JPH10158618A - Pressure-sensitive adhesive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a pressure-sensitive adhesive compsn. excellent in tackiness, adhesive strength, cohesive strength, and durability by compounding an acrylic resin, a rubber-base resin, a reaction accelerator (a chelate compd. and/or an aziridine compd.), and a curative. SOLUTION: This compsn. is prepd. by compounding an acrylic resin (A), a rubber-base resin (B), a chelate compd. (C1) and/or an aziridine compd. (C2) as the reaction accelerator, and pref. 0.1-10 pts.wt. curative (D). Ingredient A is prepf. a copolymer of a (meth)acrylic ester, a vinyl ester of a satd. monocarboxylic acid, and other copolymerizable vinyl monomers having an average mol.wt. of 300-10,000 and a mol.wt. distribution of 1-5. Ingredient B is pref. polybutene or polyisobutylene having an average mol.wt. of 500-5,000. Pref. examples of ingredient C1 are coordination compds. such as acetylacetonates of Al, Fe, and Zn, A pref. example of ingredient C2 is N,N'- hexamethylene-1,6-bis(1-aziridinecarboxamide).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pressure-sensitive adhesive composition having excellent tackiness, adhesiveness, cohesive strength and durability.

[0002]

2. Description of the Related Art Conventionally, as a component of a pressure-sensitive adhesive, an elastic material such as natural rubber or synthetic rubber, or an acrylate-based synthetic resin has been used, but a rubber-based resin is excellent in tackiness and adhesiveness. However, acrylic resins are inferior in cohesive strength and durability, but are inferior in tackiness, adhesiveness and the like. In order to solve these disadvantages, various studies have been made for the purpose of combining the advantages of both, and a pressure-sensitive adhesive obtained by graft-polymerizing a vinyl-based monomer such as an acrylate ester onto a rubber-based resin such as natural rubber or synthetic rubber. And pressure-sensitive adhesives obtained by copolymerizing polybutene with acrylates, vinyl esters and the like (Japanese Patent Publication No. 50-37689).

[0003]

However, in the former technique, the durability was not sufficiently satisfactory, and no good tackiness was obtained. Regarding the latter technology (Japanese Patent Publication No. 50-37689),
As a result of a detailed study by the present inventors, it has been found that the compatibility between polybutene and an acrylic resin is still poor, and phase separation occurs. That is, in the technology disclosed in the above-mentioned publication, when an acrylic monomer or the like is copolymerized in a solution in which polybutene is dissolved in an organic solvent, the resulting solution contains an acrylic oligomer and a large amount of residual monomer, and unreacted polybutene. And polybutene was phase-separated from the solution, and satisfactory satisfactory tackiness, adhesive strength, cohesive strength, etc. could not be obtained.

[0004] Under such circumstances, the present invention solves the above-mentioned problems by tackiness, adhesive strength, cohesive strength,
An object of the present invention is to provide a pressure-sensitive adhesive composition having excellent properties of an adhesive resin such as durability and excellent stability over time and having both characteristics of an acrylic resin and characteristics of a rubber resin.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve such problems, and as a result, they have obtained acrylic resin (A), rubber resin (B) and reaction accelerator (C). It has been found that a pressure-sensitive adhesive composition containing a chelate compound (C-1) and / or an aziridine compound (C-2), preferably further containing a curing agent, meets the above object, The present invention has been completed. In the present invention, it is also preferable to add a tackifier. The pressure-sensitive adhesive composition of the present invention is tacky, adhesive,
It has excellent low-temperature adhesiveness, aging resistance, and storage stability. In particular, it exhibits an effect far superior to that of the rubber resin itself in terms of tackiness, and also has excellent temporal stability in terms of adhesive physical properties.

In the present invention, after mixing any two of acrylic resin (A), rubber resin (B) and reaction accelerator (C), the mixture is mixed with the remaining components and heated.
Or it is preferable to mix with the remaining components while heating,
The effects of the present invention can be remarkably exhibited.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The acrylic resin (A) used in the present invention includes:
It is obtained by appropriately copolymerizing (meth) acrylic acid ester (A-1), vinyl ester of saturated monocarboxylic acid (A-2) and copolymerizable vinyl monomer (A-3) other than the above. I just need. (Meth) acrylic acid ester (A
-1) as methyl acrylate, ethyl acrylate,
Propyl acrylate, butyl acrylate, acrylic acid 2
-Methyl-3-ethyl, 3-methyl-3-ethyl acrylate, 3-methyl-3-propyl acrylate, glycidyl acrylate, hydroxyethyl acrylate,
Trifluoromethyl acrylate, trimethylsilyl acrylate, hydroxyethyl methacrylate, mono (2-methacryloyloxyethyl) phosphoric acid, diethylaminoethyl methacrylate, 2-methacryloyloxyethyl succinic acid, 2-hydroxypropyl methacrylate, methacrylic acid Hydroxypropyltrimethylammonium chloride, glycidyl (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, phenoxypolypropylene glycol (meth) acrylate, polyethylene glycol di (Meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate , Tetramethylolmethane tri (meth) acrylate, and the like. Examples of the vinyl ester of a saturated monocarboxylic acid (A-2) include vinyl acetate, vinyl propionate, vinyl ethoxyacetate, vinyl isobutyrate, vinyl butyrate, vinyl laurate, Examples include vinyl stearate, vinyl cinnamate, vinyl benzoate, vinyl formate, and the like, and copolymerizable vinyl monomers (A-
3) As itaconic acid, maleic anhydride, dibutyl maleate, fumaric acid, dibutyl fumarate, allyl glycidyl ether, vinylpyrrolidone, 1-butene, 1-hexene, 1-octene, 1-decene, acrylamide,
Acrylonitrile, styrene, (meth) acrylic acid and the like can be mentioned. However, it is not limited to these.

The mixing ratio of (A-1), (A-2) and (A-3) is such that (A-1) is 0 to 100 based on the total amount of monomers.
% By weight, preferably 40 to 95% by weight, and (A-2) is 0% by weight.
To 50% by weight, preferably 1 to 40% by weight, (A-3)
Is 0 to 50% by weight, preferably 1 to 40% by weight.
As the polymerization catalyst, azobisisobutyronitrile,
Benzoyl peroxide, lauroyl peroxide and the like, as the polymerization solvent, ethyl acetate, butyl acetate, isopropyl acetate, toluene, xylene, benzene, n-hexane,
Examples thereof include cyclohexane, acetone, methyl ethyl ketone, methanol, ethanol, propyl alcohol, isopropyl alcohol, butanol, and mineral spirit.

The polymerization reaction is carried out at 20 to 200 ° C. for about 0.5 to 50 hours under an inert atmosphere or a reducing atmosphere. The resin content of the polymer is 1 to 99% by weight,
The viscosity (25 ° C.) is 100 to 100,000 cps, preferably 500 to 50,000 cps, and the average molecular weight is 100
~ 2,000,000, preferably 300-10000,
The molecular weight distribution (weight average molecular weight / number average molecular weight) is 0.1
It is desired to be 10 to 10, preferably 1 to 5. If the molecular weight is less than 100, the pressure-sensitive adhesive composition becomes too soft, and if it exceeds 2,000,000, the viscosity becomes too large and handling becomes difficult, which is not preferable. On the other hand, when the molecular weight distribution is out of the above range, the production of the pressure-sensitive adhesive composition becomes difficult, which is not preferable.

The rubber resin (B) used in the present invention has an average molecular weight of 100 to 2,000,000, preferably 300 to 200,000, more preferably 500 to 10,000,000.
If it is 0000, it is not particularly limited, for example, natural rubber, silicone rubber, acrylic rubber, styrene butadiene rubber, acrylonitrile butadiene rubber, polybutene rubber, polyisobutylene rubber, isoprene rubber, isoprene isobutylene rubber, chloroprene rubber, polyvinyl ether rubber, fluorinated rubber Rubber, chlorinated rubber, urethane rubber and the like can be mentioned, and they are used alone or as a mixture or copolymer of two or more kinds.

[0011] Among them, polybutene and polyisobutylene are particularly preferably used, and more preferably an average molecular weight of 10
Those having 0 to 10000, preferably 300 to 5000 are suitable, and specifically, HV-50 (manufactured by Nippon Petrochemical), HV-100 (manufactured by Nippon Petrochemical), and HV-300 (manufactured by Nippon Petrochemical) as polybutene. Chemical Company), LV-10
0 (manufactured by Nippon Petrochemical), 100R (manufactured by Nippon Petrochemical), 300R (manufactured by Nippon Petrochemical), Polybis 30S
H (manufactured by NOF Corporation), Polybis 10N (manufactured by NOF Corporation), Vistanex LM (manufactured by Exxon Chemical Co., Ltd.) as polyisobutylene; , Tetrax 4T (Nippon Petrochemical Co., Ltd.), Tetrax 5T
(Nippon Petrochemical Co., Ltd.) and trade names such as Tetrax 6T (Nippon Petrochemical Co., Ltd.).

As the rubber resin (B), hydrogenated nitrile rubber, chlorosulfonated polyethylene, epichlorohydrin rubber, ethylene vinyl acetate rubber, ethylene acrylic rubber, norbornene rubber and the like are also preferably used, and are excellent in pressure sensitivity and tack. Effect.

The reaction accelerator (C) includes a chelate compound (C-1) and / or an aziridine compound (C-2). Examples of the chelate compound (C-1) include aluminum, iron, zinc, tin, titanium, nickel,
Examples include polyvalent metals such as antimony, magnesium, vanadium, chromium, and zirconium, such as acetylacetone and acetoacetate coordination compounds, and aluminum acetylacetone and zinc acetylacetone are particularly preferably used.

The aziridine compound (C-2) includes, for example, N, N'-hexamethylene-1,6-bis (1-aziridinecarboxamide), trimethylolpropane-tri-.beta.-aziridinylpropion. , Tetramethylolmethane-tri-β-aziridinylpropionate, N, N′-toluene 2,4-bis (1-aziridinecarboxamide) and the like; 6-bis (1-aziridinecarboxamide) is preferably employed. The chelate compound (C-1) and the aziridine compound (C-2) are used alone or in combination.

In the present invention, the acrylic resin (A), the rubber resin (B) and the chelating compound (C-1) and / or the aziridine compound (C-2) as the reaction accelerator (C) are contained. However, if necessary, the solvent (D) may be appropriately blended at any stage. The solvent (D) is not particularly limited as long as it dissolves each component, and includes ethyl acetate, toluene, xylene, n-hexane, cyclohexane, acetone, methyl ethyl ketone, methanol, ethanol, propyl alcohol, isopropyl alcohol, mineral spirit and the like. And used alone or in combination of two or more.

The amount of each component is based on 100 parts by weight of the acrylic resin (A) and the rubber-based resin (B).
Is 1 to 1000 parts by weight, preferably 1 to 500 parts by weight, and the reaction accelerator (C) is 0.01 to 100 parts by weight, preferably 0.01 to 50 parts by weight, more preferably 0.0 to 100 parts by weight.
1 to 10 parts by weight, and the solvent (D) is 0 to 1000 parts by weight, preferably 0 to 100 parts by weight.

In such an amount, the rubber-based resin (B)
Is less than 1 part by weight, the effect of the present invention cannot be obtained.
If the amount is more than 10 parts by weight, the necessary tackiness and cohesion as a pressure-sensitive adhesive composition will be impaired. If the amount of the reaction accelerator (C) is less than 0.01 part by weight, phase separation of the rubber-based resin (B) occurs. If the amount exceeds 100 parts by weight, the viscosity of the pressure-sensitive adhesive composition becomes too high, which is not preferable.

Next, a method for producing the pressure-sensitive adhesive composition of the present invention will be described.
An acrylic resin (A), a rubber resin (B) and a chelating compound (C-1) and / or an aziridine compound (C-2) as a reaction accelerator (C) may be contained. After mixing any two of the resin (A), the rubber-based resin (B), and the reaction accelerator (C), the mixture is preferably mixed with the remaining components and heated, or mixed with the remaining components while heating. .

For example, after mixing one of the acrylic resin (A) and the rubber resin (B) with the reaction accelerator (C), the mixture is mixed with the other resin and heated, or while heating. A method of mixing with the other resin, after mixing the acrylic resin (A) and the rubber resin (B), the reaction accelerator (C)
Or a method of mixing with the reaction accelerator (C) while heating, or mixing and heating the acrylic resin (A), the rubber resin (B), and the reaction accelerator (C) all at once. The method described above may be employed, but the method described above is particularly preferably employed. Of course, it is not limited to these methods. Hereinafter, the following method will be described in more detail.

Method (a) The rubber-based resin (B) and the chelating compound (C-1) and / or the aziridine compound (C-
2) After the solvent (D) is mixed as required, the mixture is added to the acrylic resin (A) or the acrylic resin (A) solution.
Thereafter, the mixture or the mixed solution is heated to 40 to 120 ° C.
The reaction is preferably performed at 50 to 100 ° C. for 0.1 to 100 hours, preferably 1 to 10 hours. Further, it may be added to the acrylic resin (A) or the acrylic resin (A) solution while the above heating is being performed. After the reaction, the reaction solution is obtained as the resin solution of the present invention.

Method (b) Acrylic resin (A) and isocyanate group-containing compound (C-1) and / or glycidyl group-containing compound (C-2) as a reaction accelerator (C), and a solvent ( After mixing D), it is added to the rubber-based resin (B) or the solution of the rubber-based resin (B). Then, the mixture or the mixed solution is
120 ° C., preferably 50-100 ° C., 0.1-10
The reaction is performed for 0 hour, preferably 1 to 10 hours. Further, the rubber-based resin (B) or the rubber-based resin (B) while heating as described above.
It may be added to the solution. After the reaction, the reaction solution is obtained as the resin solution of the present invention.

Method (a) As the reaction accelerator (C), an isocyanate group-containing compound (C-1) and / or a glycidyl group-containing compound (C-
2) After the solvent (D) is mixed as required, the mixture is added to a mixture obtained by mixing the acrylic resin (A) and the rubber resin (B), and if necessary, the solvent (D). Then, 40-1
20 ° C., preferably 50-100 ° C., 0.1-100
The reaction is carried out for a time, preferably 1 to 10 hours. Further, the mixture may be added to a mixture obtained by mixing the acrylic resin (A) and the rubber resin (B) and, if necessary, the solvent (D) while heating. After the reaction, the reaction solution is obtained as the resin solution of the present invention.

Method of (b) After mixing the acrylic resin (A), the rubber resin (B) and, if necessary, the solvent (D), the isocyanate group-containing compound (C- 1) And / or a glycidyl group-containing compound (C-2) and, if necessary, a solvent (D) are added to a mixed solution. Thereafter, the reaction is carried out at 40 to 120 ° C, preferably 50 to 100 ° C, for 0.1 to 100 hours, preferably 1 to 10 hours. Further, the mixture may be added to a solution obtained by mixing the reaction accelerator (C) and, if necessary, the solvent (D) while heating. After the reaction, the reaction solution is obtained as the resin solution of the present invention.

In the present invention, an aliphatic resin, an epoxy resin, an alkylphenol resin, a modified phenol resin, a xylene resin, a modified xylene resin, a coumarone indene resin, a rosin resin, an esterified rosin resin, It is also effective to mix resins such as terpene resin, terpene phenol resin, dammar resin, copal resin, shellac resin and the like.

Examples of the aliphatic resin include ethylene-vinyl acetate copolymer resin (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., Soabrene) and chlorinated olefin resin (manufactured by Nippon Paper Industries Co., Ltd., Supercron). Examples of the epoxy resin include bisphenyl. A
Phenol resins such as alkyl phenol formaldehyde resin (Taoka Kagaku Kogyo Co., Tackirole), modified phenol formaldehyde resin (Epocoat), novolak type epoxy resin (Epocoat, manufactured by Yuka Shell Epoxy Co., Ltd.) Xylene resins such as General Petrochemical Industries, Inc., xylene formaldehyde resins (Mitsubishi Chemical Corporation,
Nicanol), Coumarone indene resin such as Coumarone indene resin (Esculon, manufactured by Nippon Steel Chemical Co., Ltd.), rosin resin such as phenol-modified rosin resin resin (Tamanol manufactured by Arakawa Chemical Industries, Ltd.) Polymerized rosin esters (Pentalin, manufactured by Rika Hercules), terpene resins such as terpene polymer resins (YS resin, manufactured by Yashara Chemical Co., Ltd.), and terpene phenolic resins include terpene phenol copolymer resins (Yasuhara Chemical, YS Polystar) And the like are specific examples.

The tackifier is added in an amount of 0.0 with respect to 100 parts by weight of the resin comprising the acrylic resin (a), the rubber resin (B) and the reaction accelerator (C).
The amount is 1 to 1000 parts by weight, preferably 0.1 to 500 parts by weight, more preferably 1 to 100 parts by weight. If the amount is less than 0.01 part by weight, the characteristics of the tackifier will not be exhibited, and if it exceeds 1000 parts by weight, the characteristics of the acrylic pressure-sensitive adhesive will not be exhibited, which is not preferable.

The method of compounding is not particularly limited, and it can be added at any stage of the above production method. For example, acrylic resin (A), rubber resin (B),
The tackifier is mixed when mixing any two of the reaction accelerators (C), when mixing with the remaining components, or when mixed with the resin solution obtained by the above-mentioned production method. Etc. can be appropriately adopted.

In the present invention, it is preferable that a curing agent is further added to the above resin. Examples of the curing agent include, in addition to the above-mentioned chelate compounds and aziridine compounds, tolylene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, hexamethylene Diisocyanate, isophorone diisocyanate, 1,4-cyclohexanebismethyl isocyanate, 4,4-methylenebiscyclohexyl isocyanate, tolylene diisocyanate trifunctional alcohol adduct, isophorone diisocyanate bifunctional alcohol adduct, isophorone diisocyanate trifunctional alcohol adduct Hexamethylene diisocyanate bifunctional alcohol adduct, hexamethylene diisocyanate trifunctional alcohol adduct,
Tolylene diisocyanate trimer, isophorone diisocyanate trimer, hexamethylene diisocyanate trimer, burette type hexamethylene diisocyanate trimer, n-butyl isocyanate, n-hexyl isocyanate, trimethyl silicon isocyanate, dimethyl silicon diisocyanate, monomethyl silicon triisocyanate Isocyanate compounds such as isocyanates, specifically, Coronate L (manufactured by Nippon Polyurethane), Coronate HX (manufactured by Nippon Polyurethane), Coronate HL (manufactured by Nippon Polyurethane), NY720A (manufactured by Mitsubishi Chemical Corporation), Takenate D- 140N (manufactured by Takeda Pharmaceutical Co., Ltd.), Sumidur L (manufactured by Sumitomo Chemical Co., Ltd.), N, N, N ', N'
-Glycidyl compounds such as tetraglycidyl m-xylylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, monoglycidyl n-butane, monoglycidyl n-hexane and 1,6-diglycidyl n-hexane Specific examples include Tetrad X (manufactured by Mitsubishi Gas Chemical Company) and Tetrad C (manufactured by Mitsubishi Gas Chemical Company).

The amount of the curing agent is 0.01 to 100 parts by weight, preferably 0.05 to 50 parts by weight, more preferably 0.1 to 100 parts by weight based on 100 parts by weight of the resin.
It is desired to be 10 parts by weight. When the amount of such a compound is 0.
If the amount is less than 01 parts by weight, the cohesive strength of the pressure-sensitive adhesive layer becomes extremely low, while if it exceeds 100 parts by weight, the adhesive force of the pressure-sensitive adhesive layer becomes extremely high, which is not preferable.

Thus, the pressure-sensitive adhesive composition of the present invention is obtained. The pressure-sensitive adhesive composition comprises a chelate compound (A), a rubber resin (B) and a chelating compound (C) as a reaction accelerator (C). C-1) and / or an aziridine compound (C-2), and if necessary, a resin containing a solvent (D), preferably a resin further containing a tackifier, and preferably a curing agent. , More preferably by employing the above-mentioned or the above-mentioned production method, it is excellent in the stability over time of the adhesive properties, and in particular, the tackiness is far superior to that of the rubber resin itself.

The pressure-sensitive adhesive composition is not particularly limited as a substrate, and may be, for example, a polyethylene terephthalate film, a vinyl chloride resin film, a stretched polyethylene or polypropylene film, a cellulose triacetate-based film, a paper, a film or the like. (Including sheets). At the time of coating, the thickness after drying is 0.1 to 100
0 μm, preferably 0.5 to 500 μm, more preferably 1.0 to 100 μm. If the coating thickness is less than 0.1 μm, the adhesive strength and tackiness are extremely low,
On the other hand, if the thickness exceeds 1000 μm, the cost of the pressure-sensitive adhesive product is undesirably increased. As a coating method, for example, a method such as a lip coater, a reversible coater, a doctor plate coater or the like is adopted. Also, in addition to the above-mentioned coating method, a release paper or a release film (a release polyethylene terephthalate film, a release polyethylene film, etc.) is applied, dried, and then bonded to the base material. The transfer processing method is also very effectively employed, and the effect of the present invention is remarkably exhibited.

Then, the film with the pressure-sensitive adhesive composition is bonded to an adherend. The adherend is not particularly limited, for example, polyethylene, polyolefin resin such as polypropylene, polycarbonate resin,
Polystyrene resin, vinyl chloride resin, paper, synthetic paper, metal, cloth, wood, foam, natural rubber, synthetic rubber (isoprene rubber, styrene butadiene rubber, butyl rubber), and the like. In the case of polyethylene, polypropylene and the like), polycarbonate resin, polystyrene resin and rubber, the effects of the present invention are remarkably exhibited. Thus, the pressure-sensitive adhesive composition of the present invention is very effective in various fields such as for ordinary labels, food labels, double-sided tapes, rubber products, houses, automobiles, and electrics.

[0033]

The present invention will be specifically described below with reference to examples. In the examples, “parts” and “%” are based on weight unless otherwise specified. Example 1 Polybutene as a rubber resin; HV-100 (manufactured by Nippon Petrochemical Co., Ltd., average molecular weight: about 1,000, viscosity: about 10,000 c)
ps) 20 parts, a mixed solution of aluminum acetylacetone (10% isopropyl alcohol solution, manufactured by Nippon Chemical Industry Co., Ltd.) as a chelate compound and 30 parts of toluene,
Acrylic resin composed of 2-ethylhexyl acrylate / n-butyl acrylate / vinyl acetate / acrylic acid = 45/45/6/4 heated to 50 ° C. (average molecular weight Mw: 700,000, molecular weight distribution (weight (Average molecular weight / number average molecular weight): 2.5, resin content: 42%, solvent composition: ethyl acetate / toluene = 1/1, viscosity (25 ° C.):
(4500 cps) over one hour.
Then, the mixed solution was heated to 90 ° C. and reacted for 10 hours to obtain a resin solution (resin content: 41.5%, viscosity (25%
C): 3580 cps), and the pressure-sensitive adhesive composition of the present invention was obtained. The pressure-sensitive adhesive composition thus obtained was applied to a polyethylene terephthalate film (size: 40c
m × 15 cm, thickness: 25 μ) and hand-coated so as to have a thickness of 25 μ, and the adhesive force, ball tack, holding power and its temporal stability were evaluated by the following methods.

(Adhesive force) The polyethylene terephthalate film with the pressure-sensitive adhesive composition was adhered to a polyethylene plate (size: 15 cm × 7 cm) and measured by a 180 ° peel test after leaving at 5 ° C. and 20 ° C. for 30 minutes each. did. Furthermore, after pasting on the polyethylene plate, 70
A 180-degree peel test after standing at 1 ° C. for one week was also performed to evaluate the stability over time.

(Ball tack) The ball rolling method of JIS Z 0237. The measurement was performed according to the Dow method. The measurement was performed after the polyethylene terephthalate film with the pressure-sensitive adhesive composition was allowed to stand at 70 ° C. for 1 week. (Holding power) The polyethylene terephthalate film with the pressure-sensitive adhesive composition was SUS304 (size: 15 cm).
× 7cm), and left standing at 40 ° C for 30 minutes. A 1kg load was applied to the end, and the time (min) and the time required for the load to fall (Mm) (measurement of time until 1440 minutes and deviation). Furthermore, after pasting on the above SUS304, measurement after leaving at 70 ° C. for one week is also performed.
The aging stability was evaluated.

Example 2 2-ethylhexyl acrylate / n-butyl acrylate / acrylonitrile / acrylic acid = 41/41/15 /
Acrylic resin (average molecular weight Mw: 6000)
00, molecular weight distribution: 2.9, resin content: 43%, solvent composition: ethyl acetate / toluene / n-hexane = 40/35
/ 25, viscosity (25 ° C): 4120 cps), 100 parts, and polyisobutylene as a rubber-based resin; Vistanex MML-80 (manufactured by Exxon Chemical Co., Ltd., average molecular weight of about 73)
After mixing a resin solution consisting of 10 parts of toluene and 15 parts of toluene, the mixture was heated to 90 ° C., and N, N′-hexamethylene-1,6- was added thereto as an aziridine compound. One part of bis (1-aziridinecarboxamide) (manufactured by Mutual Pharmaceutical Co., Ltd.) is added, and the mixture is allowed to react under sealed condition for 5 hours to obtain a resin solution (resin content: 42%, viscosity (25 ° C.): 4050 cps). Thus, a pressure-sensitive adhesive composition of the present invention was obtained. The obtained pressure-sensitive adhesive composition was evaluated in the same manner as in Example 1 for adhesive strength, ball tack, holding power, and its temporal stability.

Example 3 In Example 1, 1 part of a curing agent (isocyanate-based compound (Coronate L; manufactured by Nippon Polyurethane Co.)) was added to 100 parts of the resin solution obtained in Example 1 in addition to the resin solution obtained in Example 1.
Was carried out in the same manner except that was added to obtain a pressure-sensitive adhesive composition of the present invention. The obtained pressure-sensitive adhesive composition was evaluated in the same manner as in Example 1 for adhesive strength, ball tack, holding power, and its temporal stability.

Example 4 In Example 2, 1 part of a curing agent (isocyanate compound (Coronate L; manufactured by Nippon Polyurethane Co., Ltd.)) was added to 100 parts of the resin solution obtained in Example 2 in addition to the resin solution obtained in Example 2.
Was carried out in the same manner except that was added to obtain a pressure-sensitive adhesive composition of the present invention. The obtained pressure-sensitive adhesive composition was evaluated in the same manner as in Example 1 for adhesive strength, ball tack, holding power, and its temporal stability.

Example 5 Acrylic resin (composition: 2-hexylhexyl acrylate / ethyl acrylate / vinyl acetate / octyl acrylate / acrylic acid = 51/26/5/15/3, average molecular weight Mw: 800000, molecular weight) Distribution: 3.2, resin content: 4
4%, solvent composition: ethyl acetate / toluene / acetone = 2
0/70/10, viscosity (25 ° C): 3950 cps) 1
While stirring 00 parts at 25 ° C under an inert atmosphere, a solution consisting of 2 parts of acetylacetone nickel (manufactured by Nippon Chemical Industry Co., Ltd.) and 10 parts of isopropyl alcohol as a chelate compound was added over 10 minutes, and then heated to 50 ° C. 300R (Idemitsu Petrochemical Co., Ltd., average molecular weight about 1500, viscosity about 32000c
ps), and the mixture was further heated to 90 ° C. and reacted for 5 hours to give a resin solution (resin content: 41%, viscosity (25%)
° C): 3800 cps). One part of a curing agent (isocyanate compound (Coronate L; manufactured by Nippon Polyurethane Co., Ltd.)) was added to 100 parts of the resin solution to 100 parts of the resin to obtain a pressure-sensitive adhesive composition of the present invention. The obtained pressure-sensitive adhesive composition was evaluated in the same manner as in Example 1 for adhesive strength, ball tack, holding power, and its temporal stability.

Example 6 Polybutene as a rubber resin; polybis 10N (manufactured by Idemitsu Petrochemical Co., Ltd., average molecular weight: about 1,000, viscosity: about 10,000)
(cps) 15 parts, a mixed solution consisting of 3 parts of trimethylolpropane-tri-β-aziridinylpropionate (manufactured by Mutual Pharmaceutical Co., Ltd.) as an aziridine compound and 10 parts of cyclohexanone was heated to 50 ° C. Acrylic resin composed of 2-ethylhexyl acrylate / n-butyl acrylate / vinyl pyrrolidone / acrylic acid = 46/46/5/3 (average molecular weight Mw: 650000, molecular weight distribution: 2.2, resin content: 43.8) %, Solvent composition: ethyl acetate / toluene / n-hexane = 45/45/10,
Viscosity (25 ° C.): 5410 cps) was added over 30 minutes to 100 parts. Then, the mixed solution was heated to 95 ° C. and reacted for 20 hours to obtain a resin solution (resin content: 43.5%,
(Viscosity (25 ° C.): 5200 cps). One part of a curing agent (isocyanate-based compound (Coronate L; manufactured by Nippon Polyurethane Co., Ltd.)) was added to 100 parts of the resin solution to obtain 100 parts of the resin to obtain a pressure-sensitive adhesive composition of the present invention.
The obtained pressure-sensitive adhesive composition was evaluated in the same manner as in Example 1 for adhesive strength, ball tack, holding power, and its temporal stability.

Example 7 In Example 1, polybutene; HV was used as the rubber resin.
-100 (manufactured by Nippon Petrochemical Co., Ltd., average molecular weight: about 1000,
20 parts of viscosity, about 10,000 cps), aluminum acetylacetone (manufactured by Nippon Chemical Industry Co., Ltd.)
10% isopropyl alcohol solution) 1 part, toluene 3
0 parts of the mixed solution was mixed with a natural rubber resin; DPR-40 (Ha
rdman) and a resin solution (resin content: 41) except that a mixed solution consisting of 50 parts of a 40% n-hexane solution and 0.1 part of zinc acetylacetone (manufactured by Nippon Chemical Industry Co., Ltd.) as a chelate compound was used. %, Viscosity (25
C): 3400 cps). One part of a curing agent (isocyanate-based compound (Coronate L; manufactured by Nippon Polyurethane Co., Ltd.)) was added to 100 parts of the resin solution to obtain 100 parts of the resin to obtain a pressure-sensitive adhesive composition of the present invention. The obtained pressure-sensitive adhesive composition was evaluated in the same manner as in Example 1 for adhesive strength, ball tack, holding power, and its temporal stability.

Example 8 In Example 1, polybutene; HV was used as the rubber resin.
-100 (manufactured by Nippon Petrochemical Co., Ltd., average molecular weight: about 1000,
20 parts of viscosity, about 10,000 cps), aluminum acetylacetone (manufactured by Nippon Chemical Industry Co., Ltd.)
10% isopropyl alcohol solution) 1 part, toluene 3
0 parts of the mixed solution was added to a silicone rubber resin;
A resin solution (resin content) was prepared in the same manner except that a solution consisting of 20 parts of a 40% cyclohexane solution of TU (manufactured by Shin-Etsu Silicone Co., Ltd.) and 0.1 part of aluminum acetylacetone (manufactured by Nippon Chemical Industry Co., Ltd.) as a chelate compound was used. : 4
1.5%, viscosity (25 ° C.): 3860 cps).
One part of a curing agent (isocyanate-based compound (Coronate L; manufactured by Nippon Polyurethane Co., Ltd.)) was added to 100 parts of the resin solution to obtain 100 parts of the resin to obtain a pressure-sensitive adhesive composition of the present invention. The obtained pressure-sensitive adhesive composition was evaluated in the same manner as in Example 1 for adhesive strength, ball tack, holding power, and its temporal stability.

Example 9 In Example 1, polybutene; HV was used as the rubber resin.
-100 (manufactured by Nippon Petrochemical Co., Ltd., average molecular weight: about 1000,
20 parts of viscosity, about 10,000 cps), aluminum acetylacetone (manufactured by Nippon Chemical Industry Co., Ltd.)
10% isopropyl alcohol solution) 1 part, toluene 3
0 parts of the mixed solution is chlorosulfonated polyethylene;
Hypalon (manufactured by DuPont, average molecular weight about 22000)
A resin solution (resin content: 42%, viscosity (20%), a mixed solution of 1 part of acetylacetone vanadium (10% isopropyl alcohol solution manufactured by Nippon Chemical Industry Co., Ltd.) and 30 parts of toluene as a chelate compound was used. 25
° C): 4530 cps). One part of a curing agent (isocyanate compound (Coronate L; manufactured by Nippon Polyurethane Co., Ltd.)) was added to 100 parts of the resin solution to 100 parts of the resin to obtain a pressure-sensitive adhesive composition of the present invention. The obtained pressure-sensitive adhesive composition was evaluated in the same manner as in Example 1 for adhesive strength, ball tack, holding power, and its temporal stability.

Example 10 A resin solution (resin content: 47%, viscosity (25%) was prepared in the same manner as in Example 1 except that 15 parts of a polymerized rosin ester; pentaline CJ (manufactured by Rika Hercules) was further added as a tackifier. ° C): 3680 cps). One part of a curing agent (isocyanate compound (Coronate L; manufactured by Nippon Polyurethane Co., Ltd.)) was added to 100 parts of the resin solution to 100 parts of the resin to obtain a pressure-sensitive adhesive composition of the present invention. The obtained pressure-sensitive adhesive composition was evaluated in the same manner as in Example 1 for adhesive strength, ball tack, holding power, and its temporal stability.

Example 11 In Example 2, a xylene resin; Nicanol H-80 (manufactured by Mitsubishi Gas Chemical Company) was further used as a tackifier.
A resin solution (resin content: 4
8.5%, viscosity (25 ° C.): 3310 cps).
One part of a curing agent (isocyanate compound (Coronate L; manufactured by Nippon Polyurethane Co., Ltd.)) was added to 100 parts of the resin solution to 100 parts of the resin to obtain a pressure-sensitive adhesive composition of the present invention. The obtained pressure-sensitive adhesive composition was evaluated in the same manner as in Example 1 for adhesive strength, ball tack, holding power, and its temporal stability.

Example 12 In Example 9, chlorinated polypropylene; S-813A (manufactured by Nippon Paper Industries) was further used as a tackifier.
A resin solution of the present invention (resin content: 43.2%, viscosity (25 ° C.): 4150 cps) was obtained in the same manner except that the components were blended. One part of a curing agent (isocyanate compound (Coronate L; manufactured by Nippon Polyurethane Co., Ltd.)) was added to 100 parts of the resin solution to 100 parts of the resin to obtain a pressure-sensitive adhesive composition of the present invention. The obtained pressure-sensitive adhesive composition was evaluated in the same manner as in Example 1 for adhesive strength, ball tack, holding power, and its temporal stability.

Comparative Example 1 The procedure of Example 1 was repeated, except that polybutene as the rubber resin was omitted, and the obtained pressure-sensitive adhesive composition was evaluated in the same manner as in Example 1.

Comparative Example 2 Evaluation was performed in the same manner as in Example 1 using a pressure-sensitive adhesive of a rubber resin; Bond G17 (chloroprene rubber, manufactured by Konishi).

Comparative Example 3 A pressure-sensitive adhesive composition was obtained in the same manner as in Example 1, except that the chelating compound (aluminum acetylacetone (manufactured by Nippon Chemical Industry Co., Ltd.)) was omitted as the reaction accelerator. Evaluation was performed in the same manner as in Example 1. In addition, the obtained pressure-sensitive adhesive composition was phase-separated. Table 1 shows the evaluation results of the examples and comparative examples.

[0050]

[Table 1] Adhesive force after 70 ° C for one week before long-term storage Ball tack holding force Adhesive force Ball tack holding force (g / 25mm) (Ball No.) Time Deviation (g / 25mm) (Ball No.) Time Deviation 5 ° C 20 ° C (min) (mm) 5 ° C 20 ° C (min) (mm) Example 1 756 1218 27 1440 1.0 1225 1281 26 1440 1.0 〃 2 658 1036 25 1440 1.0 1113 1127 25 1440 1.0 ３ 3 798 1267 28 1440 0.0 1337 1358 27 1440 0.0 〃 4 637 1169 29 1440 0.0 1211 1246 27 1440 0.0 ５ 5 721 1281 31 1440 0.0 1344 1358 30 1440 0.0 〃 6 679 924 26 1440 0.0 966 1008 25 1440 0.0 〃 7 581 945 29 1440 0.0 1015 1029 29 1440 0.0 ８ 8 735 1358 28 1440 0.0 1372 1456 27 1440 0.0 ９ 9 644 1050 27 1440 0.0 1057 1134 27 1440 0.0 〃 10 868 1372 32 1440 0.0 1428 1484 31 1440 0.0 〃 11 623 1155 29 1440 0.0 1169 1253 28 1440 0.0 〃 12 735 1106 28 1440 0.0 1113 1155 28 1440 0.0 Comparative Example 1 385 1155 8 1440 1.0 1155 1211 7 1440 1.0 〃 2 392 861 17 312 --- 875 917 15 327 --- 〃 3 749 1162 28 259- -1246 1 309 27 274 ---

[0051]

The pressure-sensitive adhesive composition obtained by the present invention is excellent in tackiness, adhesion, high-low temperature adhesion, aging resistance and storage stability, and in particular, tackiness is far more than that of the rubber resin itself. It has an excellent effect on the adhesive properties and excellent stability over time of each adhesive property, and is very effective for applications such as labels, double-sided tapes and industrial tapes.

Claims (7)

[Claims] An acrylic resin (A), a rubber resin (B), and a chelating compound (C-1) and / or an aziridine compound (C-2) as a reaction accelerator (C). A pressure-sensitive adhesive composition comprising: 2. The pressure-sensitive adhesive composition according to claim 1, further comprising a curing agent. 3. A curing agent is added in an amount of 0.1 to 100 parts by weight of the resin.
3. The composition according to claim 2, wherein the amount is from 0.01 to 100 parts by weight.
The pressure-sensitive adhesive composition as described in the above. 4. The rubber-based resin (B) has an average molecular weight of 100.
4 to 2,000,000.
The pressure-sensitive adhesive composition according to any one of the above. 5. The rubber-based resin (B) is polybutene and / or polyisobutylene.
4. The pressure-sensitive adhesive composition according to any one of 4. 6. After mixing any two of acrylic resin (A), rubber resin (B), and reaction accelerator (C), the remaining components are mixed and heated, or heated. 2. The composition of claim 1, which is mixed with remaining components.
6. The pressure-sensitive adhesive composition according to any one of claims 1 to 5. 7. The pressure-sensitive adhesive composition according to claim 1, further comprising 0.01 to 1000 parts by weight of a tackifier based on 100 parts by weight of the resin.