JPH05105857A - Self-adhesive composition and self-adhesive tape, label, or sheet - Google Patents

Abstract

PURPOSE:To prepare the title compsn. excellent in adhesion after aging to a plasticized vinyl chloride resin by using, as the main component, an acrylic polymer emulsion essentially comprising a specific (meth)acrylic ester and a specific copolymerizable monomer. CONSTITUTION:The title compsn. contains, as the main component, an acrylic copolymer emulsion prepd. from a monomer mixture contg. at least 60wt.% at least one (meth)acrylic ester of the formula: CH2=CR1-COOR2 (wherein R1 is H or CH3; and R2 is 4-14C alkyl) and 3-20wt.% least one monomer of the formula (wherein R4 and R5 are each the same as R1 provided they are different; R6 is H or 1-4C alkyl; and m and n are each 0-20 provided not both of them are simultaneously 0).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an acrylic pressure-sensitive adhesive composition and a pressure-sensitive adhesive tape, label or sheet using this pressure-sensitive adhesive composition.

[0002]

2. Description of the Related Art A soft vinyl chloride resin containing a plasticizer is used as a base material of a pressure-sensitive adhesive tape, label or sheet using an acrylic pressure-sensitive adhesive composition, or a soft vinyl chloride resin product containing a plasticizer. As an adherend, a pressure-sensitive adhesive tape provided with a pressure-sensitive adhesive layer made of an acrylic pressure-sensitive adhesive composition, affixing a label or a sheet, or a soft vinyl chloride resin product containing a plasticizer using a double-sided adhesive tape In the case of joining, there is a problem in that the plasticizer migrates from the soft vinyl chloride resin to the pressure-sensitive adhesive layer, which significantly reduces the adhesive performance of the pressure-sensitive adhesive layer.

Therefore, for example, Japanese Patent Laid-Open No. 53-9451.
No. 9, gazette with a resol type phenolic resin mixed with an adhesive, as described in JP-A No. 63-23078, an adhesive with nitrified cotton, or JP-A No. 1-101384. As described in the publication, various proposals have been made to improve the pressure-sensitive adhesive, such as using a crosslinkable monomer and a metal complex together in the pressure-sensitive adhesive.

However, in recent years, with the expansion of applications of adhesive tapes and the like, the required performance has become higher, and it is difficult to solve the above problems due to migration of plasticizers only by improving the above-mentioned adhesives. there were.

Therefore, as means for solving this problem, for example, as described in JP-A-56-136871 and JP-B-64-9352, molding of a soft vinyl chloride resin as an adherend is made. A method has been proposed and put to practical use in which a primer (primer coat) is first applied to the surface of an article, and then an adhesive is applied on the primer layer or an adhesive tape is applied.

[0006]

However, in other words, in these methods, the pressure-sensitive adhesive cannot be used practically unless a primer is used in combination, and therefore an extra step of coating the primer is required. Also,
For example, it is very difficult to apply a primer evenly to the surface of an adherend of a molded product made of a soft vinyl chloride resin having a large area during outdoor construction.

[0007] The present invention, without the use of primers
The purpose of the present invention is to provide a pressure-sensitive adhesive composition and a pressure-sensitive adhesive tape, a label or a sheet which are excellent in sticking property with time to a soft vinyl chloride resin containing a plasticizer.

[0008]

The invention of claim 1 of the present application is based on the general formula

[0009]

[Chemical 4]

(Wherein R ₁ is hydrogen or a methyl group, R ₂
Is one or more (meth) acrylic acid ester having 4 to 14 carbon atoms) and 60% by weight (in the monomer component) or more, and the general formula

[0011]

[Chemical 5]

(Wherein R ₃ , R ₄ , and R ₅ are hydrogen or a methyl group, provided that R ₄ and R ₅ are not the same, R ₆ is hydrogen or an alkyl group having 4 or less carbon atoms, and m and n are 0 at the same time. Not an integer of 0 to 20) and at least one monomer represented by 3 to 20
It is a pressure-sensitive adhesive composition containing an acrylic copolymer whose main component is wt% (in the monomer components).

The invention of claim 2 of the present application is based on the general formula

[0014]

[Chemical 6]

(Wherein R ₁ is hydrogen or a methyl group, R _{2 is}
Is one or more (meth) acrylic acid ester having 4 to 14 carbon atoms) (50% by weight or more (in the monomer component)), N, N-dimethylaminoethyl acrylate, N-
Main component is an acrylic copolymer containing 3 to 30% by weight (in a monomer component) of one or more kinds of monomers selected from vinyl pyridine, acryloylmorpholine, N-isopropylacrylamide and N-vinylcaprolactam as a main component monomer. It is an adhesive composition.

The invention of claim 3 of the present application is an adhesive tape, label or sheet using the adhesive composition of claim 1 or 2. The (meth) acrylic acid ester used in the present invention is represented by the following general formula.

[0017]

[Chemical 7]

In the formula, R ₁ is hydrogen or a methyl group, R ₂ is an alkyl group having 4 to 14 carbon atoms, that is, n-
A butyl group, an n-octyl group, a 2-ethylhexyl group, an isooctyl group, an isononyl group, a lauryl group, and the like, and examples thereof include n-butyl (meth) acrylate,
Examples thereof include n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, and lauryl (meth) acrylate, and one or more of them are appropriately combined and used.

When the carbon number of the alkyl group of R ₂ of the (meth) acrylic acid ester is less than 4 or more than 14,
The glass transition temperature is high, and the adhesive strength tends to decrease. In the invention of claim 1, the content ratio of the (meth) acrylic acid ester in the copolymer needs to be 60% by weight or more, and preferably 70 to 97% by weight.
If it is less than 60% by weight, the pressure-sensitive adhesive becomes too hard, and the pressure-sensitive adhesive strength is reduced especially at low temperatures. In the invention of claim 2, it is required to be 50% by weight or more, and preferably 70 to 97% by weight. If it is less than 50% by weight, the pressure-sensitive adhesive becomes too hard and the adhesive strength is lowered.

In the invention of claim 1 of the present application, as the cohesive force component which is copolymerized with the (meth) acrylic acid ester to form an acrylic copolymer, a general formula

[0021]

[Chemical 8]

(Wherein R ₃ , R ₄ , and R ₅ are hydrogen or a methyl group, provided that R ₄ and R ₅ are not the same, R ₆ is hydrogen or an alkyl group having 4 or less carbon atoms, and m and n are the same). An acrylic monomer having a polyether side chain represented by a non-zero integer of 0 to 20) is used, and examples thereof include methyltriglycol acrylate, polyethylene glycol monomethacrylate, ethoxydiethylene glycol acrylate, and methoxydipropylene glycol. (Meth) acrylate, polyethylene glycol polypropylene glycol (meth) acrylate and the like can be used.

The content of the above monomer in the copolymer is 3 to
20% by weight (in the monomer component), preferably 5 to
It is 15% by weight (in the monomer component). If the content is less than 3% by weight (in the monomer component), the cohesive force is small, and when the product is produced, the pressure-sensitive adhesive will squeeze out, and the holding force and the creep resistance will decrease. On the other hand, when it exceeds 20% by weight (in the monomer component), the pressure-sensitive adhesive becomes too hard, and the pressure-sensitive adhesive strength is lowered particularly at low temperatures, and both are not suitable as pressure-sensitive adhesives.

According to the second aspect of the present invention, N, N-dimethylaminoethyl acrylate, N-vinyl pyridine, and N-vinyl pyridine are used as the cohesive force component that is copolymerized with the (meth) acrylic acid ester to form an acrylic copolymer. Acryloylmorpholine, N-isopropylacrylamide and N
Use one or more monomers selected from vinylcaprolactam. N, N-dimethylaminoethyl acrylate, N-vinyl pyridine, acryloylmorpholine,
The content of one or more monomers selected from N-isopropylacrylamide and N-vinylcaprolactam in the copolymer is 3 to 30% by weight (in the monomer component), preferably 5 to 20% by weight (in the monomer component). ). When the content is less than 3% by weight (in the monomer component), the cohesive force is small, and when the product is manufactured, the pressure-sensitive adhesive sticks out, and the holding force and the creep resistance are deteriorated.
On the other hand, when it exceeds 30% by weight (in the monomer component), the pressure-sensitive adhesive becomes too hard, and the adhesive strength is lowered particularly at low temperature, and both are not suitable as a pressure-sensitive adhesive.

The unsaturated monomer copolymerizable with the (meth) acrylic acid ester used in the present invention is optionally used, and specific examples thereof include vinyl acetate, styrene, ethyl (meth) acrylate, and the like. Examples include methyl (meth) acrylate and (meth) acrylamide.

The content ratio of the unsaturated monomer copolymerizable with the (meth) acrylic acid ester is preferably 0 to 30% by weight (in the monomer component). If the content exceeds 30% by weight (in the monomer component), the pressure-sensitive adhesive becomes hard and the adhesive strength is likely to be lowered.

The acrylic copolymer in the present invention may be polymerized by any of solution polymerization, emulsion polymerization, bulk polymerization and suspension polymerization. The polymerization initiation method may be a thermal initiation polymerization method or a photopolymerization by ultraviolet light. Known methods such as an initiation polymerization method and a polymerization method using a redox catalyst can be adopted. More practically, the solution polymerization method is used.

Examples of the reaction solvent include esters such as ethyl acetate and methyl acetate, aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as pentane and hexane, and alicyclic hydrocarbons such as cyclohexane. Examples are exemplified, and these are used alone or in combination. Particularly preferably, a solvent such as ethyl acetate having a small chain transfer constant and a low toxicity to the human body is used.

As the polymerization initiator, known polymerization initiators such as peroxides such as benzoyl peroxide and lauryl peroxide, azo compounds such as azobisisobutyronitrile and the like can be used alone or in combination. The amount of the polymerization initiator added is usually 0.01 to 1 part by weight based on 100 parts by weight of the monomer.

The molecular weight of the acrylic copolymer is not particularly limited, but the polystyrene reduced molecular weight by gel permeation chromatography (GPC) is 100,000 to 100,000.
It is 1,000,000, preferably 300,000 to 700,000.

In the present invention, a tackifying resin and a plasticizer may be used in combination if necessary. As the tackifying resin, xylene resin, rosin resin, hydrogenated rosin resin, phenol resin, phenol-modified resin and the like can be used alone or in combination.

Examples of the plasticizer include phthalic acid esters such as dioctyl phthalate (DOP) and dibutyl phthalate (DBP), adipic acid esters such as dioctyl adipate (DOA), and epoxy plasticizers such as epoxidized soybean oil. It can be used alone or in combination.

The addition amount of the tackifying resin and the plasticizer is preferably 2 to 30 parts by weight with respect to 100 parts by weight of the acrylic copolymer. In the present invention, the acrylic copolymer,
It is preferable to crosslink for the purpose of improving the holding power and creep resistance, and maintaining the physical properties of the pressure-sensitive adhesive even at high temperatures. As the crosslinking method, a method of crosslinking by a chemical reaction with a functional group in the acrylic copolymer by using a crosslinking agent such as an epoxy crosslinking agent, an isocyanate crosslinking agent, an aziridine crosslinking agent, and a metal complex, and ultraviolet irradiation A publicly known method such as a method of crosslinking by a radical reaction such as a method and an electron beam irradiation method is appropriately adopted.

When cross-linking with an isocyanate type cross-linking agent, an epoxy type cross-linking agent, or an aziridine type cross-linking agent, it is necessary to introduce a functional group which becomes a cross-linking starting point such as a hydroxyl group or a carboxyl group into the acrylic copolymer. When a hydroxyl group is introduced, a monomer having a hydroxyl group at the terminal may be used. For example, when a hydroxyl group-containing monomer such as 2-hydroxyethyl (meth) acrylate is used,
It may be copolymerized at 1% by weight. As a crosslinking origin monomer,
When the α, β-unsaturated carboxylic acid is used, the amount used is preferably as small as possible, and is 0.5% by weight or less, preferably 0.05 to 0.1% by weight.

The degree of crosslinking of the pressure-sensitive adhesive can be confirmed by immersing it in a good solvent such as ethyl acetate or tetrahydrofuran (THF) and measuring the gel fraction. A suitable degree of crosslinking is a gel fraction in THF of 25-85%. Particularly preferred is 30 to 75%, although it varies depending on whether solvent-soluble molecules such as tackifying resin and plasticizer are added.

[0036]

In the inventions of claims 1 and 2, the present invention is a monomer that is copolymerized with a (meth) acrylic acid ester, and is a polyether type monomer as a cohesive force component of the copolymerized acrylic copolymer. An acrylic monomer having a side chain, or N, N-dimethylaminoethyl acrylate, N-vinylpyridine, acryloylmorpholine,
One or more kinds of monomers selected from N-isopropylacrylamide and N-vinylcaprolactam are used. In the pressure-sensitive adhesive obtained by copolymerizing α, β-unsaturated carboxylic acid such as (meth) acrylic acid, itaconic acid, maleic acid, fumaric acid or crotonic acid, which has been widely used as a cohesive force component, While a significant decrease in adhesive performance such as peeling force and holding force, which is thought to be due to a plasticizer that migrates or bleeds to the adhesive interface, is observed, when using these cohesive force components,
The performance of the adhesive hardly deteriorates.

Therefore, in the invention of claim 3 of the present application, an adhesive tape, label or sheet suitable for a soft vinyl chloride resin, which does not deteriorate the adhesive performance of the adhesive even when the plasticizer is transferred, is obtained. Be done.

[0038]

EXAMPLES Examples of the present invention will be described below. Example 1 (1) Production of Adhesive In a reactor equipped with a thermometer, a stirrer, a cooling pipe and a dropping funnel, 95 parts by weight of n-butyl acrylate, methyltriglycol acrylate (manufactured by Kyoeisha Yushi Co., Ltd .: trade name "light acrylate" 5 parts by weight of MTG-A ") is dissolved in 100 parts by weight of ethyl acetate and polymerized for 8 hours at 80 ° C. in a nitrogen stream with 0.2 part by weight of benzoyl peroxide as an initiator to obtain a pressure-sensitive adhesive solution. It was

(2) This adhesive solution was applied on a 38 μm thick polyester film so that the layer thickness after drying would be 70 μm, and dried at 100 ° C. for 5 minutes. Then, the obtained pressure-sensitive adhesive layer was irradiated with an electron beam to be crosslinked to obtain a pressure-sensitive adhesive tape on which the crosslinked pressure-sensitive adhesive layer was formed.

(3) Measurement of physical properties Test pieces were cut out from this adhesive tape, and a peeling force test and a holding force test were conducted. The results are shown in Table 1. The test method is as follows.

Peel force test As an adherend, a vinyl chloride resin (polymerization degree 1100) 10
Use a soft vinyl chloride resin plate (30 × 80 × 5 mm) consisting of 0 parts by weight, 50 parts by weight of dioctyl phthalate, 2 parts by weight of epoxidized soybean oil, 3 parts by weight of metallic stabilizer and 15 parts by weight of ground calcium carbonate. I was there. 2 to this adherend
A 5 × 125 mm pressure-sensitive adhesive tape test piece was attached by pressing back and forth once with a 2 kg roller. Then, the adherend to which the adhesive tape was attached was accelerated in the atmosphere at 90 ° C. to transfer the plasticizer in the adherend to the adhesive layer in the adhesive tape. Immediately after application and after aging acceleration, the test piece was subjected to a 180 ° peel test in accordance with JIS Z0237 to measure the change in peel force.

Holding power test Adhesive tape was adhered to an adherend by the same operation as above to accelerate aging, and then, in accordance with JIS Z0237, 1 at 40 ° C.
A holding force test was performed with a load of kg, and the time until the adhesive tape dropped was measured. In this test, the sticking area is 2
It was set to 5 × 25 mm.

Example 2 Monomer composition was changed to 2-ethylhexyl acrylate 65
Parts by weight, 15 parts by weight of vinyl acetate, and 20 parts by weight of polyethylene glycol monomethacrylate (manufactured by NOF CORPORATION: trade name "Blenmer PE") except that the adhesive solution was obtained in the same manner as in Example 1 to obtain an adhesive tape. Then, a physical property test was conducted. The results are shown in Table 1.

Example 3 Monomer composition was changed to 69.8 parts by weight of n-butyl acrylate, 10 parts by weight of ethyl acrylate, 20 parts by weight of ethoxydiethylene glycol acrylate (Kyoeisha Yushiki: trade name "light acrylate EC-A"), 2 —A pressure-sensitive adhesive solution was obtained in the same manner as in Example 1 except that 0.2 part by weight of hydroxymethacrylate was used. To this adhesive solution, 10 parts by weight of a xylene-based tackifying resin (manufactured by Mitsubishi Oil Co., Ltd .: trade name "Oligotech 2300"), 10 parts by weight of dioctyl phthalate as a plasticizer, and an isocyanate-based crosslinking agent (Japan Polyurethane) Co., Ltd .: trade name "Coronate L") 1.0 part by weight is added, and the adhesive solution is coated on a polyester film having a thickness of 38 μm so that the layer thickness after drying is 70 μm, and the temperature is 100 ° C.
It was dried in the inside for 5 minutes to obtain a pressure-sensitive adhesive tape on which a crosslinked pressure-sensitive adhesive layer was formed, and a physical property test was conducted. The results are shown in Table 1.

Comparative Example 1 An adhesive tape was obtained in the same manner as in Example 1 except that the monomer composition was 93 parts by weight of isooctyl acrylate and 7 parts by weight of acrylic acid. The results are shown in Table 1.

Comparative Example 2 Monomer composition was changed to 2-ethylhexyl acrylate 70
Parts by weight, ethoxydiethylene glycol acrylate (manufactured by Kyoeisha Yushi Co., Ltd .: trade name "light acrylate EC-
A ") An adhesive tape was obtained in the same manner as in Example 1 except that the amount was 30 parts by weight, and a physical property test was conducted. The results are shown in Table 1.

[0047]

[Table 1]

As is clear from Table 1, as in the examples of the present invention, a monomer that is copolymerized with a (meth) acrylic acid ester, and a polyacrylic acid is used as a cohesive force component of the copolymerized acrylic copolymer. The one using an acrylic monomer having an ether type side chain is excellent in sticking property with time to a soft vinyl chloride resin containing a plasticizer. On the contrary,
As in the comparative example, even when conventional acrylic acid is used as the cohesive force component or an acrylic monomer having a polyether side chain is used, a plasticizer is used in a range outside of the specific limited amount. It is inferior in the ability to stick to the soft vinyl chloride resin it contains over time. Example 4 A monomer composition was prepared by adding 95 parts by weight of n-butyl acrylate,
An adhesive tape was obtained in the same manner as in Example 1 except that 5 parts by weight of N, N-dimethylaminoethyl acrylate was used, and a physical property test was conducted. The results are shown in Table 2.

Example 5 The monomer composition was changed to 2-ethylhexyl acrylate 65
An adhesive tape was obtained in the same manner as in Example 1 except that the amount of vinyl acetate was 15 parts by weight, vinyl acetate was 15 parts by weight, and N, N-dimethylaminoethyl acrylate was 20 parts by weight. The results are shown in Table 2.

Example 6 A monomer composition was prepared by adding 70 parts by weight of isononyl acrylate,
An adhesive solution was obtained in the same manner as in Example 1 except that 20 parts by weight of n-butyl methacrylate and 10 parts by weight of N, N-dimethylaminoethyl acrylate were used. To this adhesive solution, 15 parts by weight of a rosin-based tackifying resin (manufactured by Arakawa Chemical Co., Ltd .: trade name "Super Ester A-115") was added, and an adhesive tape was obtained in the same manner as in Example 1 and a physical property test was conducted. .. The results are shown in Table 2.

Example 7 Example 1 was repeated except that the monomer composition was 69.8 parts by weight of n-butyl acrylate, 30 parts by weight of N, N-dimethylaminoethyl acrylate, and 0.2 of 2-hydroxyethyl methacrylate. Similarly, an adhesive solution was obtained. Add xylene resin-based tackifying resin (product name: Oligotech 2300, manufactured by Mitsubishi Oil Co., Ltd.) to this adhesive solution.
0 parts by weight, 10 parts by weight of dioctyl phthalate as a plasticizer, and 1.0 parts by weight of an isocyanate type crosslinking agent (“Coronate L” manufactured by Nippon Polyurethane Industry Co., Ltd.) as a crosslinking agent were added, and this adhesive solution having a thickness of 38 μm was added. The adhesive tape was coated on a polyester film and dried at 100 ° C. for 5 minutes to obtain an adhesive tape having a crosslinked adhesive layer formed thereon. The physical property test of this adhesive tape was performed in the same manner as in Example 1. The results are shown in Table 2.

Comparative Example 3 Monomer composition was changed to 79 parts by weight of n-butyl acrylate,
A pressure-sensitive adhesive tape was obtained in the same manner as in Example 1 except that 20 parts by weight of ethyl acrylate and 1 part by weight of N, N-dimethylaminoethyl acrylate were used.
The results are shown in Table 2.

Comparative Example 4 Monomer composition was changed to 2-ethylhexyl acrylate 65
Parts by weight, N, N-dimethylaminoethyl acrylate 3
An adhesive tape was obtained in the same manner as in Example 1 except that the amount was 5 parts by weight, and a physical property test was conducted. The results are shown in Table 2.

The results of Comparative Example 1 are shown in Table 2 again.

[0055]

[Table 2]

As is clear from Table 2, as in the examples of the present invention, a monomer copolymerizable with a (meth) acrylic acid ester, and N was used as a cohesive force component of the copolymerized acrylic copolymer. , N-dimethylaminoethyl acrylate having a specific amount is excellent in sticking property with time to a soft vinyl chloride resin containing a plasticizer. On the other hand, even when conventional acrylic acid is used as the cohesive force component or N, N-dimethylaminoethyl acrylate is used as in the comparative example, if the specific amount is out of the range, It is inferior in applicability over time to a soft vinyl chloride resin containing an agent.

Example 8 A monomer composition was prepared by adding 95 parts by weight of n-butyl acrylate,
An adhesive tape was produced in the same manner as in Example 1 except that 5 parts by weight of N-vinylpyridine was used, and the physical properties were measured.
The results are shown in Table 3.

Example 9 Monomer composition was changed to 2-ethylhexyl acrylate 65
Parts by weight, vinyl acetate 15 parts by weight, N-vinyl pyridine 2
An adhesive tape was produced in the same manner as in Example 1 except that the amount was 0 part by weight, and the physical properties were measured. The results are shown in Table 3.

Example 10 Monomer composition was added to 70 parts by weight of isononyl acrylate,
An adhesive solution was obtained in the same manner as in Example 1 except that 20 parts by weight of n-butyl methacrylate and 10 parts by weight of N-vinylpyridine were used. To this adhesive solution, 15 parts by weight of a rosin-based tackifying resin (manufactured by Arakawa Chemical Co., Ltd .: trade name "Super Ester A-115") was added, and an adhesive tape was obtained in the same manner as in Example 1 and a physical property test was conducted. .. The results are shown in Table 3.

Example 11 Except that the monomer composition was 69.8 parts by weight of n-butyl acrylate, 0.2 parts by weight of 2-hydroxyethyl methacrylate, and 30 parts by weight of N-vinylpyridine.
An adhesive solution was obtained in the same manner as in Example 1. To this adhesive solution, 10 parts by weight of a xylene resin-based tackifying resin (trade name "Oligotech 2300" manufactured by Mitsubishi Petroleum Co., Ltd.), 10 parts by weight of dioctyl phthalate as a plasticizer, and an isocyanate-based crosslinking agent (Japan Polyurethane) as a crosslinking agent. Co., Ltd .: "Coronate L") 1.0 part by weight is added, and this adhesive solution is applied onto a polyester film having a thickness of 38 μm,
It was dried at 100 ° C. for 5 minutes to obtain a pressure-sensitive adhesive tape on which a crosslinked pressure-sensitive adhesive layer was formed. The physical property test of this adhesive tape was performed in the same manner as in Example 1. The results are shown in Table 3.

Comparative Example 5 The monomer composition was changed to 79 parts by weight of n-butyl acrylate,
20 parts by weight of ethyl acrylate, 1 N-vinyl pyridine
A pressure-sensitive adhesive tape was obtained in the same manner as in Example 1 except that the weight part was used, and a physical property test was conducted. The results are shown in Table 3.

Comparative Example 6 The monomer composition was changed to 2-ethylhexyl acrylate 65.
An adhesive tape was obtained in the same manner as in Example 1 except that the amount was 35 parts by weight and the amount of N-vinylpyridine was 35 parts by weight. The results are shown in Table 3.

The results of Comparative Example 1 are shown in Table 3 again.

[0064]

[Table 3]

As is clear from Table 3, as in the examples of the present invention, the monomer copolymerized with the (meth) acrylic acid ester, and N was used as the cohesive force component of the copolymerized acrylic copolymer. -The one using a specific amount of vinyl pyridine is excellent in sticking property with time to a soft vinyl chloride resin containing a plasticizer. On the other hand, as in the comparative example, even when the conventional acrylic acid is used as the cohesive force component or N-vinylpyridine is used, those used within the specific amount range contain the plasticizer. It is inferior in pasting property to soft vinyl chloride resin.

Example 12 A monomer composition was prepared by adding 95 parts by weight of n-butyl acrylate,
An adhesive tape was produced in the same manner as in Example 1 except that 5 parts by weight of acryloylmorpholine was used, and the physical properties were measured. The results are shown in Table 4.

Example 13 Monomer composition was changed to 2-ethylhexyl acrylate 65
An adhesive tape was produced in the same manner as in Example 1 except that the amount was 15 parts by weight, vinyl acetate was 15 parts by weight, and acryloylmorpholine was 20 parts by weight. The results are shown in Table 4.

Example 14 A monomer composition was prepared by adding 70 parts by weight of isononyl acrylate,
An adhesive solution was obtained in the same manner as in Example 1 except that 20 parts by weight of n-butyl methacrylate and 10 parts by weight of acryloylmorpholine were used. To this adhesive solution, 15 parts by weight of a rosin-based tackifying resin (manufactured by Arakawa Chemical Co., Ltd .: trade name "Super Ester A-115") was added, and an adhesive tape was obtained in the same manner as in Example 1 and a physical property test was conducted. .. The results are shown in Table 4.

Example 15 Adhesion was performed in the same manner as in Example 1 except that the monomer composition was n-butyl acrylate 69.8 parts by weight, 2-hydroxyethyl methacrylate 0.2 parts by weight, and acryloylmorpholine 30 parts by weight. An agent solution was obtained. To this adhesive solution, 10 parts by weight of a xylene resin-based tackifying resin (manufactured by Mitsubishi Oil Co., Ltd .: trade name "Oligotech 2300"),
10 parts by weight of dioctyl phthalate as a plasticizer and 1.0 part by weight of an isocyanate cross-linking agent (“Coronate L” manufactured by Nippon Polyurethane Co., Ltd.) as a cross-linking agent were added, and this adhesive solution was applied onto a polyester film having a thickness of 38 μm. After coating, it was dried at 100 ° C. for 5 minutes to obtain a pressure-sensitive adhesive tape on which a crosslinked pressure-sensitive adhesive layer was formed. The physical property test of this adhesive tape was performed in the same manner as in Example 1. The results are shown in Table 4.

Comparative Example 7 A monomer composition was prepared by adding 79 parts by weight of n-butyl acrylate,
An adhesive tape was obtained in the same manner as in Example 1 except that 20 parts by weight of ethyl acrylate and 1 part by weight of acryloylmorpholine were used, and a physical property test was conducted. The results are shown in Table 4.

Comparative Example 8 Monomer composition was changed to 2-ethylhexyl acrylate 65
A pressure-sensitive adhesive tape was obtained in the same manner as in Example 1 except that the amount of acryloylmorpholine was 35 parts by weight, and the physical properties were tested. The results are shown in Table 4.

The results of Comparative Example 1 are shown in Table 4 again.

[0073]

[Table 4]

As is clear from Table 4, as in the examples of the present invention, acryloyl was used as a monomer which is a monomer copolymerizable with a (meth) acrylic acid ester, and which is a cohesive force component of the copolymerized acrylic copolymer. Those using a specific amount of morpholine are excellent in sticking property with time to a soft vinyl chloride resin containing a plasticizer. On the other hand, as in the comparative example,
Even when conventional acrylic acid is used as the cohesive force component, or when acryloylmorpholine is used, those used in a range outside the specific amount are inferior in stickiness with time to a soft vinyl chloride resin containing a plasticizer. There is.

Example 16 A monomer composition was prepared by adding 95 parts by weight of n-butyl acrylate,
An adhesive tape was produced in the same manner as in Example 1 except that the amount of N-isopropylacrylamide was 5 parts by weight, and the physical properties were measured. The results are shown in Table 5.

Example 17 Monomer composition was changed to 2-ethylhexyl acrylate 65
An adhesive tape was produced in the same manner as in Example 1 except that the amount was 15 parts by weight, vinyl acetate was 15 parts by weight, and N-isopropylacrylamide was 20 parts by weight. The results are shown in Table 5.

Example 18 A monomer composition was prepared by adding 70 parts by weight of isononyl acrylate,
An adhesive solution was obtained in the same manner as in Example 1 except that 20 parts by weight of n-butyl methacrylate and 10 parts by weight of N-isopropylacrylamide were used. To this adhesive solution, 15 parts by weight of a rosin-based tackifying resin (manufactured by Arakawa Chemical Co., Ltd .: trade name "Super Ester A-115") was added, and an adhesive tape was obtained in the same manner as in Example 1 and a physical property test was conducted. ..
The results are shown in Table 5.

Example 19 The same as Example 1 except that the monomer composition was 69.8 parts by weight of n-butyl acrylate, 0.2 parts by weight of 2-hydroxyethyl methacrylate, and 30 parts by weight of N-isopropylacrylamide. To obtain an adhesive solution.
In this adhesive solution, 10 parts by weight of a xylene resin-based tackifying resin (manufactured by Mitsubishi Oil Co., Ltd .: trade name "Oligotech 2300"), 10 parts by weight of dioctyl phthalate as a plasticizer, and an isocyanate-based crosslinking agent (Japan Polyurethane Co .: "Coronate L") 1.0 part by weight was added, and this adhesive solution was applied onto a polyester film having a thickness of 38 μm, dried at 100 ° C. for 5 minutes, and crosslinked an adhesive layer. A pressure-sensitive adhesive tape formed with was obtained. The physical property test of this adhesive tape was performed in the same manner as in Example 1. The results are shown in Table 5.

Comparative Example 9 A monomer composition was prepared by adding 79 parts by weight of n-butyl acrylate,
An adhesive tape was obtained in the same manner as in Example 1 except that 20 parts by weight of ethyl acrylate and 1 part by weight of N-isopropylacrylamide were used, and a physical property test was conducted. The results are shown in Table 5.

Comparative Example 10 Monomer composition was changed to 2-ethylhexyl acrylate 65
An adhesive tape was obtained in the same manner as in Example 1 except that the amount was 35 parts by weight and N-isopropylacrylamide was 35 parts by weight. The results are shown in Table 5.

The results of Comparative Example 1 are shown in Table 5 again.

[0082]

[Table 5]

As is clear from Table 5, as in the examples of the present invention, the monomer copolymerizable with the (meth) acrylic acid ester, and N was used as the cohesive force component of the copolymerized acrylic copolymer. -The one using a specific amount of isopropylacrylamide is excellent in sticking property with time to a soft vinyl chloride resin containing a plasticizer. On the other hand, as in the comparative example, even when conventional acrylic acid is used as the cohesive force component or N-isopropylacrylamide is used, those used within a specific amount range contain a plasticizer. It is inferior in pasting property to soft vinyl chloride resin.

Example 20 A monomer composition was prepared by adding 95 parts by weight of n-butyl acrylate,
N-vinyl caprolactam is 5 parts by weight except that
An adhesive tape was produced in the same manner as in Example 1, and the physical properties were measured. The results are shown in Table 6.

Example 21 Monomer composition was changed to 2-ethylhexyl acrylate 65
An adhesive tape was produced and physical properties were measured in the same manner as in Example 1 except that parts by weight, vinyl acetate 15 parts by weight, and N-vinylcaprolactam 20 parts by weight were used. The results are shown in Table 6
Shown in.

Example 22 A monomer composition was prepared by mixing 70 parts by weight of isononyl acrylate with
An adhesive solution was obtained in the same manner as in Example 1 except that 20 parts by weight of n-butyl methacrylate and 10 parts by weight of N-vinylcaprolactam were used. To this adhesive solution, 15 parts by weight of a rosin-based tackifying resin (manufactured by Arakawa Chemical Co., Ltd .: trade name "Super Ester A-115") was added, and an adhesive tape was obtained in the same manner as in Example 1 and a physical property test was conducted. .. The results are shown in Table 6.

Example 23 The same as Example 1 except that the monomer composition was 69.8 parts by weight of n-butyl acrylate, 0.2 parts by weight of 2-hydroxyethyl methacrylate, and 30 parts by weight of N-vinylcaprolactam. To obtain an adhesive solution. To this adhesive solution, 10 parts by weight of a xylene resin-based tackifying resin (manufactured by Mitsubishi Oil Co., Ltd .: trade name "Oligotech 2300"),
10 parts by weight of dioctyl phthalate as a plasticizer and 1.0 part by weight of an isocyanate cross-linking agent (“Coronate L” manufactured by Nippon Polyurethane Co., Ltd.) as a cross-linking agent were added, and this adhesive solution was applied onto a polyester film having a thickness of 38 μm. After coating, it was dried at 100 ° C. for 5 minutes to obtain a pressure-sensitive adhesive tape on which a crosslinked pressure-sensitive adhesive layer was formed. The physical property test of this adhesive tape was performed in the same manner as in Example 1. The results are shown in Table 6.

Comparative Example 11 A monomer composition was prepared by adding 79 parts by weight of n-butyl acrylate,
An adhesive tape was obtained in the same manner as in Example 1 except that 20 parts by weight of ethyl acrylate and 1 part by weight of N-vinylcaprolactam were used, and a physical property test was conducted. The results are shown in Table 6.

Comparative Example 12 Monomer composition was changed to 2-ethylhexyl acrylate 65
An adhesive tape was obtained in the same manner as in Example 1 except that the amount of the adhesive tape was 35 parts by weight and the amount of N-vinylcaprolactam was 35 parts by weight. The results are shown in Table 6.

The results of Comparative Example 1 are shown in Table 6 again.

[0091]

[Table 6]

As is clear from Table 6, as in the examples of the present invention, a monomer copolymerizable with a (meth) acrylic acid ester, and N was used as a cohesive force component of the copolymerized acrylic copolymer. -The one using a specific amount of vinylcaprolactam is excellent in sticking property with time to a soft vinyl chloride resin containing a plasticizer. On the other hand, as in the comparative example, conventional acrylic acid is used as the cohesive force component, or N
-Even when vinylcaprolactam is used, the one used in a range outside the specific amount is inferior in the ability to stick to a soft vinyl chloride resin containing a plasticizer with time.

Example 24 70 parts by weight of n-butyl acrylate, 24 parts by weight of 2-ethylhexyl acrylate, 5 parts by weight of methyltriglycol acrylate, 1 part by weight of polyethylene glycol methacrylate, a photopolymerization initiator (manufactured by Merck: trade name "Darocur" 2959 ") 0.1 part by weight was stirred and mixed until uniform. This mixed solution was placed in an ultraviolet-transparent glass container, and dissolved oxygen was removed by purging with nitrogen gas. Further, the glass container was irradiated with ultraviolet rays to partially polymerize it. At this time, the viscosity was 550 cps and the conversion rate was 4.0%.

To the obtained reactive thickening composition, 0.03 part by weight of hexanediol diacrylate and 1 part by weight of a photopolymerization initiator (manufactured by Merck: trade name "Darocur 2959") were added and mixed. The mixed solution was coated on a PET film with a thickness of 38 μm whose surface was corona-treated with a comma coater so that the thickness was 70 μm, and the oxygen concentration was 30
Using an ultra-high pressure mercury lamp as a radiation source in an inert zone of 0 ppm, the lamp intensity of the irradiation surface was 8 mw / cm ² [36
The lamp height was set so that the intensity value measured with a light intensity measuring instrument UVR-1 (manufactured by Tokyo Optical Instruments Co., Ltd.) having a maximum sensitivity of 5 nm] was 2 minutes, and an adhesive tape was obtained. A physical property test was conducted in the same manner as in Example 1. The results are shown in Table 7.

Example 25 A monomer composition was prepared by adding 60 parts by weight of n-butyl acrylate and
An adhesive tape was obtained in the same manner as in Example 24 except that 32 parts by weight of isooctyl acrylate, 7 parts by weight of N-vinylcaprolactam, and 1 part by weight of N, N-dimethylaminoethyl acrylate were used. A physical property test was conducted in the same manner. The results are shown in Table 7. Example 26 Monomer composition of n-butyl acrylate 70 parts by weight, ethyl acrylate 20 parts by weight, acryloyl morpholine 8
An adhesive tape was obtained in the same manner as in Example 24, except that the amount was 2 parts by weight and the amount of N-vinylpyridine was 2 parts by weight. The results are shown in Table 7.

Example 27 A monomer composition was prepared by adding 60 parts by weight of n-butyl acrylate and
An adhesive tape was obtained in the same manner as in Example 24, except that 30 parts by weight of 2-ethylhexyl acrylate, 5 parts by weight of vinyl acetate, and 5 parts by weight of N-isopropylacrylamide were used, and a physical property test was performed in the same manner as in Example 1. went. The results are shown in Table 7.

Comparative Example 13 Monomer composition was changed to 70 parts by weight of n-butyl acrylate,
Isooctyl acrylate 20 parts by weight, acrylic acid 10
An adhesive tape was obtained in the same manner as in Example 24 except that the weight part was used, and a physical property test was performed in the same manner as in Example 1.
The results are shown in Table 7.

The results of Comparative Example 1 are shown in Table 7.

[0099]

[Table 7]

As is clear from Table 7, as in the examples of the present invention, a monomer that is copolymerized with a (meth) acrylic acid ester, and a polyacrylic acid is used as a cohesive force component of the copolymerized acrylic copolymer. Those using a specific amount of an acrylic monomer having an ether type side chain are excellent in sticking property with time to a soft vinyl chloride resin containing a plasticizer. On the other hand, as in the comparative example, the one using conventional acrylic acid as the cohesive force component is inferior in the time-sensitive sticking property to the soft vinyl chloride resin containing the plasticizer.

[0101]

Since the pressure-sensitive adhesive composition according to the invention of claims 1 and 2 of the present application has the above-mentioned constitution, even if the plasticizer in the soft vinyl chloride resin migrates into the pressure-sensitive adhesive, The adhesive strength does not decrease.

Since the pressure-sensitive adhesive tape, label or sheet according to the invention of claim 3 of the present application is constructed as described above,
Even if the plasticizer is transferred, the adhesive performance of the adhesive layer does not deteriorate, and the adhesive layer can be suitably used as an adhesive tape, label or sheet for soft vinyl chloride resin.

Claims (3)

[Claims] 1. A general formula: (In the formula, R ₁ is hydrogen or a methyl group, and R ₂ has 4 carbon atoms.
~ 14 alkyl groups) (meth) acrylate 1
60% by weight or more (in the monomer component) of the seeds and the general formula: (In the formula, R ₃ , R ₄ , and R ₅ are hydrogen or a methyl group, provided that R ₄ and R ₅ are not the same, R ₆ is hydrogen or an alkyl group having 4 or less carbon atoms, and m and n are not 0 at the same time. An integer of 1 to 20) and 3 to 20% by weight (in the monomer component) of at least one monomer represented by the formula (1) are mainly contained in the acrylic copolymer. 2. A general formula: (In the formula, R ₁ is hydrogen or a methyl group, and R ₂ has 4 carbon atoms.
~ 14 alkyl groups) (meth) acrylate 1
50% by weight or more of seeds (in the monomer component) and N, N--
3 to 30% by weight of one or more monomers selected from dimethylaminoethyl acrylate, N-vinylpyridine, acryloylmorpholine, N-isopropylacrylamide and N-vinylcaprolactam (in the monomer component)
A pressure-sensitive adhesive composition comprising an acrylic copolymer having as a main component a monomer as a main component. 3. An adhesive tape, label or sheet comprising the adhesive composition according to claim 1 or 2.