JP2001139631A - Hydrocarbon resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aromatic hydrocarbon resin excellent in heat stability and hue. SOLUTION: This hydrocarbon resin is a copolymer of a specific styrene monomer (I) and a specific aliphatic monomer (II) and has a molar ratio of (I)/(II) of (99.5/0.5)-(50/50), a wt. average mol.wt. of 300-7,000, a mol.wt. distribution of 1.1-7, and a softening point of 50-160.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel hydrocarbon resin, and more particularly to an aromatic hydrocarbon resin having excellent heat resistance.

[0002]

2. Description of the Related Art As a tackifying resin blended in rubber-based pressure-sensitive adhesives and ethylene-vinyl acetate copolymer-based and styrene block copolymer-based hot melt adhesives, low molecular weights such as styrene, vinyltoluene and α-methylstyrene are used. It is known to use body and petroleum resins. But,
These resins do not exhibit high adhesive strength due to insufficient compatibility with the ethylene / vinyl acetate copolymer. In addition, petroleum resins produced from ordinary unsaturated hydrocarbon-containing fractions have problems such as insufficient hue, heat-resistant hue, heat-resistance stability and the like.

The present inventors have proposed to improve these problems by isopropenyltoluene and an arbitrary fraction selected from a fraction having 4 to 5 carbon atoms by-produced during petroleum refining and petroleum cracking. It has been previously proposed to use a polymer obtained by polymerizing at a specific ratio, and to use a homopolymer of isopropenyltoluene. (Japanese Patent Laid-Open No. 49-118729)
JP, JP-A-49-128945, JP-B-54
-34033)

However, in recent years, as the demands on the market have increased, there has been a demand for resins having further improved performance. When using an adhesive, it may be heated for a long time in order to maintain the continuity of the work.Therefore, there is little change in viscosity of the adhesive composition and generation of an odor due to decomposition. Is desired.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide an aromatic hydrocarbon resin having excellent heat resistance and excellent hue in order to solve the above problems.

[0006]

According to the present invention, there is provided at least one styrene monomer (I) represented by the following general formula (1):

Embedded image (In the formula, R ¹ , R ² , R ³ and R ⁴ may be the same or different and are a hydrogen atom or an alkyl group having 4 or less carbon atoms.) Selected from compounds represented by the following formula (2) A copolymer with at least one aliphatic monomer (II),

Embedded image (Wherein, R ^{5 to} R ¹⁰ may be the same or different and are a hydrogen atom or an alkyl group having 4 or less carbon atoms, A is an alkylene group having 4 or less carbon atoms, and n is 0 or 1. .) (A) The molar ratio of (I) / (II) is 99.5 / 0.5-
50/50, and (B) a weight average molecular weight of 300 to 7
000, (C) a hydrocarbon resin having a molecular weight distribution of 1.1 to 7, and (D) a softening point of 50 to 160.

[0007]

DETAILED DESCRIPTION OF THE INVENTION The hydrocarbon resin of the present invention is selected from at least one styrene monomer (I) represented by the following general formula (1) and a compound represented by the following general formula (2). At least one aliphatic monomer (I
It is a resin obtained by copolymerization of I). This resin is a combination of a styrene-based monomer represented by the general formula (1) and an aliphatic-based monomer represented by the general formula (2), a binary copolymer, a terpolymer, and a quaternary copolymer. Any of multi-component copolymers such as coalescing may be used.

[0008]

Embedded image In the formula, R ¹ , R ² , R ³ and R ⁴ may be the same or different and are a hydrogen atom or an alkyl group having 4 or less carbon atoms.
Examples of the alkyl group having 4 or less carbon atoms include, for example, a methyl group, an ethyl group, a propyl group,
Alkyl group. Among them, a methyl group and an ethyl group are particularly preferable.

[0009]

Embedded image In the formula, R ^{5 to} R ¹⁰ may be the same or different and are a hydrogen atom or an alkyl group having 4 or less carbon atoms, A is an alkylene group having 4 or less carbon atoms, and n is 0 or 1.

Examples of the alkyl group having 4 or less carbon atoms include an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group and a butyl group. Among them, a methyl group and an ethyl group are particularly preferable. Examples of the alkylene group having 4 or less carbon atoms include an alkylene group having 1 to 4 carbon atoms such as a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, and an isobutylene group. Among them, a methylene group and an ethylene group are preferable, and a methylene group is particularly preferable.

Specific examples of the styrene monomer (I) represented by the general formula (1) include styrene, vinyl toluene, α-methyl styrene, isopropenyl toluene and the like. These styrene monomers (I) may be used alone or in combination of two or more.

Preferred examples of the aliphatic monomer (II) represented by the general formula (2) include, for example, R ^{7 to} R ¹⁰
Is hydrogen, n is 1 and A is a methylene group, a compound of the following formula (2-1), and R ⁵ , R ⁶ and R ^{8 to} R ¹⁰
Is a hydrogen, and n is 0 and a compound of the following formula (2-2) can be mentioned.

Embedded image

Embedded image

Specific examples of the aliphatic monomer (II) represented by the general formula (2) include diisobutylene,
Examples thereof include 5,5-dimethyl-2-hexane and 2,5,5-trimethyl-2-hexene, and diisobutylene is particularly preferable.

The content ratio of the styrenic monomer and the aliphatic monomer in the hydrocarbon resin of the present invention is 99.5 / 0.5 to 50/50, preferably 9 in molar ratio.
The ratio is 9/1 to 60/40.

The production of the hydrocarbon resin of the present invention can be carried out by copolymerizing the styrene monomer and the aliphatic monomer in the presence of a catalyst.

The catalyst used for the polymerization is generally known as a Friedel-Crafts catalyst, for example, various complexes of aluminum chloride, aluminum bromide, dichloromonoethylaluminum, titanium tetrachloride, tin tetrachloride and boron trifluoride. And the like.

The amount of the catalyst used is preferably in the range of 0.01 to 5.0% by weight, more preferably 0.05 to 3.0% by weight, based on the total amount of the styrene monomer and the aliphatic monomer.
It is preferably in the range of 0% by weight.

In addition, at the time of the polymerization reaction, at least one selected from aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbons is used in order to remove reaction heat and suppress the increase in viscosity of the reaction mixture. It is preferred to carry out the polymerization reaction in different hydrocarbon solvents. As preferred hydrocarbon solvents, aromatic hydrocarbons such as toluene, xylene, ethylbenzene, mesitylene, cumene, cymene, or mixtures thereof, or aliphatic hydrocarbons such as pentane, hexane, heptane, octane and / or cyclopentane And a mixture with cycloaliphatic hydrocarbons such as cyclohexane and methylcyclohexane. In the polymerization, the amount of the hydrocarbon solvent is preferably adjusted so that the initial concentration of the monomer in the reaction mixture is in the range of 10 to 80%.

The polymerization temperature can be appropriately selected depending on the type of the monomer and the catalyst used and the amount thereof.
It is preferable to carry out in the range of 30 ° C to 50 ° C. Further, the polymerization time is generally about 0.5 to 5 hours, usually,
The polymerization is almost complete in 1-2 hours.

As the polymerization mode, either a batch type or a continuous type can be adopted. Also, multi-stage polymerization can be performed.

After the completion of the polymerization, the catalyst residue is removed by washing. Usually, it is preferable to use an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide or the like is dissolved, or an alcohol such as methanol, and it is particularly preferable to wash and demineralize with methanol. After the washing is completed, unreacted monomers, polymerization solvent and the like are distilled off under reduced pressure to obtain the hydrocarbon resin of the present invention.

The hydrocarbon resin of the present invention preferably has a weight average molecular weight of 300 to 7000, more preferably 60 to 7000.
It is in the range of 0-5000. The molecular weight distribution represented by the weight average molecular weight / number average molecular weight of the hydrocarbon resin of the present invention is 5
The following are preferable, and 1.1 to 4 are more preferable. The softening point of the hydrocarbon resin of the present invention is preferably in the range of 50 to 160, and more preferably in the range of 60 to 140.

The hydrocarbon resin of the present invention may further contain, if necessary, various compounding agents such as a weather stabilizer, an antioxidant and the like within a range not to impair the object of the present invention.

The hydrocarbon resin of the present invention can also be used as a compound such as a tackifier for hot melt adhesives and pressure-sensitive adhesives, a printing ink, an adhesive for paints, a thermal transfer ink ribbon binder and a toner. .

[0025]

EXAMPLES Examples of the present invention will be shown below to explain the present invention more specifically, but the present invention is not limited by these examples.

In the present invention, the physical properties of the resin were measured by the following methods. (A) Hue A Gardner number was measured in accordance with JIS K 5400. (B) Softening point The softening point was measured by the ring and ball method according to JIS K 2207. (C) Weight average molecular weight It was measured under the following conditions using gel permeation chromatography. Solvent: THF Temperature: 40 ° C. Column: TSK gel G7000HXL TSK gel G4000HXL (2 pieces) manufactured by Tosoh Corporation TSK gel G2000HXL TSK guard column HXL (d) Melt viscosity Measured using an Emirror viscometer. (E) Heat resistant hue A test tube having an inner diameter of 18 mm and a length of 180 mm containing 10 g of a sample was placed in an aluminum block heater heated to 180 ° C, and the hue after 72 hours was measured by the Gardner method. (F) Thermal decomposability A 15 g sample was placed in an Emmirror viscometer heated to 200 ° C., and the melt viscosity after 3 hours was measured with stirring. (G) Resin composition It was measured under the following conditions using gas chromatography. Measuring device: GC-9A manufactured by Shimadzu Corporation Column temperature: 200 ° C

Example 1 Preparation of IPT / DIB Copolymer with Softening Point of 96 ° C. 140 g of isopropenyltoluene (IPT) was placed in a 1 L four-necked flask equipped with a stirrer, a thermometer, and a vent tube equipped with a condenser. , Diisobutylene (DIB) 60
g and 200 g of dehydrated and purified toluene are charged and stirred well. The uniformly dispersed mixture is cooled to 5 ° C. by using an alcohol bath cooled with dry ice. On the other hand, under a nitrogen atmosphere, 0.3 g of boron trifluoride phenolate complex (1.7 equivalents of phenol) and 10 times the amount of dehydrated and purified toluene were placed in a 25 mL dropping funnel for supplying the catalyst, and the dropping funnel was charged. Is attached to a 1 L 4-neck flask.

Thereafter, the catalyst is gradually supplied to the reactor to start the reaction. The temperature of the reaction mixture is kept at 5 ° C. by using an alcohol bath cooled with dry ice. The supply of the catalyst is completed in 10 minutes, and the reaction is performed after 2 hours while maintaining the temperature at 5 ° C. After the polymerization is completed, 1N is added to the reaction mixture.
An aqueous NaOH solution was added to stop the polymerization reaction. The obtained reaction mixture was washed with a large amount of water five times, and then the solvent and unreacted monomer were distilled off under reduced pressure by an evaporator to remove IPT /
150 g of DIB copolymer was obtained. The yield was 75%.

The above polymerization conditions (monomer supply ratio, catalyst amount)
Table 1 shows the results of the resin properties (resin composition, softening point, hue, melt viscosity, molecular weight Mw, molecular weight distribution, heat-resistant hue, and thermal decomposability) of the obtained IPT / DIB copolymer.

Example 2 Preparation of IPT / DIB copolymer having a softening point of 115 ° C. 180 g of isopropenyl toluene (IPT) was placed in a 1-L four-necked flask equipped with a stirrer, a thermometer, and a vent tube equipped with a condenser. , Diisobutylene (DIB) 20
g and 200 g of dehydrated and purified toluene are charged and stirred well. The uniformly dispersed mixture is cooled to 5 ° C. by using an alcohol bath cooled with dry ice. On the other hand, in a 25 mL dropping funnel for supplying a catalyst, 0.3 g of boron trifluoride phenolate complex (1.7 times equivalent of phenol) and 10 times the amount of dehydrated and purified toluene were put in a nitrogen atmosphere and 10 times the amount of the catalyst. Is attached to a 1 L 4-neck flask.

Thereafter, the catalyst is gradually supplied to the reactor to start the reaction. The temperature of the reaction mixture is kept at 5 ° C. by using an alcohol bath cooled with dry ice. The supply of the catalyst is completed in 10 minutes, and the reaction is performed after 2 hours while maintaining the temperature at 5 ° C. After the polymerization is completed, 1N is added to the reaction mixture.
An aqueous NaOH solution was added to stop the polymerization reaction. The obtained reaction mixture was washed with a large amount of water five times, and then the solvent and unreacted monomer were distilled off under reduced pressure by an evaporator to remove IPT /
148 g of DIB copolymer was obtained. The yield was 74%.

The above polymerization conditions (monomer supply ratio, catalyst amount)
Table 1 shows the results of the resin properties (resin composition, softening point, hue, melt viscosity, molecular weight Mw, molecular weight distribution, heat-resistant hue, and thermal decomposability) of the obtained IPT / DIB copolymer.

Example 3 Preparation of αMS / DIB Copolymer with Softening Point of 96 ° C. A 1 L four-necked flask equipped with a stirrer, a thermometer, and a vent tube equipped with a condenser was charged with α-methylstyrene (α).
MS) 140 g, diisobutylene (DIB) 60 g and dehydrated and purified toluene 200 g are charged and stirred well.
The uniformly dispersed mixture is cooled to 5 ° C. by using an alcohol bath cooled with dry ice. On the other hand, under a nitrogen atmosphere, 0.3 g of boron trifluoride phenolate complex (1.7 equivalents of phenol) and 10 times the amount of dehydrated and purified toluene were placed in a 25 mL dropping funnel for supplying the catalyst, and the dropping funnel was charged. Is attached to a 1 L 4-neck flask.

Thereafter, the catalyst is gradually supplied to the reactor to start the reaction. The temperature of the reaction mixture is kept at 5 ° C. by using an alcohol bath cooled with dry ice. The supply of the catalyst is completed in 10 minutes, and the reaction is performed after 2 hours while maintaining the temperature at 5 ° C. After the polymerization is completed, 1N is added to the reaction mixture.
An aqueous NaOH solution was added to stop the polymerization reaction. The obtained reaction mixture was washed five times with a large amount of water, and then the solvent and unreacted monomer were distilled off under reduced pressure using an evaporator to obtain αMS /
158 g of DIB copolymer was obtained. The yield was 79%.

The above polymerization conditions (monomer supply ratio, catalyst amount)
Table 1 shows the results of the resin properties (resin composition, softening point, hue, melt viscosity, molecular weight Mw, molecular weight distribution, heat-resistant hue, and thermal decomposability) of the obtained αMS / DIB copolymer.

Comparative Example 1 180 g of isopropenyl toluene (IPT) was placed in a 1 L four-necked flask equipped with a stirrer, a thermometer, and a vent tube equipped with a condenser.
Aliphatic unsaturated hydrocarbon fraction (C5 fraction) of composition 20
g and 110 g of dehydrated and purified toluene are stirred well. The uniformly dispersed mixture is cooled to 5 ° C. by using an alcohol bath cooled with dry ice. On the other hand, in a 25 mL dropping funnel for supplying a catalyst, 0.36 g of a boron trifluoride phenolate complex (1.7 equivalents of phenol) and 10 times the amount of dehydrated and purified toluene were placed in a nitrogen atmosphere, and the dropping funnel was charged. Is attached to a 1 L 4-neck flask.

Thereafter, the catalyst is gradually supplied to the reactor to start the reaction. The temperature of the reaction mixture is kept at 5 ° C. by using an alcohol bath cooled with dry ice. The supply of the catalyst is completed in 10 minutes, and after 2 hours, the reaction is carried out while maintaining 5 ° C. After the polymerization is completed, 1N is added to the reaction mixture.
An aqueous NaOH solution was added to stop the polymerization reaction. The obtained reaction mixture was washed five times with a large amount of water, and then the solvent and unreacted monomer were distilled off under reduced pressure by an evaporator to obtain 164 g of an isopropenyl toluene / aliphatic hydrocarbon copolymer. At this time, the yield was 81%.

The above polymerization conditions (monomer supply ratio, catalyst amount)
And resin properties of the obtained isopropenyltoluene / aliphatic hydrocarbon copolymer (resin composition, softening point, hue, melt viscosity, molecular weight Mw, molecular weight distribution, heat-resistant hue, thermal decomposition)
Table 1 shows the results.

Comparative Example 2 200 g of α-methylstyrene (αMS) and 200 g of dehydrated and purified toluene were charged into a 1-L four-necked flask equipped with a stirrer, a thermometer, and a vent tube equipped with a condenser, and thoroughly stirred. The uniformly dispersed mixture is cooled to 5 ° C. by using an alcohol bath cooled with dry ice. On the other hand, 0.30 g of a boron trifluoride phenolate complex (1.7 equivalents of phenol) and toluene dehydrated and purified were placed in a 25 mL dropping funnel for supplying the catalyst under nitrogen atmosphere.
Add 0 volume and attach the dropping funnel to a 1 L 4-neck flask.

Thereafter, the catalyst is gradually supplied to the reactor to start the reaction. The temperature of the reaction mixture is kept at 5 ° C. by using an alcohol bath cooled with dry ice. The supply of the catalyst is completed in 10 minutes, and the reaction is performed after 2 hours while maintaining the temperature at 5 ° C. After the polymerization is completed, 1N is added to the reaction mixture.
An aqueous NaOH solution was added to stop the polymerization reaction. The obtained reaction mixture was washed five times with a large amount of water, and then the solvent and unreacted monomer were distilled off under reduced pressure by an evaporator to obtain 164 g of α-methylstyrene homopolymer. The yield was 82%.

The above polymerization conditions (monomer supply ratio, catalyst amount)
Table 1 shows the results of the resin physical properties (resin composition, softening point, hue, melt viscosity, molecular weight Mw, molecular weight distribution, heat-resistant hue, and thermal decomposability) of the obtained α-methylstyrene homopolymer.

[Table 1]

[Table 2]

[0042]

The aromatic hydrocarbon resin obtained according to the present invention has excellent heat resistance and excellent hue.
It can be suitably used for applications such as tackifiers for adhesives, paper treatment agents, thermal transfer ink ribbon binders, and toner compounding agents.

Claims (2)

[Claims] 1. A styrene monomer (I) represented by the following general formula (1): (In the formula, R ¹ , R ² , R ³ and R ⁴ may be the same or different and are a hydrogen atom or an alkyl group having 4 or less carbon atoms.) Selected from compounds represented by the following formula (2) A copolymer with at least one aliphatic monomer (II), (Wherein, R ^{5 to} R ¹⁰ may be the same or different and are a hydrogen atom or an alkyl group having 4 or less carbon atoms, A is an alkylene group having 4 or less carbon atoms, and n is 0 or 1. (A) The molar ratio of (I) / (II) is 99.5 / 0.5-5.
0/50, and (B) the weight average molecular weight is 300 to 70.
00, (C) a hydrocarbon resin having a molecular weight distribution of 1.1 to 7, and (D) a softening point in a range of 50 to 160. 2. The styrene monomer (I) is at least one monomer selected from isopropenyltoluene, α-methylstyrene, vinyltoluene and styrene, and the aliphatic monomer (II) is diisobutylene. The hydrocarbon resin according to claim 1, wherein: