JPS6322885A - Composition for pressure-sensitive adhesive - Google Patents

Abstract

PURPOSE:A composition for pressure-sensitive adhesive, having high softening point and low melt viscosity, showing stable bond strength and cohesive force, blended with a specific hydrocarbon resin obtained by polymerizing a fraction containing aliphatic unsaturated hydrocarbon, etc., as a tackifier. CONSTITUTION:(A) A fraction containing aliphatic unsaturated hydrocarbon and having -20-100 deg.C boiling point is blended with (B) a fraction containing an aliphatic inner olefin to give a mixture prepared in such a way that it has 10-60mol% 1,3-conjugated diene component, 40-90mol% aliphatic inner olefin component containing dihydrodicyclopentadiene, etc., <=25mol% end monoolefin component and <=5mol% cyclopentadiene component. The blended fractions are polymerized in the presence of a Friedel-Crafts catalyst to give a hydrocarbon resin, which is blended with a tackifier to give the aimed composition for pressure-sensitive adhesive resin. EFFECT:Showing improved effects in tack.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a pressure-sensitive adhesive composition, and more particularly, the present invention relates to a pressure-sensitive adhesive composition, and more particularly, a composition containing a specific aliphatic unsaturated hydrocarbon-containing fraction and a specific aliphatic internal olefin as main components. The present invention relates to a pressure-sensitive adhesive composition containing a hydrocarbon resin obtained by polymerizing a mixed fraction consisting of internal olefin-containing fractions as a tackifying agent.

Conventionally, in the field of pressure sensitive adhesives and hot melt adhesives, natural rosin-based resins such as rosin or its modified products, and alkyd resins have been used as tackifying agents.

It is known that xylylene resin, epoxy resin, etc. can be used. Among these tackifier resins, rosin-based resins such as maleated rosin are said to be the most superior, but these rosin-based resins rely on natural products for their raw materials, so they have become less popular in recent years. Unable to cope with significant demand growth.

Hydrocarbon resins, which can be produced industrially at low cost and easily, are attracting attention as tackifiers that can replace conventional rosin-based resins, and many hydrocarbon resins have been proposed. In general, hydrocarbon resins include aromatic hydrocarbon resins produced from fractions containing aromatic unsaturated hydrocarbons, aliphatic hydrocarbon resins produced from fractions containing aliphatic hydrocarbons, and unsaturated There are aliphatic aromatic copolymerized hydrocarbon resins that are copolymerized with hydrocarbon-containing fractions, and each is used as a tackifying agent for appropriate purposes.

Even when these hydrocarbon resins are used as tackifying agents for pressure-sensitive adhesives and hot-melt adhesives, none of these hydrocarbon resins have stable and excellent adhesive strength or cohesive strength.
Moreover, it has the disadvantage of being inferior in tack power.

The present inventors have improved the above-mentioned drawbacks found in conventional hydrocarbon resins, and have a high softening point and low melt viscosity.
Moreover, as a result of studying hydrocarbon resins that can exhibit excellent performance when blended as a tackifying agent in adhesive compositions, we found that aliphatic unsaturated hydrocarbon fractions with specific compositions and an internal olefin-containing fraction containing an aliphatic internal olefin with a specific composition as a main component, in the presence of a Friedel-Krach type catalyst, thereby achieving the above object. It was discovered that a hydrocarbon resin based on the above-mentioned method can be obtained, and the present invention was achieved.

The aliphatic hydrocarbon resin obtained by the present invention can be used as is as a tackifier for pressure-sensitive adhesives and hot-melt adhesives. A pressure-sensitive adhesive composition containing this aliphatic hydrocarbon resin as a tackifying agent is characterized by exhibiting stable adhesive force and cohesive force as well as excellent tack strength.

To summarize the present invention, the present invention provides (a) a fraction with a boiling point in the range of -10 to +100'O, and a range in which the 1,3-conjugated diene component in the total unsaturated components is 30 mol% or more; , an aliphatic unsaturated hydrocarbon-containing fraction in which the terminal monoolefin component is in the range of 30 mol% or less and the cyclopentadiene component is in the range of 5 mol% or less, and (b) in the total unsaturated components,
The aliphatic internal olefin component containing at least dihydrodicyclopentadiene is in the range of 80 mol% or more, the terminal monoolefin component is in the range of 15 mol% or less, and the cyclopentadiene component is in the range of 5 mol% or less. An aliphatic internal olefin-containing fraction is defined as an aliphatic fraction containing dihydrodicyclopentadiene in the range of 10 to 60 mol% of the 1,3-conjugated diene component among the unsaturated components in the mixed fraction. System internal olefin component is 40 to 9
Range of 0 mol%, terminal monoolefin component is 25 mol%
Caking the hydrocarbon resin obtained by mixing the following range and the cyclopentadiene component within the range of 5 mol% or less, and polymerizing this mixed fraction in the presence of a Friedel Krach type catalyst. The gist of the present invention is a pressure-sensitive adhesive composition which is characterized in that it is blended as an imparting agent.

The polymerization raw materials used in the present invention are an aliphatic unsaturated hydrogen-containing fraction (a) with a specific composition and an internal olefin-containing fraction (b) whose main component is an aliphatic internal olefin with a specific composition. ), the aliphatic unsaturated hydrocarbon-containing fraction (a) has a boiling point of -20 to +1
00℃ range, 1.3-
It is an aliphatic unsaturated hydrocarbon-containing fraction in which the conjugated diene component is in the range of 20 mol% or more, the terminal upper olefin is in the range of 30 mol% or less, and the cyclopentadiene component is in the range of 5 mol% or less. More preferably, the aliphatic unsaturated hydrocarbon-containing fraction (a) has an aliphatic unsaturated hydrocarbon content of −1O to +5
It is a fraction in the range of 0°C, the 1,3-conjugated diene component in the total unsaturated components is in the range of 30 mol% or more, the terminal monoolefin component is in the range of 20 mol% or less, and the cyclopentadiene component is 3 mol It is a fraction containing aliphatic unsaturated hydrocarbons in the range of % or less. Specific examples of the 1,3-conjugated diene component contained in the aliphatic unsaturated hydrocarbon-containing fraction include 1,3-butadiene, 153-pentadiene, and isoprene. Further, as the unsaturated hydrocarbon components contained in the aliphatic unsaturated hydrocarbon-containing fraction, in addition to the 1.3-conjugated diene component, the 2-
Aliphatic internal olefins such as butene, 2-methyl-2-butene, 2-pentene, cyclopentene, 1-butene, imbutylene, 1-pentene, 2-methyl-1-7'
Ten.

There is no problem even if the terminal monoolefin such as 3-methyl-1-butene, cyclopentadiene and other olefins are contained within the above range, and the aliphatic unsaturated hydrocarbon-containing fraction (a) may contain aliphatic saturated hydrocarbon components within the above-mentioned range in addition to the unsaturated components, in which case all of the aliphatic unsaturated hydrocarbon-containing fractions Although the content of the disturbing component is arbitrary, it is usually in the range of 30% by weight or more, preferably 40% by weight or more. Further, as the aliphatic unsaturated hydrocarbon-containing fraction, a single component or a mixture of two or more of the above 1,3-conjugated dienes can be used, and if the above-mentioned composition range is within the above-mentioned range, It is also possible to use mixtures of 1.3-conjugated dienes and the unsaturated components mentioned above.

As the aliphatic unsaturated hydrocarbon-containing fraction (a), if the unsaturated fraction in the above-mentioned range produced by thermal decomposition of petroleum is in the above-mentioned composition range, this aliphatic unsaturated hydrocarbon-containing fraction (a) is used. The contained fraction can be used as is. In addition, when the composition of the terminal monoolefin component or cyclopentadiene component in this unsaturated hydrocarbon-containing fraction is large, after heat soaking this unsaturated hydrocarbon-containing fraction by a known method, it is possible to By collecting the fraction, the aliphatic unsaturated hydrocarbon-containing fraction can be obtained. Also,
The above 1.3- contained in this unsaturated hydrocarbon-containing fraction
When the composition of the conjugated diene component is small, this uncomplicated hydrocarbon-containing fraction is added with the above 1.

A 3-conjugated diene component can also be added to obtain the aliphatic unsaturated hydrocarbon-containing fraction.

The aliphatic internal olefin-containing fraction (b) used in the present invention is such that the aliphatic internal olefin component containing at least dihydrodicyclopentadiene in the total unsaturated components is 80 mol% or more. , an aliphatic internal olefin-containing fraction having a terminal monoolefin content of 15 mol % or less and a cyclopentadiene component of 5 mol % or less, and more preferably, among all unsaturated components,
The aliphatic internal olefin component containing at least dihydrodicyclopentadiene is in the range of 85 mol% or more, the terminal monoolefin component is in the range of 10 mol% or less, and the cyclopentadiene component is in the range of 3 mol% or less. It is a fraction containing aliphatic internal olefins. The aliphatic internal olefins contained in the aliphatic internal olefin-containing fraction include chain aliphatic internal olefins and alicyclic internal olefins, and specifically include dihydrodicyclopentadiene. In addition, 2-butene, 2-methyl-2
Examples include -butene, 2-pentene, and cyclopentene. In addition to the aliphatic internal olefins, unsaturated components contained in the aliphatic internal olefin-containing fraction include l-butene, imbutylene, 1-pentene, 2-methyl-1-butene, -Terminal monoolefins such as methyl-1-butene, cyclopentadiene, and other olefins may be contained within the above ranges. In addition to the aliphatic unsaturated hydrocarbon component, it may contain an aliphatic saturated hydrocarbon component; in that case, the total undisturbed components in the aliphatic internal olefin-containing fraction Although the content is arbitrary, it is usually 30% by weight or more, preferably 40% by weight or more.

Specifically, the aliphatic internal olefin-containing fraction (b) is, for example, 8 points produced by thermal decomposition of petroleum, usually -10 to +100'C1, preferably 20 to 50
By contacting an aliphatic unsaturated hydrocarbon-containing fraction in the range of °C and hydrogen in the presence of a hydrogenation catalyst, the diene component is partially hydrogenated to internal olefins, the terminal monoolefins are isomerized to internal olefins, The aliphatic internal olefin-containing fraction is obtained. Usual hydrogenation catalysts are used as hydrogenation catalysts, specifically palladium, rhodium, ruthenium, platinum, iridium, osmium,
Examples include catalysts in which metals such as iron, cobalt, nickel, chromium, molybdenum, and tungsten are supported on various carriers such as activated carbon, alumina, and silica. In addition, in order to suppress further hydrogenation and disappearance of the isomerized internal olefin, it is also preferable to use a catalyst partially poisoned with a sulfur compound or the like as the metal catalyst. The reaction is carried out under pressure, usually 1 to 150 kg/c, 2-Q, preferably 5 to 50 kg/c.
The temperature during the zero reaction, which is in the range of Kg/cm2-G, is usually in the range of room temperature to 200°C, preferably in the range of 40 to 150°C. The composition of the fraction obtained by this partial hydroisomerization treatment usually satisfies the above composition range, and can be used as is as the aliphatic internal olefin-containing fraction.

Composition of a mixed fraction consisting of the aliphatic unsaturated hydrocarbon-containing fraction (a) and the internal olefin-containing component (b) whose main component is the aliphatic internal olefin, which is the polymerization raw material used in the present invention. is 1. of all unsaturated components in it.
3-conjugated diene component ranges from 10 to 60 mol%, aliphatic internal olefin component ranges from 40 to 90 mol%,
It is necessary that the terminal monoolefin component is in the range of 1 to 25 mol% and the cyclopentadiene component is in the range of 5 mol%, and more preferably the 1,3-conjugated diene component in all the unsaturated components therein. is in the range of 15 to 50 mol%,
This is a mixed fraction in which the terminal monoolefin component is in the range of 20 mol% or less and the cyclopentadiene component is in the range of 3 mol% or less. Here, 1 of the total unsaturated components in the mixed fraction
．． When the 3-conjugated diene component is more than 60 mol % and the aliphatic internal olefin component is less than 10 mol %, the physical properties of the resulting hydrocarbon resin are such that the melt viscosity becomes significantly high and gel-like substances are produced as by-products. It becomes easier. In addition, when the 1,3-conjugated diene component in the total unsaturated components is less than 20 mol% and the aliphatic internal olefin component is more than 80 mol%, the physical properties of the resulting hydrocarbon resin may be increased. become unable to do so. Furthermore, if the terminal monoolefin component in the total unsaturated components in the mixed fraction exceeds 10 mol %, the resulting hydrocarbon resin will have a low softening point. Furthermore, if the cyclopentadiene component in the total unsaturated components in the mixed fraction exceeds 5 mol %, the resulting hydrocarbon resin will produce more gel-like insoluble resin and will have a lower hue.

In the present invention, the mixed fraction of polymerization raw materials is polymerized in the presence of a free-solat fluorine catalyst. Here, specific examples of Friedel-Kraf type catalysts include aluminum chloride, aluminum bromide, boron trifluoride, various complexes of boron trifluoride, tin chloride, tin bromide, and diantimony chloride. , antimony bromide, titanium chloride, and the like. Among these Friedel Krach type catalysts, the use of aluminum chloride provides a high yield of 1
This is preferable because a hydrocarbon resin having a good hue and a high softening point can be obtained. The proportion of the free-sol fluorine catalyst used is usually 0.1 to 10 mol %, preferably 0.5 to 2 mol %, based on the total unsaturated components in the mixed fraction of the polymerization raw material.
The range is mole %.

In the present invention, the polymerization reaction of the polymerization raw material in the presence of a free sol fluorine catalyst can be carried out in the absence of a solvent or in the presence of a solvent. When carried out in the presence of a solvent, specific examples of the solvent used include aliphatic hydrocarbons such as butane, pentane, hexane, heptane, and octane, benzene,
Examples include aromatic hydrocarbons such as toluene, xylene, ethylbenzene, cumene, cymene, and diisopropylbenzene. When a solvent is used, its usage ratio is usually 0.05 to 1, preferably 0.1 to 0.5 as a weight ratio to all unsaturated components in the mixed fraction.
is within the range of

The polymerization reaction is usually carried out at -10 to +150°C, preferably at 10°C.
The time required for the 1-polymerization reaction, which is carried out at a temperature in the range of 1 to 120°C, varies depending on the reaction size of the catalyst used and other conditions, but is usually in the range of 1 to 5 hours. , catalyst decomposition treatment, deashing treatment,
A hydrocarbon resin useful as a tackifier for pressure-sensitive adhesives and hot-melt adhesives can be obtained by processing by conventional methods such as distilling off the solvent.

Next, the present invention will be specifically explained using examples. The method for evaluating the physical properties and performance of hydrocarbon resins is shown below.

[Evaluation method of resin physical properties] (1) Measuring method of softening point It was measured by the method of JIS K-2531.

(2) Melt viscosity measurement method Using an EMILA rotational viscometer manufactured by EMILA (Denmark), the melt viscosity was measured at a temperature of 200° C. and a shear rate of 344 seC1.

(3) Compatibility with other polymers: ethylene-vinyl acetate copolymer, natural rubber, styrene-
The compatibility with isoprene-styrene block copolymer and modified rosin was measured by the following method, and the results were evaluated in the following three stages.

0: Transparent Δ: Transparent ×: Opaque ■Mitsui Polychemical product EVAFLEX 410 (vinyl acetate content: 19% by weight) or 21O (vinyl acetate content: 28% by weight) and hydrocarbon resin were heated at 180°C in amounts of 'J'. The mixture was mixed on a plate and coated on a polyester film to a thickness of about 1 inch, and the transparency of the coating was evaluated.

(2) A hydrocarbon resin in an amount equal to that of natural rubber was dissolved in a 10% solution of natural rubber in toluene, and this was coated on a polyester film to a thickness of about 80p, and the transparency of the coating film was evaluated.

(2) Compatibility with styrene-in-plane-styrene block copolymer (TR-1107 manufactured by Shell Chemical Co., Ltd.) was measured in the same manner as (2).

(4) Heat resistance 25 g of hydrocarbon resin was placed in a test tube with an inner diameter of 15 mm and a length of 180 mm, heated in an oil bath at 200° C. for 3 hours, and the hue was measured by the Gardner method.

(5) Softening point According to the method of JTS K-5665.

(6) Melt viscosity Using an Emira type rotary density meter, shear rate 176 Sec -
Measured on a molten product at 200°C in 1 [Hot melt adhesive evaluation method] 100 parts of adhesive raw material resin, 100 parts of commercially available SIS-based broblock copolymer Cauliflex TI'l-1107 (shell product), 30 parts of mineral oil (Shell product Shellflex 371N) and stabilizer (Ilkanox 10)
10) Add 3 parts and knead in a kneader at 150°C for 30 minutes to adjust the adhesive. Next, hot coat the adhesive on a polyester film (Lumirror, a Toshi product, thickness 25 mm). It was coated to a thickness of 55 pots using a melt m cooler, and its adhesive strength and cohesive force were measured by the method of JIS Z-1522, and its tack was measured by the Dow method (20°C).

Reference Example 1 6g, a wire mesh catalyst charge source was fixed in advance to the stirring blade of an autoclave (manufactured by St19304). 284 g of a palladium-based catalyst PGC-C manufactured by Nippon Engelhard Co., Ltd. is placed in this basket. 6. Next, 2100 g of a C5 fraction obtained by thermal decomposition of naphtha and 1.81 g of ethyl mercaptan are added into an autoclave. Then, add hydrogen from a hydrogen cylinder at a temperature of 90 to 100℃ and a pressure of 10 to 20 Kg/cm2.
The reaction was carried out for about 9 hours. After cooling and depressurizing, the contents were taken out. This hydrogenation reaction solution was designated as fraction A, and its composition along with the raw materials are shown in Table 1.

Reference Example 2 The CstJ fraction (the remaining fraction after isoprene was extracted from the CsfJ fraction) was treated under the same conditions as in Reference Example 1. This hydrogenation reaction solution was designated as fraction B, and its composition is shown in Table 2 along with the raw materials.

Table 1 Table 2 Table 3 shows the M1 value of the 1,3-pentadiene fraction from which imprene and pentane have been removed. This fraction is designated as C fraction. This C fraction x 08 g (ffi synthetic component 75 g) A fraction 124 g (polymerization component 75 g) prepared in Reference Example 1 was mixed in a pressure cylinder. The composition of the mixed fraction is shown in Table 4. First, suspend 2.0 g of anhydrous aluminum chloride pulverized product in 15 g of xylylene in a glass autoclave under a nitrogen atmosphere, and add the mixed distillate from a pressure cylinder in about 20 minutes while maintaining the reaction temperature at 60°C. was added dropwise. After 2 hours of polymerization, the catalyst was decomposed with methanol in the usual manner, washed with water, and concentrated to obtain 71 g of resin. Softening point: 94°C, melt viscosity: 80 cps1
The hue was 6.

Table 3 Polymerization Example 2 Predetermined amounts of fractions shown in Table 4 were mixed in a pressure cylinder. In advance, 20 g of anhydrous aluminum chloride pulverized product was suspended in the specified amount of solvent shown in Table 5 in a nitrogen atmosphere in a 1-vertical glass autoclave, and while the temperature was maintained at 60°C, the mixed distillate was poured from a pressure cylinder in about 15 minutes. Let it drip. 2
After reacting for a period of time, the catalyst was decomposed with methanol, washed with water, and concentrated to obtain a resin (the yield of each resin and the resin physical properties are shown in Table 5).

Comparative Polymerization Example 1 Distillation 25-3 obtained by distilling the remaining fraction (Spen) Cs fraction after extracting isoprene from CsfJ at normal pressure
The composition of the 5°C fraction is shown in Table 4.

This fraction is designated as E fraction.

A predetermined amount of E fraction shown in Table 4 was taken into a pressure cylinder and mixed. In advance, 2.0 g of anhydrous aluminum chloride pulverized product was suspended in a predetermined amount of solvent shown in Table 6 in a 11 glass autoclave under N2 atmosphere, and while maintaining the temperature at 60°C, the mixed fraction was extracted from a #pressure cylinder. is added dropwise over approximately 15 minutes. After reacting for 2 hours, the catalyst was decomposed with methanol, washed with water, and concentrated to obtain a resin. Table 5 shows the yield and physical properties of each resin.

Table 5 [Evaluation results as a hot melt adhesive] Application 1 to 2
．． Comparative Examples 1 to 2 Using the resins obtained in Examples 1 and 2 and Comparative Polymerization Example 1 and reprint resin (Wingtack Plus manufactured by Gudoyer), respectively, and adjusting the adhesive, adhesive tape was prepared. I looked into the matter. The results are shown in Table 6.

Table 6

Claims (3)

[Claims] (1) (a) It is a distillate with a boiling point in the range of -20 to +100°C, and the 1,3-conjugated diene component in the total unsaturated components is 2
The range is 0 mol% or more, the terminal monoolefin component is 30 mol% or less, and the cyclopentadiene component is 5 mol%.
An aliphatic unsaturated hydrocarbon-containing fraction within the following range and (b) a range in which the aliphatic internal olefin component containing at least dihydrodicyclopentadiene in the total unsaturated components is 80 mol% or more, The terminal monoolefin component is in the range of 15 mol% or less and the cyclopentadiene component is in the range of 5
The fraction containing aliphatic internal olefins is in the range of 10 to 60 mol % of the 1,3-conjugated diene component among the unsaturated components in the mixed fraction, and the fraction containing dihydrodiolefin is Mixing such that the aliphatic internal olefin component containing cyclopentadiene is in the range of 40 to 90 mol%, the terminal monoolefin component is in the range of 25 mol% or less, and the cyclopentadiene component is in the range of 5 mol% or less,
A pressure-sensitive adhesive composition characterized in that a hydrocarbon resin obtained by polymerizing this mixed fraction in the presence of a Friedel-Crafts type catalyst is blended as a tackifying agent. (2) The adhesive composition according to claim 1, wherein the adhesive is a hot melt type adhesive. (3) The aliphatic internal olefin-containing fraction is brought into contact with an aliphatic unsaturated hydrocarbon-containing fraction with a boiling point of -10 to +100°C produced by thermal decomposition of petroleum and hydrogen in the presence of a hydrogenation catalyst. The pressure-sensitive adhesive composition according to claim 1, which is a fraction obtained by