JP5345599B2 - Release agent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a releasable treating agent, which can form a releasable plane having moderate force and requires no selectivity to a base material because low-temperature baking is possible at the time of forming the releasing plane, and further, in which regardless of excellent materials capable of writing with a pen and the like on the formed releasing plane, the materials for forming the releasing plane are useful also for environmental friendliness. <P>SOLUTION: The releasable treating agent contains a resin having a siloxane segment, wherein the resin contains a polysiloxane-modified polyhydroxy polyurethane resin derived from the reaction of a 5-membered cyclic carbonate compound and an amine-modified polysiloxane compound. <P>COPYRIGHT: (C)2012,JPO&amp;INPIT

Description

  The present invention relates to a releasable treatment agent, and more specifically, in a product using an adhesive such as an adhesive tape, an adhesive label, and an adhesive sheet, a substrate back surface such as a tape or a sheet that is in contact with the adhesive surface, and a release paper. It is related with the peelable processing agent which can make the surface of a peelable.

  Conventionally, as the releasable treatment agent used for the above purpose, there are known polymer compounds and polysiloxane compounds such as acrylic acid-based, polyester-based and polyamide-based compounds having a long-chain alkyl group bonded thereto. By using these compounds, the release surface is formed by imparting peelability to the back surface of the pressure-sensitive adhesive tape or pressure-sensitive adhesive sheet or the surface of the release paper. And among the above-mentioned, it is well-known that a polysiloxane type compound is excellent in characteristics, such as peelability and residual adhesiveness (for example, refer patent documents 1-3 etc.).

  However, polysiloxane compounds have too strong peelability, making it difficult to obtain an appropriate peel force, and require high-temperature baking when applied to a substrate. There was a problem that could not be used. Moreover, since the adhesiveness with respect to a base material is inadequate depending on the base material to be used, there existed a fault that it could not be utilized for all kinds of base materials.

  In addition, since the conventional polysiloxane compound having a strong peeling performance has a small critical surface tension, there is a problem with respect to the writing property that writing cannot be performed on the peeling surface formed by applying the compound. Further, when a pressure-sensitive or heat-sensitive adhesive is applied to such a peeled surface, there is a problem that a repellency phenomenon often occurs and a good coated surface cannot be formed.

  As a method for solving the above-mentioned problems, the present applicant has previously been able to perform low-temperature baking by using a silicone copolymer, and has good adhesion to a substrate and writing on a release surface. An excellent releasability treatment agent that has been combined has been proposed (see Patent Document 4 and Patent Document 5).

  On the other hand, due to the recent increase in environmental problems, many manufacturers are actively working on environmental measures, and there is a movement to construct products using materials with excellent environmental conservation. On the other hand, releasable tapes, releasable sheets, release paper, etc. that use releasable treatment agents are difficult to recycle after use and become a large amount of waste, so the development of environmentally friendly products is required. . On the other hand, the conventional technologies as described above have room for improvement in terms of solutions from the viewpoint of global environmental protection problems.

As a useful thing from the said viewpoint, the polyhydroxy polyurethane resin using a carbon dioxide as a raw material is known, for example, as seen in nonpatent literatures 1 and 2. However, the actual situation is that the application development is not progressing. This is because the characteristics are clearly inferior to those of polyurethane-based resins, which are compared as high-molecular compounds of the same type (see Patent Documents 6 and 7).
On the other hand, the global warming phenomenon, which is thought to be caused by the ever-increasing carbon dioxide in recent years, has become a global problem, and the reduction of carbon dioxide emissions has become an important issue worldwide. . In addition, from the perspective of exhaustible petrochemical resources (petroleum), the shift to renewable resources such as biomass and methane has become a global trend, and technological development from the perspective of application to global environmental protection issues is extremely important. It has become a thing.

  Against the background as described above, the polyhydroxy polyurethane resin has been reviewed again. In other words, carbon dioxide, the raw material for this resin, is an easily available and sustainable carbon resource, and plastics made from carbon dioxide are effective in solving problems such as global warming and resource depletion. This is because it can be a simple means.

Japanese Patent Laid-Open No. 01-215857 Japanese Patent Laid-Open No. 02-298551 Japanese Patent Laid-Open No. 03-41153 JP-A-01-126389 JP 02-1113015 A US Pat. No. 3,072,613 JP 2000-319504 A

N. Kihara, T. Endo, J. Org. Chem., 1993, 58, 6198 N. Kihara, T. Endo, J. Polymer Sci., Part A Polmer Chem., 1993, 31 (11), 2765

  In recent years, fields of application such as pressure-sensitive adhesive tapes, pressure-sensitive adhesive labels, and pressure-sensitive adhesive sheets have been expanding, and accordingly, further improvement in performance with respect to releasable treatment agents has been required. On the other hand, as described above, peelable tapes, peelable sheets, release paper, etc. are difficult to recycle after use and become a large amount of waste. Development is anxious.

  Accordingly, an object of the present invention is to form a peelable treatment layer (peeling surface) having an appropriate peeling force, and since it can be baked at a low temperature when forming the peeling surface, there is no selectivity for the substrate. Furthermore, another object of the present invention is to provide a releasable treatment agent in which the material for forming the release surface also contributes to environmental conservation while being writable with a pen or the like on the formed release surface.

  The above object is achieved by the present invention described below. That is, the present invention relates to a releasable treating agent containing a resin having a siloxane segment, wherein the resin is derived from a reaction between a 5-membered cyclic carbonate compound and an amine-modified polysiloxane compound. A releasable treating agent comprising a resin is provided.

  According to the present invention, as a resin having a siloxane segment, a specific polysiloxane-modified polyhydroxypolyurethane resin is used to form a release surface, which can be baked at a low temperature and has excellent selectivity and no applicability to the substrate. The release surface formed can be written with a pen or the like, and has an appropriate release force. Further, the above-mentioned resin characterizing the present invention is a releasable treatment agent that is also useful from the viewpoint of global environmental conservation because carbon dioxide, which is a global warming gas, can be used as its raw material. Products imparted with peelability by a chemical treatment agent become environmentally friendly products that contribute to global environmental conservation.

Infrared absorption spectrum of epoxy compound A (trade name: Epicoat 828, manufactured by Japan Epoxy Resin Co., Ltd.) used in Production Example 1. The infrared absorption spectrum of the 5-membered cyclic carbonate compound (1-A) obtained in Production Example 1. The GPC elution curve of a 5-membered cyclic carbonate compound (1-A). Mobile phase: THF, column: TSK-Gel GMHXL + G2000HXL + G3000HXL, detector: IR

Next, the present invention will be described in more detail with reference to preferred embodiments.
The polysiloxane-modified polyhydroxypolyurethane resin characterizing the present invention is obtained from the reaction of a 5-membered cyclic carbonate compound with an amine-modified polysiloxane compound.

  The 5-membered cyclic carbonate compound used in the present invention can be produced by reacting an epoxy compound and carbon dioxide as shown by the following [Formula-A]. More particularly, the epoxy compound is oxidized in the presence or absence of an organic solvent and in the presence of a catalyst at a temperature of 40 ° C. to 150 ° C. under atmospheric pressure or slightly elevated pressure for 10 to 30 hours. Obtained by reacting with carbon.

  Examples of the epoxy compound that can be used above include the following compounds.

  The epoxy compounds listed above are preferable compounds used in the present invention, and the present invention is not limited to these exemplified compounds. Accordingly, not only the compounds exemplified above, but also any other compounds that are currently commercially available and can be easily obtained from the market can be used in the present invention.

The 5-membered cyclic carbonate compound as described above can be produced by reacting an epoxy compound with carbon dioxide, and examples of the catalyst used in the reaction include the following base catalyst and Lewis acid catalyst. .
Examples of the base catalyst include tertiary amines such as triethylamine and tributylamine, cyclic amines such as diazabicycloundecene, diazabicyclooctane, and pyridine, lithium chloride, lithium bromide, lithium fluoride, and sodium chloride. Alkaline metal salts, alkaline earth metal salts such as calcium chloride, quaternary ammonium salts such as tetrabutylammonium chloride, tetraethylammonium bromide, benzyltrimethylammonium chloride, carbonates such as potassium carbonate and sodium carbonate, zinc acetate, lead acetate Metal acetates such as copper acetate and iron acetate, metal oxides such as calcium oxide, magnesium oxide and zinc oxide, and phosphonium salts such as tetrabutylphosphonium chloride.

  Examples of the Lewis acid catalyst include tin compounds such as tetrabutyltin, dibutyltin dilaurate, dibutyltin diacetate, and dibutyltin octoate.

  The amount of the catalyst is 0.1 to 100 parts by mass, preferably 0.3 to 20 parts by mass, per 50 parts by mass of the epoxy compound. If the amount used is less than 0.1 parts by mass, the effect as a catalyst is small, and if it exceeds 100 parts by mass, various performances of the final resin may be deteriorated. However, in the case where the residual catalyst causes a serious performance deterioration, it may be configured to be removed by washing with pure water.

  Examples of the organic solvent that can be used in the reaction of the epoxy compound and carbon dioxide include dimethylformamide, dimethylsulfoxide, dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, and tetrahydrofuran. These organic solvents and other poor solvents such as methyl ethyl ketone, xylene, toluene, tetrahydrofuran, diethyl ether, and cyclohexanone may be used in a mixed system.

  The polysiloxane-modified polyhydroxypolyurethane resin used in the present invention comprises, as shown by the following [Formula-B], a 5-membered cyclic carbonate compound obtained as described above and an amine-modified polysiloxane compound in an organic form. It can obtain by making it react at the temperature of 20 to 150 degreeC in presence of a solvent.

  Examples of the amine-modified polysiloxane compound used in the above reaction include the following compounds.

  The amine-modified polysiloxane compounds listed above are preferable compounds used in the present invention, and the present invention is not limited to these exemplified compounds. Accordingly, not only the above-exemplified compounds but also any other compounds that are currently commercially available and can be easily obtained from the market can be used in the present invention.

  In the polysiloxane-modified polyhydroxypolyurethane resin obtained as described above, the proportion of the polysiloxane segment in the resin molecule is such that the content is 10 to 75% by mass with respect to the resin molecule. It is preferable. If it is less than 10 mass%, the expression of the peelable function accompanying the surface energy based on the polysiloxane segment will be insufficient. On the other hand, if it exceeds 75% by mass, the performance of the polysiloxane-modified polyhydroxyurethane resin such as mechanical strength and abrasion resistance becomes insufficient, such being undesirable. More preferably, it is 20-70 mass%, More preferably, it is 30-60 mass%.

  Moreover, the number average molecular weight (standard polystyrene conversion value measured by GPC) of the polysiloxane-modified polyhydroxypolyurethane resin of the present invention is preferably 2,000 to 100,000, more preferably about 5,000 to 70,000. It is.

  In the polysiloxane-modified polyhydroxypolyurethane resin of the present invention, the hydroxyl group produced by the reaction of the 5-membered cyclic carbonate group with the amine-modified polysiloxane compound brings about further improvement in the performance of the peelable treatment agent of the present invention. Become. Since the hydroxyl group has hydrophilicity, the adhesion to the substrate can be improved, and further the peelability can be improved by utilizing the reaction between the hydroxyl group and a crosslinking agent.

  The hydroxyl value of the polysiloxane-modified polyhydroxypolyurethane resin of the present invention is preferably 20 to 300 mgKOH / g. When the hydroxyl value is less than the above range, the effect of reducing carbon dioxide is insufficient, while when it exceeds the above range, various physical properties as a polymer compound are insufficient.

  The film formed from the polysiloxane-modified polyhydroxypolyurethane resin described above functions sufficiently as a peelable treatment layer (release layer) as it is, but it is also preferable to form a crosslinked film by combining with a crosslinking agent. It is a form. Specifically, if a cross-linked film is formed by combining with a cross-linking agent that reacts with a hydroxyl group in the polysiloxane-modified polyhydroxy polyurethane resin, the releasable treatment layer (release layer) is more stable. Peeling performance and heat resistance can be imparted. As the crosslinking agent that can be used in this case, any crosslinking agent that reacts with a hydroxyl group can be used and is not particularly limited. For example, an alkyl titanate compound or a polyisocyanate compound can be mentioned, and a known polyisocyanate compound conventionally used for crosslinking of a polyurethane resin is preferable. Examples include adducts of polyisocyanates having the following structural formula and other compounds.

  Further, the releasable treatment agent of the present invention is suitable for coating on a base sheet when used, improving film formability, and adjusting the content of the polysiloxane segment to achieve an appropriate peel force. Therefore, various conventionally known binder resins can be mixed and used. As the binder resin, those capable of chemically reacting with a crosslinking agent such as the above-mentioned polyisocyanate adduct are preferable, but those having no reactivity can also be used in the present invention.

  As these binder resins, conventionally used various resins can be used and are not particularly limited. For example, acrylic resin, polyurethane resin, polyester resin, polybutadiene resin, silicone resin, melamine resin, phenol resin, polyvinyl chloride resin, cellulose resin, alkyd resin, modified cellulose resin, fluorine resin, polyvinyl butyral resin, epoxy resin, polyamide resin Etc. can be used. Also, resins obtained by modifying various resins with silicone or fluorine can be used. When these binder resins are used in combination, the amount used is preferably 5 to 90% by mass, more preferably about 10 to 60 parts by mass with respect to 100 parts by mass of the polysiloxane-modified polyhydroxypolyurethane resin of the present invention.

  The base material to which the peelable treatment layer (peeling surface) is to be formed using the peelable treatment agent of the present invention is not particularly limited, and known materials such as paper, laminated paper, and synthetic resin film are used. It can be arbitrarily selected and used.

  Paper base materials include high-quality paper, kraft paper, semi-glassine paper, glassine paper, imitation paper, copy paper, newspaper paper, resin-laminated paper obtained by laminating various types of paper with plastic resin, and water-soluble in various types of paper. And various coated papers and synthetic papers that have been subjected to a water-resistant resin, a moisture-proof coat, and a sizing treatment.

  Film base materials include polyolefin film, polyester film, polyamide film, acetate film, polycarbonate film, polyvinyl chloride film, polyvinylidene chloride film, various biodegradable films, various plant-derived films, and various metal-deposited films. And various metal oxide vapor-deposited films.

  Although the method of forming a peelable treatment layer (peeling surface) using the peelable treatment agent of the present invention is not particularly limited, the following methods may be mentioned. A product obtained by dissolving or dispersing a polysiloxane-modified polyhydroxypolyurethane resin in an appropriate organic solvent is used as a releasable treatment agent of the present invention, and for example, a wire bar method, a gravure printing method, a screen printing method, a gravure plate It can be applied by a forming means such as the reverse roll coating method used and dried. The drying temperature is preferably in the range of 50 to 120 ° C. The thickness of the peelable treatment layer is preferably 0.001 to 5.00 μm. If it is less than 0.001 μm, the peeling performance deteriorates, and if it exceeds 5.00 μm, the release sheet is wound into a roll shape, or the trouble due to bulkiness when laminated and the peelable treatment layer and the coating back surface are blocked during storage. This is not preferable because of fear. More preferably, it is 0.01-2.0 micrometers.

The releasable treatment agent of the present invention has excellent releasability because the non-adhesiveness of the polysiloxane segment is imparted because the polysiloxane segment is oriented on the surface when applied to a substrate sheet or the like. It becomes possible to form the peelable treatment layer shown. At the same time, the hydroxyl group of the polysiloxane-modified polyhydroxypolyurethane resin interacts strongly with the substrate sheet at the interface, so that excellent performance such as excellent adhesion to the substrate and flexibility can be obtained. Further, from the viewpoint of reducing greenhouse gases, according to the release treating agent of the present invention using a resin incorporating carbon dioxide in the structure of that, the provision of environmentally friendly products that could not be reached by conventional Is possible.

  Next, the present invention will be described in more detail with reference to specific production examples, polymerization examples, examples, and comparative examples, but the present invention is not limited to these examples. In the following examples, “part” and “%” are based on mass unless otherwise specified.

<Production Example 1> (Production of 5-membered cyclic carbonate compound)
In a reaction vessel equipped with a stirrer, a thermometer, a gas introduction pipe and a reflux condenser, a divalent epoxy compound A represented by the following formula A (Japan Epoxy Resin Co., Ltd., Epicoat 828; epoxy equivalent 187 g / mol) 100 parts, 100 parts of N-methylpyrrolidone and 1.5 parts of sodium iodide were added and dissolved uniformly. FIG. 1 is an infrared absorption spectrum of the divalent epoxy compound A. Thereafter, the mixture was heated and stirred at 80 ° C. for 30 hours while bubbling carbon dioxide at a rate of 0.5 liter / min.

  After completion of the reaction, the obtained solution was gradually added to 300 parts of n-hexane with high speed stirring at 300 rpm. Thereafter, the produced powdery product was filtered with a filter, and the filtrate was further washed with methanol to remove N-methylpyrrolidone and sodium iodide. The powder was dried in a drier to obtain 118 parts (yield 95%) of a white powder 5-membered cyclic carbonate compound (1-A).

As shown in FIG. 2, the infrared absorption spectrum (Horiba FT-720) of the obtained product was such that the peak derived from the epoxy group in the vicinity of 910 cm ⁻¹ disappeared substantially in the product, and 1,800 cm ^−1. Absorption of a carbonyl group of a cyclic carbonate group not present in the raw material was confirmed in the vicinity. Moreover, the number average molecular weight of the product was 414 (polystyrene conversion, Tosoh; GPC-8220) as shown in FIG. In the obtained 5-membered cyclic carbonate compound (1-A), 19% of carbon dioxide was immobilized.

<Production Example 2> (Production of 5-membered cyclic carbonate compound)
Instead of using the divalent epoxy compound A used in Production Example 1, a divalent epoxy compound B represented by the following formula B (manufactured by Toto Kasei Co., Ltd., YDF-170; epoxy equivalent 172 g / mol) was used. The reaction was conducted in the same manner as in Production Example 1 to obtain 121 parts (yield 96%) of a white powder 5-membered cyclic carbonate compound (1-B). The obtained product was confirmed by infrared absorption spectrum, GPC and NMR in the same manner as in Production Example 1. As a result, 20.3% of carbon dioxide was immobilized in the obtained 5-membered cyclic carbonate compound (1-B).

<Production Example 3> (Production of 5-membered cyclic carbonate compound)
Instead of the divalent epoxy compound A used in Production Example 1, a divalent epoxy compound C represented by the following formula C (manufactured by Nagase ChemteX Corporation, EX-212; epoxy equivalent 151 g / mol) was used. The reaction was conducted in the same manner as in Production Example 1 to obtain 111 parts (yield 86%) of a colorless and transparent liquid 5-membered cyclic carbonate compound (1-C). The obtained product was confirmed by infrared absorption spectrum, GPC and NMR in the same manner as in Production Example 1. As a result, 22.5% of carbon dioxide was immobilized in the obtained 5-membered cyclic carbonate compound (1-C).

<Exemplary polymerization examples 1 to 3> (Production of polysiloxane-modified polyhydroxypolyurethane resin)
Using the 5-membered cyclic carbonate compounds obtained in Production Examples 1 to 3, polysiloxane-modified polyhydroxypolyurethane resins used in the examples were synthesized by the following procedure. First, a reaction vessel equipped with a stirrer, a thermometer, a gas introduction tube, and a reflux condenser was replaced with nitrogen, and each 5-membered cyclic carbonate compound and N in the solution were added so that the solid content of the solution was 35%. -Methylpyrrolidone was added and dissolved uniformly. Next, a predetermined equivalent amount of each amine-modified polysiloxane compound described in Table 1 was added and stirred for 10 hours at a temperature of 90 ° C., and reacted until no amine-modified polysiloxane compound could be confirmed. Table 3 shows the properties of the obtained three types of polysiloxane-modified polyhydroxypolyurethane resins with a solid content of 35%.

<Comparative polymerization example 1> (Production of polyhydroxypolyurethane resin)
A reaction vessel equipped with a stirrer, a thermometer, a gas introduction pipe and a reflux condenser was replaced with nitrogen so that the 5-membered cyclic carbonate compound obtained in Production Example 1 and the solid content of the liquid were 35%. N-methylpyrrolidone was added and dissolved uniformly. Next, a predetermined equivalent of hexamethylene diamine was added and stirred for 10 hours at a temperature of 90 ° C. until the amine compound could not be confirmed. The properties of the obtained polyhydroxypolyurethane resin were as shown in Table 1.

<Comparative polymerization example 2> (Production of polyurethane resin)
The polyurethane resin used in the comparative example was synthesized as follows. First, a reaction vessel equipped with a stirrer, a thermometer, a gas introduction tube and a reflux condenser was replaced with nitrogen, and in this vessel, 150 parts of polybutylene adipate having an average molecular weight of about 2,000, 1,4-butanediol 15 In a mixed organic solvent consisting of 200 parts of methyl ethyl ketone and 50 parts of dimethylformamide, 62 parts of water-added MDI was dissolved in 171 parts of dimethylformamide while stirring well at 60 ° C. The solution was gradually added dropwise, and after completion of the addition, the reaction was carried out at 80 ° C. for 6 hours.
This solution had a viscosity of 3.2 MPa · s (25 ° C.) at a solid content of 35%. The film obtained from this solution had a breaking strength of 45 MPa, a breaking elongation of 480%, and a thermal softening temperature of 110 ° C. Further, a blending solution comprising 100 parts of the resin solution, 3 parts of silicone oil (SH-200, manufactured by Toray Dow Corning Co., Ltd.) and 300 parts of methyl ethyl ketone was used as a peelable treatment agent for comparative tests.

下記のようにして、比較例で用いるポリシロキサン変性ポリウレタン樹脂を合成した。上記式Ｄで表され、かつ、平均分子量が約３，２００であるポリジメチルシロキサンジオール１５０部および１，４−ブタンジオール１０部を、２００部のメチルエチルケトンと５０部のジメチルホルムアミドからなる混合有機溶媒を加え、また、４０部の水添加ＭＤＩを１２０部のジメチルホルムアミドに溶解したものを徐々に滴下し、滴下終了後、８０℃で６時間反応させた。この溶液は、固形分３５％で１．６ＭＰａ・ｓ（２５℃）の粘度を有し、この溶液から得られたフィルムは破断強度２１ＭＰａで破断伸度２５０％を有し、熱軟化温度は１３５℃であった。 <Comparative polymerization example 3> (Production of polysiloxane-modified polyurethane resin)

The polysiloxane modified polyurethane resin used in the comparative example was synthesized as follows. A mixed organic solvent comprising 150 parts of polydimethylsiloxane diol represented by the above formula D and having an average molecular weight of about 3,200 and 10 parts of 1,4-butanediol, comprising 200 parts of methyl ethyl ketone and 50 parts of dimethylformamide. In addition, 40 parts of water-added MDI dissolved in 120 parts of dimethylformamide was gradually added dropwise, and after completion of the addition, the mixture was reacted at 80 ° C. for 6 hours. This solution has a solid content of 35% and a viscosity of 1.6 MPa · s (25 ° C.). A film obtained from this solution has a breaking strength of 21 MPa and a breaking elongation of 250%, and the heat softening temperature is 135. ° C.

<Examples 1-3 and Comparative Examples 1-3>
Using the resin solutions (solid content 35%) prepared in Example Polymerization Examples 1 to 3 and Comparative Polymerization Examples 1 to 3, respectively, a cross-linking agent was added thereto, and the releasable treatment agent (coating solution) shown in Table 2 Was prepared. Using the obtained liquid releasable treatment agent, it is applied after diluting with a solvent so as to have a solid content of 0.5 g / m ² on the surface of a 30 μm thick polyethylene terephthalate film (manufactured by Toray) by gravure printing. did. Then, this was heat-dried at 90 degreeC for 3 minute (s), and the peelable sheet | seat was created, respectively.

<Comparative example 4>
A silicone resin coating composition was prepared by dissolving 100 parts of a silicone resin (manufactured by Shin-Etsu Chemical Co., Ltd., KS-841) and 1 part of a catalyst (manufactured by Shin-Etsu Chemical Co., Ltd., PL-7) in 1,000 parts of toluene. Using this, in the same manner as described above, it was applied onto a substrate sheet to form a peelable treatment layer to obtain a peelable sheet.

<Evaluation>
On each peelable sheet prepared as described above, an acrylic pressure-sensitive adhesive tape having a width of 20 mm (manufactured by Sekisui Chemical Co., Ltd.) is pressure-bonded with a rubber roller having a weight of 2 kg, and at room temperature (23 ° C., humidity 46%). The samples were left for 1 day and 3 days at high temperature (40 ° C., humidity 90% or more). Thereafter, the peel strength, residual adhesion rate, drop-off property, writing property, and environmental compatibility of each sample were evaluated. The evaluation method and evaluation criteria at that time are as follows.

(Peeling power)
An adhesive tape having a width of 20 mm is applied to the peelable treatment layer of each peelable sheet, stored at 40 g at 20 g / cm ² under a load condition for 24 hours, and then at an angle of 180 ° using a tensile tester, 300 mm / The force (g) when the adhesive tape was peeled off at a rate of minutes was measured at 20 ° C. It can be evaluated that the smaller the force value obtained in this peel force test, the better the peel force.

(Residual adhesion rate)
The pressure-sensitive adhesive tape after measuring the peeling force was applied to a stainless steel plate # 280 by reciprocating once on a 2 kg tape roller to obtain a measurement sample. On the other hand, a clean adhesive tape that has not been used for the peel strength test is attached to stainless steel plate # 280 as a blank, and after 30 minutes, the adhesive tape is used at a 180 ° angle and a speed of 300 mm / min using a tensile tester. The force (g) when peeled off was measured at 20 ° C. And the percentage with respect to a blank (320g / 20mm) was computed, and this was made into the residual adhesive rate. The closer this value is to 100%, the better the residual adhesion rate.

(Drop off)
For the sample after reciprocating the gauze with a load of 50 g / cm ² to the peelable treatment layer of each peelable sheet obtained by using each peelable treatment agent of Examples and Comparative Examples, the peelable treatment layer The degree of dropout was visually observed to evaluate the dropout. Evaluation was performed according to the following criteria.
○: No peeling off of the peelable treatment layer.
X: Dropping of the peelable treatment layer is observed.

(Writing)
Write letters with a commercially available oil-based magic ink on the peelable treatment layer of each peelable sheet obtained using each of the peelable treatment agents of Examples and Comparative Examples, and visually observe the presence or absence of ink repelling during writing. The evaluation was based on the following criteria.
○: No ink repellency.
X: Ink repelling is observed.

<Environmental compatibility>
A judgment was made as to whether or not carbon dioxide was immobilized.

  The releasable treatment agent comprising the specific polysiloxane-modified polyhydroxypolyurethane resin of the present invention can be baked at a low temperature, has no applicability to the substrate, and has excellent applicability. It can be written with a pen or the like and has an appropriate peeling force. This is because when the peelable treatment layer is formed by the peelable treatment agent of the present invention, the polysiloxane-modified polyhydroxypolyurethane resin is oriented with the polysiloxane segment as the surface, thereby imparting the non-stickiness of the polysiloxane segment. By doing so, it becomes possible to form a peelable treatment layer exhibiting excellent peelability. At the same time, the hydroxyl group of the polysiloxane-modified polyhydroxypolyurethane resin interacts strongly at the interface with the substrate sheet, so that excellent performance such as good adhesion to the substrate and flexibility can be obtained. In addition, from the viewpoint of reducing global warming gas, by using a resin incorporating carbon dioxide in its structure, according to the peelable treatment agent of the present invention, an environmental protection product that could not be achieved with conventional products Can be provided.

Claims (6)

  In the peelable treatment agent containing a resin having a siloxane segment, the resin is composed of a polysiloxane-modified polyhydroxypolyurethane resin derived from a reaction between a 5-membered cyclic carbonate compound and an amine-modified polysiloxane compound. A releasable treatment agent.   The peelable treatment agent according to claim 1, wherein the five-membered cyclic carbonate compound is obtained by reacting an epoxy compound with carbon dioxide. The peelable treatment agent according to claim 2 , wherein the polysiloxane-modified polyhydroxypolyurethane resin incorporates 1 to 25% by mass of carbon dioxide reacted in the structure .   The peelable treatment agent according to any one of claims 1 to 3, wherein the polysiloxane-modified polyhydroxypolyurethane resin contains a polysiloxane segment in a proportion of 10 to 75% by mass in the resin molecule.   Furthermore, the peelable processing agent of any one of Claims 1 thru | or 4 which contains other resin as a binder.   The releasable treatment agent according to any one of claims 1 to 5, wherein the polysiloxane-modified polyhydroxypolyurethane resin is crosslinked with a crosslinking agent that reacts with a hydroxyl group constituting the resin.

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