JPS61255918A - Hydrogenated 5c petroleum resin and hot melt adhesive composition prepared therefrom - Google Patents

Abstract

PURPOSE:A hydrogenated 5C petroleum resin which can give the titled composition excellent in (initial) tack, holding power, heat resistance, weather resistance and transparency over a wide range of temperature of use, obtained by hydrogenating a specified petroleum resin. CONSTITUTION:A petroleum resin is obtained by polymerizing stock which is prepared by distilling a -10-100 deg.C-boiling by-product distillate from petroleum thermal cracking to adjust its total diolefin content and total olefin content to 15-30wt% and 15-30wt%, respectively, at 50-140 deg.C in the presence of a Friedal-Crafts catalyst. This petroleum resin is dissolved in a hydrocarbon solvent and hydrogenated at a temperature of normal temperature to 350 deg.C and a H2 pressure of normal pressure to 350kg/cm<2> in the presence of a catalyst such as a metal such as Ni or Pt or an oxide to obtain the titled petroleum resin having, in the main chain, 50-80wt% units of hydrogenated 5C diolefin and 50-20wt% units of hydrogenated 5C olefin and having a number-average MW of 700-1,500, a softening point of 70-130 deg.C, a glass transition point of 55-100 deg.C, a hue <=1, an initial tack (rolling ball tack) of 4-15 as measured on a mixture of 80pts.wt. this resin with 100pts.wt. Clayton G 1657 saturated thermoplastic block copolymer elastomer) and a holding power (1kg at 75 deg.C) of 0-0.6mm as measured on the same mixture.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a novel hydrogenated C5 petroleum resin, which has a good color and can be used as a tackifier for hot melt adhesive compositions. It is a useful substance suitable for many things. The present invention also relates to superior hot melt adhesive compositions obtained using the novel hydrogenated 05 petroleum resins described above. More specifically, the hot melt adhesive composition of the present invention includes:
It consists of the above petroleum resin as a tackifier, a saturated thermoplastic block copolymer elastomer, and a necessary T/C softener.

Conventionally known adhesive compositions are classified into three types: solvent type using an organic solvent, aqueous emulsion type, and hot melt type. Although the melt-cut portion has excellent physical properties, energy is required to recover the solvent, and solvent pollution associated with solvent recovery is a problem.

The aqueous emulsion type tends to cause entrainment due to shrinkage during application, and also has problems with the water drying process and water pollution. On the other hand, the hot-melt type is superior in terms of high-speed application, energy saving, and pollution-free properties.

Against this background, there is a demand for the development of hot melt adhesives with excellent performance.

Conventionally, naturally occurring resins such as terpene-based resins, rosin-based resins, and hydrogenated rosin-based resins have been widely used as tackifiers for hot-melt adhesives, and terpene-based resins have particularly excellent tackifying properties. It has been awarded a prize because of its effectiveness. However, since it is a natural product, it is unstable in terms of price and supply. Therefore, in recent years, petroleum resins have tended to be used instead of natural products, but they have poor tackifying effects, insufficient heat resistance, and problems with color, odor, etc.

On the other hand, as a thermoplastic elastomer, it has recently been recognized that polystyrene-hydrogenated polydiene-polystyrene block copolymer elastomer has the best quality, heat resistance, and weather resistance, and is effective for this elastomer. There is a need for the development of tackifiers.

(Prior art) In order to improve the drawbacks of conventional petroleum resins, attempts have been made to hydrogenate cyclopentadiene resins and aromatic petroleum resins, but although both improve hue, odor, and heat resistance, , initial adhesive strength (rolling ball tack), adhesive strength and holding power are unbalanced and insufficient. That is, when the initial adhesive strength is increased, the holding strength and adhesive strength decrease.

(holding force); conversely, when the holding force and adhesive force are increased, the initial adhesive force tends to decrease.

In addition, the resin is made of two components: a hydrogenated petroleum resin having a number average molecular weight of 400 to 800, a softening point of 40 to 70°C, and a glass transition point of less than 45°C, and a polystyrene-hydrogenated polydiene-polystyrene block copolymer elastomer. Pressure adhesive formulations have also been proposed (%Kasho 6O-15477
).

However, since this hydrogenated petroleum resin has a low softening point and glass transition point, it has the advantage of high initial adhesion at low temperatures without the addition of a softener. The disadvantage is that the creep property is low.

(Problem to be solved) The inventors of the present invention have solved the problem at a wide range of operating temperatures from low to high temperatures.
With the aim of developing a hot melt adhesive composition with an excellent balance of initial adhesive strength, adhesive strength, and holding power, as well as excellent heat resistance, weather resistance, and color, O That is, it is an object of the present invention to provide a new hydrogenated C5 petroleum resin that is particularly suitable for use as a tackifier, which is a component of hot melt adhesive compositions, and which has an excellent hue. There is. A second object of the present invention is to provide a hot melt adhesive composition containing the above-mentioned novel hydrogenated 05 petroleum resin as a tackifier. It is suitable for producing transparent adhesive tapes with excellent balance of color and hue.

(Means for solving the problem) □ That is, the present invention is a fraction obtained by removing cyclopentadiene from a fraction of -10 to 100°C that is produced as a by-product during thermal decomposition of petroleum. Diolefin content is 1
5 to 30% by weight and a total olefin content of 15 to 30% by weight using a Friedel Krach catalyst;
A resin was obtained by polymerization at ~140°C, and 50 to 80% by weight of units hydrogenated with C5 diolefin, and 50 to 80% by weight of units hydrogenated with 05 olefin, which were produced by hydrogenating this resin according to a conventional method. Contains 20% by weight, 70-1
Softening point of 30℃, glass transition point of 55-100℃, 70
It has a number average molecular weight of 0 to 1500, and Kraton ■
When 80 parts by weight is mixed with 100 parts by weight of G1657 (trade name of saturated thermoplastic block copolymer elastomer manufactured by Shell), the initial adhesive strength (rolling ball tack) is 4 to 15.
and holding force (load 1kg, temperature 75℃) is 0~0.6
The present invention relates to a hot-melt pressure-sensitive adhesive composition comprising a hydrogenated 05 petroleum resin, which is a hydrogenated 05 petroleum resin, a saturated M plastic block copolymer elastomer, and a softener if necessary. The hot melt adhesive composition obtained by the present invention has an excellent balance of initial adhesive strength, adhesive strength, and holding power, and is heat resistant at a wide range of operating temperatures from low to high temperatures.

Excellent weather resistance and transparency.

The hydrogenated C5 petroleum resin which is the tackifier of the present invention can be produced as follows.

As a raw material, 10 to 10 by-products are produced during thermal decomposition of petroleum.
A C5 fraction from which cyclopentadiene is removed or its content is reduced from a 0°C fraction, or a spent C5 fraction (S-
Cs) is used as a raw material whose fraction has a total diolefin content of 15 to 30% by weight and a total olefin content of 15 to 30% by weight by a method such as distillation. When the monoolefin content in the raw material is 30% by weight or more,
This is not preferable because the amount of low molecular weight substances produced is large, and a resin with a high softening point and glass transition point cannot be obtained, and therefore the tackifying effect (particularly the holding power) of the resin is insufficient.

If the diolefin content exceeds 30% by weight, gel-like substances tend to form (however, if a solvent is used, it should not exceed 30% by weight based on the raw material containing the solvent).
If it is less than 15% by weight, the yield of the resin will be low and a resin with a high softening point and glass transition point will not be obtained, and therefore the tackifying effect (holding power in %) of the resin will not be sufficient, which is not preferable.

A petroleum resin, which is a raw material for hydrogenated 05 petroleum resin, can be obtained by polymerizing the above raw materials at a polymerization temperature of 50 to 140° C. in the presence of a Friedel-Krauch type catalyst. ! F! As a lVC catalyst, it consists of a fatty acid ester and an aluminum halide, with G per mole of pseudo).
3) Using a catalyst having a composition of 1.5 to 6.0 moles, the amount of catalyst is 0.0% of aluminum halide relative to the raw material.
By polymerizing using 5 to 1.5% by weight at a temperature of 70 to 140°C, a resin with a sharp molecular weight distribution and high cyclized dust in the diene polymer portion can be obtained, and when it is hydrogenated, the softening point and glass This is preferable because it yields a hydrogenated 05 petroleum resin that has a high transition point, a sharp molecular weight distribution, and a high tackifying effect.

Since polymerization is usually an exothermic reaction, it is generally carried out in the presence of a solvent for the purpose of controlling the reaction or preventing the formation of gel. However, when the 5-C5 fraction is used, the reaction can be sufficiently controlled without adding a new solvent, and no gel is formed, so that the polymerization can be carried out without a solvent.

As a solvent during polymerization, aliphatic hydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons, halogenated hydrocarbons, etc. can be used alone or in combination, and aromatic hydrocarbons are preferably used.

The hydrogenated C5 petroleum resin can be obtained by hydrogenating the petroleum resin produced under the above conditions, and the hydrogenation reaction may be carried out according to a conventional method. For example, by dissolving petroleum resin in a hydrocarbon solvent such as hegysan, heptane, octane, cyclohexane, benzene, toluene, xylene, etc., or by melting the resin as it is, nickel, palladium, platinum, cobalt, etc.
Hydrogenation may be carried out in the presence of a metal or oxide catalyst such as ruthenium or rhodium at room temperature to 350° C. and at a hydrogen pressure of normal pressure to 350 kg/d.

The resin thus obtained is almost completely hydrogenated, with 50 to 80% by weight of units in which C5 diolefins are added to water in the main chain, and 50 to 80% by weight units in which C5 olefins are hydrogenated. It contains 20% by weight, has a number average molecular weight of 700 to 1500, a softening point of 70°C to 130°C, a glass transition point of 55°C to 100°C, and a hue of 1 or less.

If the number average molecular weight is 700 or less, the softening point is 70°C or less, and the glass transition point is 55°C or less, the holding power at high temperatures will decrease, which is undesirable.2On the contrary, if the average molecular weight is 1
500 or more, a softening point of 130° C. or more, and a glass transition point of 100° C. or more are undesirable because the initial adhesive strength (at a particularly low temperature) decreases.

Here, the number average molecular weight is G
The values were measured by PC, the glass transition point by the TBA method, the softening point by JIS K 2531-60 (ring and ball method), and the hue by ASTM D-154-581C. Further, when the hydrogenated 05 petroleum resin obtained by the above method was mixed with 100 parts by weight of Kraton's G1657 saturated thermoplastic block copolymer Enstomer and 80 parts by weight, the rolling ball tack was 4 to 15.
, and holding power (weight 1kg, temperature 75℃, humidity 50℃)
%) to provide a hot melt adhesive composition having physical properties of 0 to 0.6 dew.

Here, the ball tack number (initial adhesive strength) is JI
The holding force was determined according to the S Z-0237-1980 method and the JIS Z-0237-1980 method. However, the load was 1 kII, the temperature was 75° C., and the humidity was 50%.

An additional feature of the hydrogenated C5 petroleum resin of the present invention is that it has a high proportion of cyclized structures in the resin, which means that the diene/monoolefin ratio in the C5 fraction, which is the polymerization feedstock, is Despite the fact that the polymer has a large number of diene units, the glass transition point (Tg) of the hydrogenated C5 petroleum resin obtained by hydrogenation treatment is not significantly different from that of the resin before hydrogenation, i.e. 10 Below ℃, it is indicated by. The fact that Tg changes little due to hydrogenation despite K having a large number of diene units means that the proportion of double bonds in the polymer before hydrogenation is small, and this means that a significant portion of diene units are This is one evidence that it is cyclized. Another feature is that the molecular weight distribution is sharp, and Mw/Mn is in the range of 1.3 to 2.0. Furthermore, the adhesive strength (JIS Z-0237-198
0) is as high as 450-7001725m. Another feature is that the difference between the softening point and Tg is large, that is, 25 to 40°C.

The hydrogenated C5 petroleum resin of the present invention further comprises 35% of the petroleum resin.
It is characterized by ~72% by weight having a cyclized structure, which is approximately 70~90% of the hydrogenated diene unit.
% by weight indicates cyclization.

The hot-melt adhesive composition of the present invention is obtained by using the hydrogenated resin obtained by the above method as a tackifier and adding a thermoplastic block copolymer elastomer thereto. An antioxidant may also be added.

As a saturated thermoplastic block copolymer elastomer,
Preferably, polystyrene-polybutadiene-polystyrene, polystyrene-polyisoprene-polystyrene in which the polybutadiene or polyisoprene block is hydrogenated is used. Saturated thermoplastic block copolymer elastomers have excellent heat resistance, weather resistance, and color.

The number average molecular weight of this saturated thermoplastic block copolymer elastomer is from 20.000 to 500.000, preferably from 50.000 to 200.000.

The elastomer used in the adhesive composition is generally an elastomer with a high molecular weight and a low glass transition point, which is highly effective in imparting mechanical strength to the adhesive layer and increasing the retention force of the adhesive layer. It's helpful. On the other hand, as a tackifying agent, a relatively low molecular weight resin is generally used, and this is thought to fill the gaps between the macromolecular elastomers and improve compatibility with the material to be bonded. Therefore, since the elastomer has a high molecular weight side, the tackifier does not need to contain too many high molecular weight components, and containing too many low molecular weight components will weaken the adhesive strength, so the tackifier should have a molecular weight within an appropriate range. It is desirable to have a narrow molecular weight distribution.

If the adhesive composition obtained by blending hydrogenated 05 petroleum resin and saturated thermoplastic block copolymer elastomer is too hard or feels dry, a softener may be added as desired. I can do it.

As the softener, liquid resins such as polybutene and polybutadiene, or nandene-based and paraffin-based process oils can be used, but polybutene and purified process oils are preferred from the viewpoint of heat resistance and weather resistance.

The blending ratio of the hot melt adhesive is not particularly strictly regulated and can be used in any ratio, but from the viewpoint of performance and processing, it is preferably 50 to 150 parts by weight of the hydrogenated resin to 100 parts by weight of the thermoplastic elastomer. It is preferable to select 70 to 120 parts by weight of the softener, and 0 to 80 parts by weight, preferably 10 to 50 parts by weight of the softener.

The hot-melt adhesive composition obtained as described above has an excellent balance of tack, adhesive strength, and holding power in a wide operating temperature range from low to high temperatures, and has excellent heat resistance, weather resistance, and transparency. It is also excellent.

(Example) Examples will be shown below to further clarify the content of the present invention, but the present invention is not limited by these examples.

Reference Example 1 (Method for producing raw petroleum resin) 3.01 (23.1 mmol) of aluminum chloride and 0.991 (13.4 mmol) of methyl acetate were heated and mixed in advance to form a catalyst. This catalyst is mixed with a stirrer,
After loading a glass autoclave equipped with a thermometer and a monomer addition funnel, it was heated with 30 ml of benzene.
Diluted in ml. While maintaining this autoclave at 90°C, the boiling points of -10 to 1% of the thermal decomposition products of petroleum fractions were
Distillate 300 having the composition shown in Table 1 obtained from the fraction at 00°C
ml was added dropwise from the dropping funnel over about 30 minutes. After the dropwise addition was completed, the reaction was carried out with stirring at 90° C. for 1 hour, and then the catalyst was decomposed with an aqueous alkali solution and further washed with water repeatedly to remove the catalyst. Next K.

The polymerization liquid was taken out, unreacted raw material oil and benzene as a solvent were distilled off under normal pressure, and low polymers were further distilled off under reduced pressure. The petroleum resin obtained had a volume of 58 Jl and contained no gel content. In addition, the diolefin component ratio in the resin is 61.5
wt%, and its physical properties are as shown in Table 2.

Table 1 Composition of raw materials The total amount of monoolefins in the raw materials is 23.1% by weight, the total amount of dienes is 23.7% by weight, and the diene/monoolefin weight ratio is about 1.

Table 2 Physical Properties of Petroleum Resin Reference Example 2 (Production method of raw petroleum resin) A catalyst was prepared by heating and mixing 3.31 # (25.4 mmol) of aluminum chloride and 1.09 # (14.7 mmol) of methyl acetate in advance. This catalyst is mixed with a stirrer,
After placing it in a glass autoclave equipped with a thermometer and a monomer addition funnel, it was mixed with 30% of benzene.
Diluted in ml. While maintaining this autoclave at 80°C, the boiling points of -10 to 1 of the thermal decomposition products of petroleum fractions were
Distillate 300 having the composition shown in Table 3 obtained from the fraction at 00°C
rnl' (CI-) over about 30 minutes. After the dropwise addition was completed, the reaction was carried out with stirring at 90° C. for 1 hour, and then the catalyst was decomposed with an alkaline aqueous solution and further washed with water repeatedly to remove the catalyst. Next, the polymerization liquid was taken out, and the unreacted raw material oil and the solvent benzene were distilled off at normal pressure.
Further, under reduced pressure, the low-polymerization product was distilled off. The obtained petroleum resin had a rating of 55.9 and contained no gel content. In addition, the diolefin component ratio in the resin is 67.0w
t%, and its physical properties are as shown in Table 4.

Table 3 Composition of the raw material The total monoolefin in the raw material is 21.4% by weight, the total diene is 21.6% by weight, and the diene/monoolefin weight ratio is about 1.

Table 4 Physical Properties of Petroleum Resin Example 1 (Hydrogenation of Petroleum Resin) In a stainless steel autoclave 11, 250I of the same resin obtained in Reference Example 1 and 250 ml of cyclohexane were added.
and Nickel catalyst (50%) 10
After adding I, the inside was replaced with hydrogen and the hydrogen pressure was 9/c to 60.
d. Hydrogenation was carried out at a temperature of 200°C for 6 hours. After the reaction was completed, the contents were taken out and the catalyst was removed by filtration, and then cyclohexane was distilled off first at normal pressure and then under reduced pressure to obtain about 2451 resins added with a water source. When this resin was analyzed by infrared absorption spectrum and NMR spectrum, it was found that 2
No absorption based on heavy bonds was observed. The physical properties of this resin are shown in Table 5.

Table 5 Physical Properties of Hydrogenated Resin Example 2 (Hydrogenation of Petroleum Resin) In a stainless steel autoclave of 11, the same resin 2509 obtained in Reference Example 2 and 250 ml of cyclohexane were added.
and nickel-fink soil catalyst with nickel 50%) 10
After adding I, the inside was replaced with hydrogen, and the hydrogen pressure was 60 kg/c.
i! , hydrogenation was carried out at a temperature of 200° C. for 6 hours. After the reaction was completed, the contents were taken out, the catalyst was removed by filtration, and cyclohexane was distilled off first at normal pressure and then under reduced pressure to obtain hydrogenated resin approximately 2451i. When this resin was analyzed by infrared absorption spectrum and NMR spectrum, no absorption based on double bonds was observed. The physical properties of this resin are shown in Table 6.

Table 6 Physical properties of hydrogenated resin Example 3 Saturated thermoplastic block copolymer “Krayton G165
Using 100 parts of 7J, 60 parts of the resin obtained in Example 2 and 220 parts of toluene as a solvent were uniformly mixed to prepare an adhesive.

This adhesive is applied to a 25μ thick polyester film.
After applying m cloth, dry it to form an adhesive film Km with a thickness of 50 μm.
Manufactured.

14. Adhesive strength was 1551/25 mm, and holding power was 0.3 U.

Initial adhesive strength, adhesive strength and holding strength are JIS Z023
7-1980. Note that the holding force is determined by measuring the distance that the adhesive tape shifts over a period of 2 hours under the conditions of a load of 1 kg, a temperature of 75°C, and a humidity of 50%, and the initial adhesive strength is the result of measurement at 23°C.

“Example 4 Saturated thermoplastic block copolymer [Fure45F00165
A pressure-sensitive adhesive was prepared by uniformly mixing 100 parts of the resin obtained in Example 2 and 220 parts of toluene as a solvent with 4100 parts of the adhesive.

Apply this adhesive onto a 25μ thick polyester film.
cI! ! After 1 cloth, it was dried to prepare an adhesive film with a thickness of 50 μm.

The obtained adhesive had an initial adhesive strength (ball shop) of 5, an adhesive strength of 745 J'/25 m, and a holding power of 0.6.

Examples 5 to 6 and Comparative Examples 1 to 2 Example 1 to 100 parts of Kraton G1657
and 80 parts each of the resin obtained in Example 2 and a commercially available hydrogenated cyclopentadiene resin and hydrogenated aromatic petroleum resin as a comparative example, and 2 toluene as a solvent.
An adhesive film was prepared in the same manner as in Example 3 using 20 parts.

Table 7 shows the test results of the obtained adhesive.

Examples 7 to 8 and Comparative Examples 3 to 4 Example 1 to 100 parts of Kraton G1657
and the resin obtained in Example 2, and as a comparative example, 100 parts each of the commercially available hydrogenated cyclopentadiene resin used in Comparative Example 1 and the commercially available hydrogenated aromatic petroleum resin used in Comparative Example 2, and as a softening agent. An adhesive film was prepared in the same manner as in Example 3 using 25 parts of polybutene and 220 parts of toluene as a solvent.

Table 8 shows the test results of the obtained adhesive.

As can be seen from this experimental result, the hydrogenated C5 petroleum resin of the present invention has an excellent balance of initial adhesion, adhesion, and holding power compared to commercially available hydrogenated petroleum resins. It is clear that the holding power is high.

(Effects of the Invention) The novel hydrogenated 05 petroleum resin of the present invention can be blended with a saturated thermoplastic block copolymer elastomer and further added with a softener if necessary, so that it can be used as a conventional natural product. To provide a hot melt adhesive composition of quality that can be substituted for certain terpene resins, rosin resins, etc.

Claims (5)

[Claims] (1) Main chain contains 50-80% by weight of units hydrogenated with C_5 diolefin, 50-20% by weight of units hydrogenated with C_5 olefin, number average molecular weight 700-15
00, has a softening point of 70 to 130°C, a glass transition point of 55 to 100°C, and a hue of 1 or less, and 80 parts by weight for 100 parts by weight of Kraton (R) G1657 saturated thermoplastic block copolymer elastomer.
Initial adhesive strength (rolling ball tack) when mixed by weight part: 4 to 1
5 and holding force (load 1 kg, temperature 75°C) is 0 to 0.
Hydrogenated C_5 petroleum resin that is 6 mm. (2) (A) 100 parts by weight of saturated thermoplastic block copolymer elastomer, (B) 50 to 80% by weight of units with hydrogenated C_5 diolefin in the main chain, 50 to 20 parts by weight of units with hydrogenated C_5 olefin %, has a number average molecular weight of 700 to 1500, a softening point of 70 to 130°C, a glass transition point of 55 to 100°C, a hue of 1 or less, and 100 parts by weight of Kraton (R) G1657 saturated thermoplastic block copolymer elastomer However, when 80 parts by weight was mixed, the initial adhesive strength (rolling ball tack) was 4 to 15 and the holding power (
A hot melt adhesive composition comprising 50 to 150 parts by weight of a hydrogenated C_5 petroleum resin having a load of 1 kg and a temperature of 75°C of 0 to 0.6 mm, and (C) 0 to 80 parts by weight of a softener. (3) The hot melt adhesive composition according to claim 2, wherein the saturated thermoplastic block copolymer elastomer is a block copolymer of styrene and hydrogenated polydiene. (4) The hot melt adhesive composition according to claim 2 or 3, wherein the hydrogenated petroleum resin is 50 to 120 parts by weight based on 100 parts by weight of the saturated thermoplastic block copolymer elastomer. . (5) The hot melt adhesive according to any one of claims 2 to 4, wherein the softener is present in an amount of 10 to 50 parts by weight based on 100 parts by weight of the saturated thermoplastic block copolymer elastomer. Composition.