JPS6031234B2 - Cationic release agent - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a release agent used as a back treatment agent for pressure-sensitive adhesive tapes and adhesive sheets, and a surface treatment agent for release paper, and particularly to a release treatment agent mainly composed of a cationic polymer. Conventionally, known release agents for this purpose include (long mirror alkyl) polymer compounds such as acrylic acid-based, polyester-based, and polyamide-based polymers with long mirror alkyl groups bonded to them, and polyorganosiloxane-based (silicon) compounds. It is widely used by applying it to the back of adhesive tape, the back of adhesive sheet, or the surface of release paper. However, in order for these release agents to exhibit sufficient functionality, they must have good releasability with the adhesive, excellent adhesion to tape or sheet substrates, good heat resistance, and good releasability with the adhesive during feeding. It is important to have properties such as no compatibility with adhesives, and it is also important to be easy to process without requiring any special operations during the processing process. The antinomic nature of being fixed is fundamental. However, the conventional release treatment agents mentioned above lack either the release effect on the adhesive, the sustainability of the effect over time, or the adhesion to the base material, or, like silicone, they use a cross-linking agent during treatment, making it special. At present, there is still no satisfactory treatment agent that requires extensive heat treatment. The present inventors conducted various studies on a release agent that does not have the above-mentioned drawbacks, and were able to complete the present invention. It aims to satisfy the contradictory properties mentioned above. That is, the present invention provides polymers of quaternary ammonium salt monomers having one vinyl group and one to three long chain groups bonded to nitrogen atoms in one molecule, or these quaternary ammonium salt monomers. A pressure-sensitive adhesive whose main component is a copolymer with a pinyl monomer containing at least 50 mol% or more, and the quaternary ammonium salt is a compound represented by the general formula [1] or [B]. A cationic release agent for tapes or adhesive sheets. (However, in the formula [1], R is a hydrogen atom or a methyl group, R
2 is an alkyl group having 1 to 3 carbon atoms, at least one of R3, R4, and R5 is an alkyl group having 8 to 26 carbon atoms, and the others are hydrogen atoms or alkyl groups having 1 to 3 carbon atoms, and Z represents -○- or -NH-, and X represents a halogen or an alkyl sulfate having 1 to 3 carbon atoms. In addition, [0) in the formula, R6 is an alkyl group having 8 to 26 carbon atoms,
X represents halogen. ) Examples of the compound represented by formula [1] include diethyl[2-(methacryloxyl)ethyl]cetylammonium, dimethyl[2-(acryloxyl)ethyl]stearyl bromide, meccrylamidopropylene dimethyl behe Examples include nyl ammonium bromide. Also, the expression

Examples of the compound represented by [0] include lauryl-4-vinylpyridinium chloride, stearyl-4-vinylpyridinium furomide, and behenyl-4-vinylpyridinium chloride. On the other hand, the vinyl monomer used in the copolymer of the present invention
Suitable examples include vinyl acetate, lower alkyl acrylate or methacrylate having 1 to 4 carbon atoms, glycidyl methacrylate, but are not limited thereto. As mentioned above, the release agent of the present invention is characterized by having a cationic polymer, which is a quaternary ammonium salt, as its main component, so it is particularly excellent for negatively charged substrates such as kraft paper and cellophane paper. On the other hand, due to the bonding of long-chain groups such as long-chain alkyl groups, it exhibits a strong peeling effect against adhesives, and fully satisfies the above-mentioned contradictory properties. In addition, in the processing process, it is easy to work as it does not require any special operations as it can be simply dissolved in a solvent and applied, and unlike silicone, it does not smudge against oil-based ink, making it possible to print beautifully on the treated surface. It has the practical feature that it can be carried out. Furthermore, it has various excellent properties such as extremely little deterioration in effectiveness due to sewing days, good heat resistance, and no affinity with adhesives during flooding. The release agent of the present invention will be explained in more detail with reference to Examples below. In addition, in the examples, parts represent parts by weight. Example 1 Dimethyl [2 (methacryloxyl)
Add 10 parts of ethyl cetyl ammonium chloride, 15 parts of toluene, and 53 parts of methanol, and heat until the mixed solution becomes completely transparent and dissolved. Next, azobisisobutyronitrile (A
A solution in which 1 part of IBN) was dissolved in 3 $ of toluene was added dropwise over half an hour into the reaction mixture maintained at 40°C under a nitrogen atmosphere, and after the dropwise addition was completed, the temperature was raised to 60°C. 6 at the same temperature
Allow time to polymerize. After the polymerization was completed, the mixture was cooled to room temperature and poured onto 100 parts of acetone to precipitate the polymer, which was then over-dried to obtain a white powdery polymer. The polymer thus obtained was dissolved in a toluene-ethyl alcohol mixed solvent (mixing ratio of 1:1), and the solution was applied as a fixative on kraft paper and cellophane paper at a rate of 0.2±0.1 μm/day. Apply and dry as shown. In this way, 24 strips of rubber-based adhesive polyester tape (manufactured by Nichiban Co., Ltd.) with a weight of 2 kg were placed on the coated base material prepared.
Paste by moving the rubber roller 9 back and forth 5 times,
The peeling force was determined by measuring the load when peeling in the 180 degree direction at a peeling rate of 30 skins/min using an autograph (P-10 model manufactured by Shimadzu Corporation). At the same time, a similar operation was performed on a homogeneous base material to which no release agent was applied, and the ratio of the peeling force at this time to the above-mentioned peeling force was expressed as relative peeling force. On the other hand, a sample to which adhesive tape was attached was kept at a temperature of 50 ± 1°C for 2 hours with a load applied for 20 minutes, and after being left at room temperature for 2 hours, the peeling force was determined in the same manner to determine the heat resistance. It was judged. The results of these measurements are shown in Tables 1 and 2, and as is clear from the tables, the peeling force is excellent and sufficient peeling performance is maintained even after being kept at high temperatures. In addition, the comparative example is stearyl methacrylate 2
2 parts, 13 parts of acrylic acid in ethyl acetate with 70 CO
The peeling force was measured using a polymer solution obtained by polymerizing for a period of time and applying the same amount in the same manner as above. Example 2 Into a reactor similar to Example 1, 10 parts of dimethyl[2-(methacryloxyl)ethyl]stearylfuromide, 15 parts of toluene, and 5 parts of methyl alcohol were added, and AIB was added.
A solution of NI part dissolved in 30 parts of Treso was added as a polymerization initiator in the same manner as in Example 1, polymerized at 60 qo for 6 hours, and then added to acetone to obtain a white powdery polymer. Each peel force was measured by the method described in Example 1. Each peel force shows excellent values as shown in Tables 1 and 2. Example 3 In a reaction vessel similar to Example 1, 88.7 g of methacrylamide propyl diethylstearylammonium bromide was added.
11.3 parts of butyl acrylate, 150 parts of toluene and 53 parts of methyl alcohol were added dropwise in the same manner as in Example 1, using a solution of YamaBNI dissolved in 3 parts of toluene as a polymerization initiator. The peeling force was measured by the method described in Example 1 for a white powdery polymer obtained by polymerizing for a period of time and pouring onto acetone. Each peeling force shows excellent peeling properties as shown in Tables 1 and 2. Example 4 Methacrylamide in a reaction vessel similar to Example 1. Lopyrudimethylbehenyl ammonium bromide 92
1 part, 8 parts of glycidyl methacrylate, 150 parts of toluene, and 53 parts of methyl alcohol were added, and a solution of MBNI part dissolved in 3 parts of toluene was used as a polymerization initiator. The peeling force of the white powdery polymer obtained by dipping onto acetone was measured by the method described in Example 1, and the results are shown in Tables 1 and 2. Example 5 Into a reaction vessel similar to Example 1, 100 parts of staryruvinylpyridinium chloride, 15 parts of toluene, and 53 parts of methanol were added, and as in Example 1, a solution of MBN in toluene (1:30 ) in a nitrogen atmosphere at 4000 ml,
The mixture was polymerized at 60q○ for 6 hours, poured onto acetone to precipitate the polymer, and was over-dried to obtain a white powdery polymer. The peeling performance was measured in the same manner as in Example 1, and the results are shown in Tables 1 and 2. Example 6 In a reaction vessel similar to Example 1, 8 parts of behenyl-4-pinylpyridinium bromide, 11 parts of glycidyl methacrylate, 150 parts of toluene, and 53 parts of methanol were placed, and as in Example 1, toluene of AIBN was added. solution (1:30
) were added dropwise in a nitrogen atmosphere, polymerized at 60°C for 6 hours, and poured onto acetone to precipitate the polymerization. Then, the precipitate was filter dried to obtain a white powdery polymer. Table 1 shows the results of measuring the peeling performance in the same manner as in Example 1.
and shown in Table 2. Table 1 Table 2

Claims (1)

[Scope of Claims] 1. A polymer of a quaternary ammonium salt monomer having one vinyl group and one to three long-chain alkyl groups or long-chain substituted alkyl groups bonded to a nitrogen atom in one molecule; or At least 5 of these quaternary ammonium salt monomers
The main component is a copolymer with a vinyl monomer containing 0 mol% or more, and the quaternary ammonium salt is a compound represented by the general formula [I] or [II]. A cationic release agent for pressure-sensitive adhesive tapes or adhesive sheets. (However, in the [I] formula, R_1 is a hydrogen atom or a methyl group,
R_2 is an alkyl group having 1 to 3 carbon atoms, R_3, R_4,
At least one of R_5 is an alkyl group having 8 to 26 carbon atoms, the others are hydrogen atoms or alkyl groups having 1 to 3 carbon atoms, Z is -O- or -NH-, and X is halogen or a carbon number 1 to 3 alkyl sulfates are shown. Further, in the formula [II], R_6 represents an alkyl group having 8 to 26 carbon atoms, and X represents a halogen. ) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼