JPH0249086A - Tacky agent composition - Google Patents

Abstract

PURPOSE:To obtain the subject resin composition capable of exhibiting excellent tacky force even by a small amount of a tackifier by blending a specific alpha- olefinic polymer with a coumarone resin and petroleum-based hydrocarbon resin in specified amounts. CONSTITUTION:The objective composition obtained by blending (A) 100 pts.wt. polymer consisting of a 6-20C alpha-olefin (mixture) having 10000-500000 (preferably 20000-300000) average molecular weight expressed in terms of polystyrene and a value of (Mw/Mn) within the range of 5-15 with (B) 1-30 pts.wt. (preferably 3-20 pts.wt.) coumarone resin and/or petroleum-based hydrocarbon resin as a tackifier. Although the component (A) is obtained by using a Ziegler-Natta type catalyst, above all, a combination of a highly active supported titanium catalyst with an organoaluminum compound is preferred.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a pressure-sensitive adhesive composition, and more particularly to a pressure-sensitive adhesive composition used for pressure-sensitive adhesive tapes and pressure-sensitive adhesive sheets (labels).

[Prior Art] Conventionally, there are several types of adhesives, and they are classified as follows depending on the composition of the adhesive.

(1) Rubber adhesive (2) Acrylic adhesive (3) Vinyl ether adhesive (4) Silicone adhesive Rubber adhesive uses rubber as an elastomer base and adds some low-molecular substance to it. This is an adhesive obtained by adjusting the viscoelasticity of the system.

Base elastomers include natural rubber (NR), polyisoprene (IR), and styrene-butadiene rubber (SBR).
, butyl rubber (IIR), etc. are used. These rubber pressure-sensitive adhesives usually contain at least 50 to 60 parts by weight of various tackifiers.

[Problems to be Solved by the Invention] The present invention exhibits superior adhesive strength compared to conventional rubber-based adhesives even when the amount of tackifier such as coumaron resin or petroleum-based hydrocarbon resin is small. and N as a base polymer.
The present invention provides a rubber adhesive using a specific α-olefin rubber without using R%SBR or IIR.

[Means for Solving the Problems] As a result of intensive research into the above problems, the present inventors have found that
a) Polystyrene equivalent number average molecular weight is 10.000 to 5
00,000 and a MwZMn value in the range of 5 to 15, 100 parts by weight of a polymer consisting of one or more α-olefins selected from α-olefins having 6 to 20 carbon atoms, and b) Coumaron resin. It has been discovered that a composition containing 1 to 30 parts by weight of a petroleum-based hydrocarbon resin and/or a petroleum-based hydrocarbon resin exhibits excellent adhesive strength, and the present invention has been achieved based on these findings.

The present invention will be explained in detail below.

Examples of the polymer composed of one or more α-olefins selected from α-olefins having 6 to 20 carbon atoms used in the present invention include polyhexene-1, polyhebutene-1,
polyoctene-1, polynonene-1, polydecene-1,
Polyundecene-1, polydodecene-1, hexene-1
/octene-1 copolymer, hexene-1/decene-1 copolymer, hexene-1/dodecene-1 copolymer, hexene-1/tetradecene-1 copolymer, hexene-1/hexadecene-1 copolymer coalescence, hexene-1/4-methylpentene-1 copolymer, octene-1/decene-1 copolymer, octene-1/dodecene-1 copolymer, octene-1
1/tetradecene-1 copolymer, decene-1/dodecene-1 copolymer, decene-1/tetradecene-1 copolymer, hexene-1/octene-1/decene-1 copolymer,
Examples include octene-1/decene-1/dodecene-1 copolymer. Furthermore, a copolymer obtained by copolymerizing a conjugated or non-conjugated diene component can also be used. The preferable molecular weight of these polymers is a polystyrene equivalent number average molecular weight of 10,000 to 500,000, particularly 20,000 to 300, from the balance of cohesive force and adhesive force of a composition using the polymer. 000 is preferred.

In the present invention, the number average molecular weight in terms of polystyrene is 1
If it is less than 0,000, the cohesive force of the composition will be poor, and 5
If it exceeds 00.000, the adhesive force becomes low, which is not preferable. In addition, the ratio of the polymerization average molecular weight iMW to the number average molecular weight Mn (
If the molecular weight distribution index) is less than 5, the adhesive strength will be poor;
If it exceeds 5, the cohesive force decreases, which is not preferable.

These polymers can be obtained using a known Ziegler-Natta type catalyst, and a combination of a highly active supported titanium catalyst and an organoaluminum compound is particularly preferred.

Tackifiers used in the present invention include coumaron resins such as coumaron indene resins, petroleum hydrocarbons such as aliphatic hydrocarbon resins, aliphatic cyclic hydrocarbon resins, and aromatic hydrocarbon resins. Resin is used. More specifically, commercially available tackifiers, such as product names such as Kumaron RG (manufactured by Nippon Steel Corporation), Kumaron CL (manufactured by Iriuchi Shinko Co., Ltd.), Finton A-100 (manufactured by Nippon Zeon Co., Ltd.),
Examples include Escolets 1102B (manufactured by Esso Chemical Co., Ltd.) and Alcon P-90 (manufactured by Arayo Kagaku Co., Ltd.).

The ratio of the polymer of the composition of the present invention to the coumaron resin and/or petroleum hydrocarbon resin as a tackifier is 1 to 30 parts by weight of the coumaron resin and/or petroleum hydrocarbon resin to 100 parts by weight of the polymer. parts, preferably 3 to 20
Parts by weight. If the amount of the coumaron resin and/or petroleum hydrocarbon resin is less than 1 part by weight, the adhesiveness will be poor, which is not preferable, and if it exceeds 30 parts by weight, the cohesive force will be reduced, which is not preferable.

When using the composition of the present invention as a pressure-sensitive adhesive, additives such as a softener, anti-aging agent, reinforcing agent, filler, and the like may be added as necessary within a range that does not reduce adhesive strength.

[Examples] Hereinafter, the present invention will be explained in more detail based on Examples.

In the examples, "parts" and "%" are "parts by weight" and "parts" and "%" are "parts" and "%".
% of polymerization.

In the present invention, the polystyrene equivalent number average molecular weight of the polymer was measured at 135° C. using a gel permeation chromatograph model 150 manufactured by Waters Inc. and using trichlorobenzene as a solvent.

In addition, the composition of each olefin in the polymer is manufactured by JEOL Ltd.
Using NMRJNM-FX100 type carbon 13,
Measured at 120°C using trichlorobenzene as a solvent,
It was determined from the area ratio of the spectrum determined by the Lindeman and Adams calculation formula.

On the other hand, in testing the adhesive strength of the pressure-sensitive adhesive composition of the present invention, the pressure-sensitive adhesive composition was sandwiched between polyester films, heat-pressed at 130°C, left for more than a day and night, and then peeled at a peel angle of 180°C (T peeling). , and the beer strength (kg/cm ) was measured by pulling at a pulling speed of 30 mm/min.

Examples 1 to 4, Comparative Examples 1 to 3 Production of A0 polymer In a 3 g flask that had been purged with nitrogen in advance, 2 g of dehydrated and purified n-hexane 1 dehydrated and purified hexene-1 (Dialene-6, manufactured by Mitsubishi Kasei Corporation, n-hexene-1) 1. Purity 96
% or more), then 9 mmol of triisobutylaluminum, and a supported titanium catalyst (JP-A-63-1999).
223010 (prepared according to Example 1) were sequentially charged and stirred at 30°C for 1 hour. After 1 hour, 5 ml of isopropyl alcohol was added to stop the polymerization reaction. Next, the polymerization reaction solution was poured into methanol to solidify, and then dried with a roll at 100°C. The yield of the polymer is 56g1 The number average molecular weight in terms of polystyrene is 21
0,000, Mw/Mn was 6°4 (Polymer A).

Evaluation of B8 Adhesive Composition Using the polymer obtained in A, the formulation shown in Table 1 was kneaded using a roll machine to obtain an adhesive composition, and the beer strength of the composition was measured. . The results are shown in Table-1.

From the results in Table 1, it can be seen that the compositions containing coumarone resin and/or petroleum hydrocarbon resin within the scope of the present invention exhibit excellent adhesiveness.

Furthermore, it can be seen that the adhesive strength of a composition using polyisoprene as a polymer, which has been conventionally used as an adhesive, is inferior.

Examples 5 to 8 Production of A9 Polymer In Example IA, the monomers shown in Table 3 were used in place of 120 ml of hexene-1, and polymerization was carried out in the same manner as above. The properties of the produced polymer are shown in Table 2.

B. Evaluation of Adhesive Composition Using the polymer listed in Table 2, the beer strength was measured in the same manner as in Example 4B. The results are shown in Table 3.

Both polymers showed excellent adhesive strength.

Examples 9 to 10, Comparative Examples 4 to 5 A0 Polymer Production Example - Examples except that supported titanium catalyst, triisobutylaluminum, and hexene-1 were used in the quantities shown in Table 4 in IA. - Polymerized in the same manner as IA. The yield of this polymer and the polystyrene equivalent number average molecular ffi (Mn
) and the molecular weight distribution (M w /M n ) are shown in Table 4.

Below is a margin B, evaluation of adhesive composition using Escorets 1102B using polymers F, G, H, and I.
A pressure-sensitive adhesive composition was prepared by adding 10 parts to 100 parts of the polymer, and the beer strength was measured in the same manner as in Example IB. The results are shown in Table-5.

From Table 5, it is seen that if the molecular weight is too large or too small, the strength of the beer decreases, which is not preferable. Comparative Example 4 using Polymer H has a small molecular weight and a small Mw/Mn, and has a particularly low beer strength.

[Effects of the Invention] According to the present invention, a pressure-sensitive adhesive composition with excellent adhesiveness can be obtained, which can be applied to a film and used as a pressure-sensitive adhesive tape and a label. - Thermoplastic resins such as styrene block copolymers can be blended to make hot melt adhesives, and dissolved in solvents to be used as solvent-type rubber adhesives.

Table-5 Patent applicant: Japan Synthetic Rubber Co., Ltd.

Claims (1)

[Claims] (1) a) Polystyrene equivalent number average molecular weight is 10,00
0 to 500,000, and M_w/M_n value is 5
100 parts by weight of a polymer consisting of one or more α-olefins selected from α-olefins having 6 to 20 carbon atoms in the range of 15 to 15, and b) 1 part by weight of coumaron resin and/or petroleum hydrocarbon resin.
-30 parts by weight.