistance. However, in Comparative Examples 9-12, the balance of heat deterioration time and heat creep time was bad, and heat stability and heat adhesive resistance were inferior.

Examples 15-18, Comparative Examples 13-14

A hot melt adhesive composition was prepared in the same manner as in Example 8 except that the blend composition of EVA, a petroleum resin composition, a wax, and an antioxidant as a raw material of the hot melt adhesive composition was changed as shown in Table 5. The results of the heat creep test and heat deterioration test are shown in Table 5.

In addition, the hot melt adhesive compositions of Examples 15 to 18 had long heat deterioration time and heat creep resistance, and were excellent in heat stability and heat adhesive resistance. However, in Comparative Examples 13-14, both the heat deterioration time and the heat creep time were short, and the heat stability and heat adhesive resistance were deteriorated. Moreover, the heat deterioration time and heat-resistant creep time of Examples 15-17 using the resin composition (G, H, I) which mix | blended 0.03 weight part or more of a hindered amine compound are the resin composition which did not mix | blend a hindered amine compound ( It was longer than the heat deterioration time and heat-resistant creep time of Examples 8-10 using A, B, and C), and the compounding effect of a hindered amine compound was clear.

As indicated above, the aromatic petroleum resin for hot melt adhesive, the aromatic petroleum resin composition for hot melt adhesive, and the hot melt adhesive composition using them are excellent in heat stability and heat adhesive resistance.

Claims (7)

In the Floton NMR spectrum, (1) aromatic hydrogen area ratio is 39-43%, (2) olefinic double bond hydrogen area ratio is 0.7% or less, (3) hydroxyl-derived hydrogen area ratio is 0.5% or less, and molecular weight Aromatic petroleum resin for hot melt adhesive, characterized in that the distribution (Mw / Mn) is 1.75 or less. The aromatic petroleum resin for hot melt adhesive according to claim 1, wherein the hydroxyl value of the aromatic petroleum resin for hot melt adhesive is 5 mg-KOH / g or less. The raw material oil of Claim 1 or 2 refine | purified so that the boiling point range obtained by pyrolysis of petroleum may be 140-280 degreeC cracking distillate so that it may be less than 30 to 70% of inden content and 5% of dicyclopentadiene content. , Aromatic petroleum resin for hot melt adhesives, which is obtained by polymerization at a polymerization temperature of 50 to 90 ° C. using a Friedel-Crafts type catalyst. 0.03-2 weight part of hindered amine compounds are mix | blended with respect to 100 weight part of aromatic petroleum resins for hot melt adhesives in any one of Claims 1-3, The aromatic petroleum resin composition for hot melt adhesives characterized by the above-mentioned. The oxygen concentration in a blender at the time of mix | blending a hindered amine compound is controlled to 1000 ppm or less, The manufacturing method of the aromatic petroleum resin composition for hot melt adhesives of Claim 4 characterized by the above-mentioned. 50-150 weight of aromatic petroleum resin for hot melt adhesive of any one of Claims 1-3, and / or aromatic petroleum resin composition for hot melt adhesive of Claim 4 with respect to 100 weight part of ethylene- unsaturated unsaturated copolymers. And a hot melt adhesive composition comprising 10 to 100 parts by weight of a wax. The hot melt adhesive composition according to claim 6, wherein the ethylene-unsaturated ester copolymer is an ethylene-vinyl acetate copolymer.