JPH0554862B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to an adhesive composition, and more particularly, to an adhesive composition that is applied to a sheet material such as cardboard or a plastic sheet to trap harmful animals such as cockroaches and rats. More specifically, the present invention relates to an adhesive composition for trapping harmful animals that has excellent adhesiveness and retention, has high instant adhesive strength even after being applied at high temperatures, and has excellent stability. [Prior art and its problems] Conventionally, adhesive compositions for trapping harmful animals such as cockroaches and rats have been made using compositions made of polybutene and atactic polypropylene (for example, Japanese Patent Application Laid-Open No. 183701/1983). and Japanese Patent Publication No. 59-80601), and a composition comprising relatively low molecular weight polybutene and a natural resin with a softening point of 70 to 100°C (Japanese Patent Publication No. 55-30761). However, these adhesive compositions are
When applied to a sheet-like material such as a plastic sheet, it has the disadvantage that the tack decreases after being heated to a high temperature and applied, so it cannot be said to be necessarily satisfactory. Here, tack is the bonding strength that occurs at the same time as the adhesive is attached to the other party; in other words, it refers to wettability and instantaneous adhesive strength. On the other hand, JP-A-52-128225 discloses an adhesive composition in which polybutene is blended with a resin. However, this adhesive composition has poor adhesion and retention properties, and moreover, it flows under high temperatures and exhibits sagging, making it difficult to reliably capture harmful animals such as rats. It was sticky, so it was hard to say that it was satisfactory. [Object of the Invention] This invention has been made based on the above circumstances. That is, an object of the present invention is to eliminate the above-mentioned drawbacks, to have excellent adhesiveness and retention, not to show fluidity at high temperatures, and to remain tack even after being heated to high temperatures and applied. It is an object of the present invention to provide an adhesive composition having an excellent ability to capture harmful animals without deterioration. [Means for Solving the Problems] In order to solve the problems described above, the present inventor conducted intensive research and found that high molecular weight polybutenes, especially polybutenes with a number average molecular weight of 10,000 to 300,000, and low molecular weight polybutenes, especially polybutenes with a number average molecular weight of 10,000 to 300,000. The inventors have discovered that the above-mentioned problems can be solved by blending polybutene with an average molecular weight of 300 to 3000, polypropylene, especially atactic polypropylene, a specific hydrogenated resin, and an antioxidant in a specific ratio, and have thus arrived at this invention. .
That is, the outline of this invention is that high molecular weight polybutene, low molecular weight polybutene, polypropylene, at least one hydrogenated resin selected from the group consisting of hydrogenated petroleum resin and hydrogenated terpene resin, and an antioxidant. , the amount of the high molecular weight polybutene is 1 to 30 parts by weight, the amount of the low molecular weight polybutene is 20 to 95 parts by weight, the amount of the polypropylene is 1 to 40 parts by weight, and the amount of the hydrogenated resin is 1 to 30 parts by weight. This is an adhesive composition characterized in that the blending amount is 0.1 to 40 parts by weight. In this invention, high molecular weight polybutene usually refers to polybutene with a number average molecular weight of 10,000 or more, and low molecular weight polybutene usually refers to polybutene with a number average molecular weight of less than 10,000. However, the number average molecular weight of the preferable high molecular weight polybutene is 10,000 to 300,000, and the number average molecular weight of the preferable low molecular weight polybutene is 300 to 3,000.
It is. If the number average molecular weight of high molecular weight polybutene is less than 10,000, the adhesive will not exhibit good holding power, and if the number average molecular weight is greater than 300,000, the temperature and time during compounding will increase significantly, making it difficult to process. may become worse. Also, if the number average molecular weight of the low molecular weight polybutene is less than 300,
Sagging development will occur at high temperatures, and if the number average molecular weight exceeds 3000, the overall viscosity will increase and good adhesive strength may not be exhibited. Here, the polybutene refers to homopolymers and copolymers of 1-butene, cis-2-butene, trans-2-butene, and isobutene, and
It also includes a polymer mixture produced by polymerizing a mixture of the above monomers. Although a blend of two or more homopolymers obtained by polymerizing each of the above-mentioned various monomers may be used as the polybutene, in this invention, a polymer obtained by polymerizing a mixture of each of the above-mentioned monomers is used. Preference is given to using mixtures. In this case, as the mixture of the various monomers, for example, the residue obtained by extracting butadiene from the C4 fraction during the thermal decomposition of naphtha can be suitably used. The polymer mixing is carried out using aluminum chloride as a catalyst, for example, at a reaction temperature of 5 to 50%.
It can be obtained by polymerizing a mixture of the above monomers at 130° C. and a pressure of 1 to 22 kg/cm ² G. The molecular weight of the resulting polymer mixture can be determined by adjusting the reaction time and reaction temperature. In this invention, the polypropylene is
Polypropylene produced in conventional manner can be used. Among them, atactic polypropylene (hereinafter sometimes abbreviated as "APP")
is preferred. APP refers to amorphous polypropylene with an atactic molecular arrangement. Approximately a few percent of such APP is produced as a by-product during the manufacturing process of polypropylene, which has a high degree of crystallinity and has an isotactic molecular arrangement. APP may vary due to differences in the type of polypropylene it is made from, such as propylene homopolymers, or random or block copolymers of propylene and monomers such as ethylene, and differences in manufacturing processes, especially the type of solvent and separation of APP. It is known that there are various types, ranging from low molecular weight to very high molecular weight, depending on the temperature and other factors, and there are also quite different physical properties. In this invention, a viscosity of 1000 to 7000 centipoise is preferred. Note that this viscosity is a value measured at 170°C using a B-type viscometer. In this invention, at least one hydrogenated resin selected from the group consisting of hydrogenated petroleum resins and hydrogenated terpene resins is used. As the hydrogenated petroleum resin, those obtained by hydrogenating petroleum resins produced by conventional methods can be used. The petroleum resin is obtained by copolymerizing resin-like substances obtained in various processes in the petroleum refining industry and petrochemical industry, and unsaturated hydrocarbons obtained in those processes, especially in the naphtha cracking process. For example, there are aliphatic petroleum resins whose main raw material is C5 fraction and aromatic petroleum resins whose main raw material is C9 fraction. It is also classified as a ring-based petroleum resin. Here, for example, the following (all trade names) are known as petroleum resins manufactured in Japan and overseas. That is, as aliphatic petroleum resins, Hiretsu (Mitsui Petrochemical), Quinton (Nippon Zeon),
Tatsuki Roll (Sumitomo Chemical), Escorez1000 series (Exxon Chem), Piccopale (Hercules),
Wingtack (Goodyear), Sta-tac (Reichhold),
East Rez (Eastman), Imprez (ICI), CRJ−683
(Schenectady), etc., and aromatic petroleum resins include Petrozine (Mitsui Petrochemical), Neopolymer (Japan Synthetic Resin), Petcol (Toyo Soda),
Hi-Resin (Toho Petrochemical), Nevex (Neville),
Piccovar (Hercules), etc. Copolymer petroleum resins such as Hi-Resin (Toho Petrochemical), Tatsuku Ace (Mitsui Petrochemical), Clearvel (Dainippon Ink), Kryrvel (VelsicolChem), Piccotex
(Hercules), Supper Statac (Reichhold), etc. The hydrogenated petroleum resin refers to, for example, one obtained by hydrogenating the petroleum resin described above. However, regarding the above-mentioned ring group petroleum resins, there are those that have already been hydrogenated, such as Alcon (Arakawa Chemical), and in the present invention, these are also referred to as hydrogenated alicyclic petroleum resins. ing. Among these many hydrogenated petroleum resins, hydrogenated alicyclic petroleum resins, especially hydrogenated cyclopentadiene and/or copolymers of dicyclopentadiene and styrene, copolymers of dicyclopentadiene and maleic anhydride, etc. Hydrogenated combinations are preferred. In addition, hydrogenated resins suitable for this invention include:
Examples include hydrogenated alicyclic petroleum resins and hydrogenated terpene resins. The degree of hydrogenation of the hydrogenated resin varies depending on the type of resin and the proportion of the compound, but it is not necessary that all unsaturated bonds (including aromatic rings) be completely hydrogenated. Generally, if the hydrogenation rate is 100% for a completely hydrogenated product, it is sufficient if at least 30% or more is hydrogenated, preferably a hydrogenation rate of 50% or more, Particularly preferred is 70% or more. This means that mixtures of hydrogenated resins and non-hydrogenated resins may also be used, as long as the actual hydrogenation rate corresponds to the above range. If the actual hydrogenation rate is less than 20%, the tack may decrease after the pressure-sensitive adhesive composition is heated to a high temperature and applied to a sheet material. The blending ratio of each component in the adhesive composition is 1 to 30 parts by weight of the high molecular weight polybutene, preferably 5 to 20 parts by weight, and 20 to 95 parts by weight, preferably 60 to 90 parts by weight of the low molecular weight polybutene. , the polypropylene is 1 to 40 parts by weight, preferably 10 to 40 parts by weight.
30 parts by weight, and 0.1 to 40 parts by weight, preferably 0.5 to 35 parts by weight of the hydrogenated resin. here,
If the amount of the high molecular weight polybutene is less than 1 part by weight, even if the amount of other components is within the above range, the retention of the adhesive composition will decrease,
If the amount exceeds parts by weight, the tackiness may decrease even if the amounts of other components are within the above ranges. In addition, if the amount of low molecular weight polybutene is less than 5 parts by weight, the tackiness of the adhesive composition will decrease even if the amounts of other components are within the above range, and if it exceeds 95 parts by weight, the adhesive composition will decrease. However, even if the amounts of other components are within the above ranges, retention may be reduced. If the content of the polypropylene is less than 1 part by weight, the shape retention of the pressure-sensitive adhesive composition at high temperatures may decrease even if the content of other components is within the above range. If the amount exceeds 50%, even if the amounts of other components are within the above range, the adhesive composition may become too hard, resulting in a decrease in tack in winter and a decrease in trapping ability. Furthermore, if the amount of the hydrogenated resin is less than 0.1 part by weight, even if the amount of other components is within the above range, the pressure-sensitive adhesive composition may be heated to a high temperature and a sheet-like product may be formed. On the other hand, if the amount exceeds 40 parts by weight, even if the amount of other ingredients is within the above range, the tackiness and retention of the adhesive composition may deteriorate. It may decrease. The adhesive composition of the present invention contains an antioxidant in addition to the above-mentioned components. As the antioxidant, common antioxidants used in synthetic resins, rubbers, adhesives, etc. can be used. For example, phenolic oxidation such as tetrakis-[methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)]methane, 2,6-di-tert-butyl-p-cresol, etc. Inhibitors can be suitably used. By using these antioxidants, high temperatures, e.g.
It is possible to suppress thermal decomposition or deterioration of polybutene or atactic polypropylene when heated to 180°C, and further prevent the adhesive strength from decreasing after heating. Furthermore, in the present invention, various inorganic fillers such as zinc oxide, titanium dioxide, calcium carbonate, silica, and carbon black may be blended into the adhesive composition as needed. When using the adhesive composition of the present invention for capturing harmful animals, it is recommended to incorporate an appropriate sex attractant into the adhesive composition to trap harmful animals quickly, efficiently, and selectively. can be captured. The pressure-sensitive adhesive according to the present invention is prepared by combining the high molecular weight polybutene, low molecular weight polybutene, atactic polypropylene, and hydrogenated resin at a temperature of, for example, 100 to 180°C.
It can be obtained by mixing or kneading for 2 to 5 hours at a heating temperature of . There are no particular restrictions on this mixing or kneading method. Furthermore, there are no particular limitations on the method or order of mixing the antioxidant, inorganic filler, and/or attractant. The pressure-sensitive adhesive composition of the present invention typically includes, for example,
It can be applied to cardboard, cardboard, plastic sheets, cloth, wooden boards, metal plates, etc. Note that the adhesive composition of the present invention can adhere not only to rats but also to other animals, such as insects such as flies and cockroaches, and can effectively capture them. [Effects of the Invention] According to the present invention, high molecular weight polybutene, low molecular weight polybutene, polypropylene, and hydrogenated resin are blended in a specific ratio, so it has excellent retention and adhesive properties, and can be used even at high temperatures. Does not exhibit fluidity and does not cause the so-called sagging phenomenon, and
Tack does not decrease after application under high temperature, and
It is possible to provide an excellent pressure-sensitive adhesive composition that is resistant to oxidative deterioration and retains its adhesive properties even when heated to high temperatures. When this adhesive composition is used for capturing harmful animals, it can adhere to harmful animals such as flies, cockroaches, and rats, and effectively capture them. [Examples] Next, the present invention will be explained in more detail by showing examples and comparative examples of the present invention. Examples 1 to 3 High molecular weight polybutene and low molecular weight polybutene having the number average molecular weights shown in Table 1 were kneaded at 120°C for 3 hours in the blending amounts shown in Table 1, and then kneaded with the number average molecular weights shown in Table 1. Atatsukikuti polypropylene, hydrogenated resin and antioxidant were added in the amounts shown in Table 1 and kneaded at 170°C for 3 hours to obtain an adhesive composition. This adhesive composition was evaluated for tack, adhesion, retention and fluidity. Evaluation results first
Shown in the table. Note that the high molecular weight polybutene and the low molecular weight polybutene were manufactured as follows. That is, 5 g of aluminum chloride was placed in a 500 ml autoclave, the pressure inside the autoclave was reduced using a vacuum pump, and then 50 g of n-butane was added as a solvent, and the aluminum chloride was dispersed in the solvent by stirring. Then 42% isobutene,
A mixture consisting of 2.18% 1-butene and 40% n-butane (the residue obtained by extracting butadiene from the C4 fraction during the thermal decomposition of naphtha) was heated at a heating temperature of 5 to 80°C for 20 minutes.
Add for 0.5 min, and after the addition is complete, heat at 10°C for 0.5 min.
The reaction was carried out for ~2 hours (the number average molecular weight of the polybutene used in Examples 1 to 3 was adjusted by adjusting the heating temperature and reaction time). After the reaction is complete, remove unreacted gas and n-butane, and add 300 ml of water.
The reaction product was extracted with 500 ml of n-hexane in three portions, and the n-hexane was removed from the extract to obtain polybutene. Comparative Examples 1 to 4 Adhesive compositions having the formulations shown in Table 1 were obtained in the same manner as in the above Examples, and evaluated for tack, adhesion, retention and fluidity. The evaluation results are shown in Table 1.

【table】

【table】

Claims (1)

[Claims] 1. High molecular weight polybutene, low molecular weight polybutene, polypropylene, at least one hydrogenated resin selected from the group consisting of hydrogenated petroleum resin and hydrogenated terpene resin, and an antioxidant. and the blending amount of the high molecular weight polybutene is 1 to 30
Parts by weight, the blending amount of the low molecular weight polybutene is 20~
95 parts by weight, the blending amount of the polypropylene is 1 to 40
parts by weight, and the amount of the hydrogenated resin is from 0.1 to
40 parts by weight of an adhesive composition. 2. The pressure-sensitive adhesive composition according to claim 1, wherein the polypropylene is atactic polypropylene. 3. The hydrogenated petroleum resin is at least one type selected from the group consisting of hydrogenated cycloaliphatic petroleum resins, hydrogenated aromatic petroleum resins, hydrogenated copolymerized petroleum resins, and hydrogenated resin group petroleum resins. The pressure-sensitive adhesive composition according to any one of claims 1 and 2, which is the hydrogenated petroleum resin described above. 4. The hydrogenated alicyclic petroleum resin is one obtained by hydrogenating a copolymer of cyclopentadiene and/or dicyclopentadiene, one obtained by hydrogenating a copolymer of dicyclopentadiene and styrene, or one obtained by hydrogenating a copolymer of dicyclopentadiene and styrene. The pressure-sensitive adhesive composition according to claim 3, which is a hydrogenated copolymer of maleic anhydride. 5. The adhesive composition according to claim 1, wherein the hydrogenated terpene resin is a hydrogenated polyditerpene.