URETHANE-BASED ADHESIVE COMPOSITION

Abstract

A urethane-based adhesive composition with improved adhesiveness while maintaining characteristics of being gentle to the skin is provided.

The urethane-based adhesive composition of the invention contains a urethane-based adhesive, a curing agent and a hydrophilic plasticizing agent as essential components. The hydrophilic plasticizing agent is a hydrophilic high-boiling point liquid which is compatibilized with urethane to provide a plasticizing effect, and preferably has one or more hydroxyl groups or oxyethylene groups, or both of them in a molecule. A composition ratio of the solid contents of the urethane-based adhesive composition, the curing agent and the hydrophilic plasticizing agent is, based on 100 parts by mass of the urethane-based adhesive, 0.5 to 15 parts by mass of the curing agent and 10 to 80 parts by mass of the hydrophilic plasticizing agent.

Claims

1. A urethane-based adhesive composition containing a urethane-based adhesive, a curing agent and a hydrophilic plasticizing agent as essential components, wherein a composition ratio of the urethane-based adhesive, the curing agent and the solid content is, based on 100 parts by mass of solid content of the urethane-based adhesive, 0.5 to 15 parts by mass of the solid content of the curing agent and 10 to 80 parts by mass of the solid come of the hydrophilic plasticizing agent.

2. The urethane-based adhesive composition according to claim 1, wherein the hydrophilic plasticizing agent is a high-boiling point liquid which has a hydroxyl groups and/or an oxyethylene group in a molecule.

3. The urethane-based adhesive composition according to claim 2, wherein the hydrophilic plasticizing agent is a liquid having a long-chain hydrocarbon group in addition to the hydroxyl group or the oxyethylene group, with a boiling point of 150° C. or more.

4. The urethane-based adhesive composition according to claim 2, wherein the hydrophilic plasticizing agent is one or more hydrophilic plasticizing agents selected from a group consisting of octyldodecyl lactate, isostearyl glycolate, polyoxyethylene cetyl ether, polyoxyethylene lauryl ether and oleyl cetyl ether.

5. The urethane-based adhesive composition according to claim 4, wherein the hydrophilic plasticizing agent is octyldodecyl lactate.

6. A urethane-based adhesive composition sheet, wherein a urethane-based adhesive composition is kept on a surface of a flexible film.

7. The urethane-based adhesive composition sheet according to claim 6, wherein the flexible film is a polyurethane film.

8. The urethane-based adhesive composition according to claim 3, wherein the hydrophilic plasticizing agent is one or more hydrophilic plasticizing agents selected from a group consisting of octyldodecyl lactate, isostearyl glycolate, polyoxyethylene cetyl ether, polyoxyethylene lauryl ether and oleyl cetyl ether.

9. The urethane-based adhesive composition according to claim 8, wherein the hydrophilic plasticizing agent is octyldodecyl lactate.

Description

DETAILED DESCRIPTION

[0030] Hereinafter the embodiments of the present invention will be illustrated with reference to Examples. However the present invention is not intended to be limited by those embodiments.

EXAMPLES AND COMPARATIVE EXAMPLES

[0031] A urethane-based adhesive, a curing agent and a hydrophilic plasticizing agent were mixed to obtain a transparent liquid. This mixture was applied onto a polyester release film of 30 μm in thickness such that the thickness of the adhesive layer was 25 μm, and then heated at 60° C. for 12 hours so as to crosslink some of polymer chains of the urethane adhesive resin and convert the mixture from a liquid to a soft resin-like material with adhesiveness (a urethane-based adhesive composition). Subsequently a urethane film (manufactured by CosMED Pharmaceutical Co. Ltd) as a support was laminated onto the urethane-based adhesive composition to transfer it to the urethane film. Thus a urethane-based adhesive composition sheet was obtained.

[0032] The physical property of the obtained urethane-based adhesive composition sheet was evaluated and its surface texture was observed. Samples with adhesive deposit remaining on the skin when peeling them after applying on the skin were excluded, and the adhesion property was evaluated by a ball tack test. The results were summarized in Table 1 (Examples) and Table 2 (Comparative Examples).

[0033] The ball tack test was performed to measure a ball tack value on a slope using the procedure in accordance with JIS Z 0237. The measured values were evaluated as follows: ball tack value of 6 or less represents weak adhesion; ball tack value of 7 represents moderate adhesion; and ball tack value of 8 or more represents strong adhesion. Samples exhibiting the adhesion property corresponding to the ball tack value of 7 or more are deemed to meet the purpose of the present study.

[0034] In Examples (Table 1) and Comparative Examples (Table 2) described below, CYABINE SP-205 (a medium adhesive type urethane-based adhesive: TOYO INK CO., LTD.) composed of polyurethane polyol was used as the urethane-based adhesive. In these tables, the used amount of solid content of each component other than the urethane-based adhesive is expressed in parts by mass based on 100 parts by mass of solid content of the urethane-based adhesive.

[0035] T501B (a polyfunctional isocyanate curing agent: TOYO INK CO., LTD.) or Sanpasuta HD739D (a polyfunctional isocyanate curing agent: VIGteQnos Corporation) was used as the curing agent. Note that Sanpasuta HD739D is known to contain silica and therefore undergo a crosslinking reaction smoothly even if the crosslinking system contains water.

[0036] Either of COSMOL 13 (octyldodecyl lactate: Nisshin OilliO Group, Ltd.), NOIGEN ET83 (polyoxyethylene lauryl ether: Dai-ichi Kogyo Seiyaku Co. Ltd.), NONION P-202 (polyoxyethylene cetyl ether: NOF CORPORATION) or polyethylene glycol 400 (NACALAI TESQUE, INC.) was used as the hydrophilic plasticizing agent.

[0037] To compare to the invention of Patent document 4, a hydrophobic plasticizing agent, a low molecular weight polyhydric alcohol was used instead of the hydrophilic plasticizing agent in some Comparative Examples. 1PM (isopropyl myristate: Wako Pure Chemical Industries, Ltd.) or IPP (isopropyl palmitate: Wako Pure Chemical Industries, Ltd.) was used as the hydrophobic plasticizing agent. Glycerin (NACALAI TESQUE, INC.) was used as the low molecular weight polyhydric alcohol.

TABLE-US-00001 TABLE 1 urethane-based plasticizing agent, adhesive curing agent polyhydric alcohol adhesive Examples (part by weight) (part by weight) (part by weight) deposit adhesiveness 1 SP-205 T501B (3) COSMOL 13 (15) absent moderate (100) adhesiveness 2 T501B (5) COSMOL 13 (40) absent strong adhesiveness 3 T501B (8) COSMOL 13 (60) absent strong adhesiveness 4 T501B (9) NOIGEN ET83 (30) absent strong adhesiveness 5 HD739D (10) NONION P202 (30) absent strong adhesiveness 6 HD739D (10) polyethylene glycol 400 (15) absent strong adhesiveness 7 HD739D (2) NONION P202 (30) absent moderate adhesiveness

TABLE-US-00002 TABLE 2 urethane-based Comparative adhesive curing agent plasticizing agent adhesive Examples (part by weight) (part by weight) (part by weight) deposit adhesiveness  1 SP-205 T501B (20) COSMOL 13 (60) absent weak (100) adhesiveness  2 T501B (3) COSMOL 13 (3) absent weak adhesiveness  3 T501B (10) COSMOL 13 (8) absent weak adhesiveness  4 T501B (3) IPM (15) absent weak adhesiveness  5 T501B (6) IPM (30) absent weak adhesiveness  6 HD739D (3) IPP (30) absent weak adhesiveness  7 HD739D (5) IPP (8) absent weak adhesiveness  8 T501B (0.3) COSMOL 13 (40) present —  9 T501B (15) NOIGEN ET83 (100) present — 10 T501B (10) glycerin (40) present —

[0038] Comparative Example 8 caused adhesive deposit because it contained too little amount of the curing agent. Comparative Examples 9 also caused adhesive deposit because it contained slightly too much amount of the curing agent and furthermore too much amount of the hydrophilic plasticizing agent.

[0039] In the invention of Patent document 4, a fatty acid ester having 10 to 30 carbons such as isostearyl laurate and isopropyl myristate is added instead of the hydrophilic plasticizing agent used in the present invention. Comparative Examples 4, 5, 6 and 7, which are similar to the invention of Patent document 4, have poor adhesion, as shown in Table 2. Thus, the urethane-based adhesive composition for the skin which is gentler to the skin and exhibits stronger adhesibility can be obtained by using the hydrophilic plasticizing agent rather than by using the fatty acid ester.

Evaluation of Permeating Amount of the Water Vapor

[0040] Five samples, Example 8 and Comparative Examples 11 to 15, were evaluated using the procedure in accordance with Testing Methods for Determination of the Water Vapor Transmission Rate of Moisture-Proof Packaging Materials (Dish Method) (JIS). Note that unwoven fabric (manufactured by Japan Vilene Company, Ltd., EW-9102) was used as a support to avoid any impact on the water vapor transmission rate of the adhesives. The adhesive had a thickness of 50 μm. In the Dish Method, the water vapor transmission amount was measured after left for 24 hours under the condition as follows: the opening area of the dish of 28.26 cm.sup.2; the amount of calcium chloride of 17 g; room temperature of 40° C.; and humidity of 75%, and the results are shown in Table 3.

[0041] In the samples used in Table 3, MASCOS 10 is an acrylic adhesive (CosMED Pharmaceutical Co. Ltd). Also, an oil gel is produced by melt-kneading 30 parts by mass of styrene-isoprene-styrene block copolymer (Kraton D1163, manufactured by Kraton Polymer Japan), 60 parts by mass of liquid paraffin (NACALAI TESQUE, INC., chemical reagents) and 0.5 parts by mass of benzoyl hydroxytoluene (NACALAI TESQUE, INC., chemical reagents) at 140° C. followed by press-formation into a sheet of 50 μm in thickness.

TABLE-US-00003 TABLE 3 Example urethane-based permeating amount Comparative adhesive curing agent plasticizing agent of water vapor Examples (part by weight) (part by weight) (part by weight) (g/m.sup.2 .Math. 24 hr) Example 8 SP-205 T501B (5) COSMOL 13 (40) 3567 Comparative (100) T501B (5) IPP (40) 2501 Example 11 Comparative T501B (5) absent 1758 Example 12 Comparative MASCOS-10 absent absent 453 Example 13 Comparative MASCOS-10 HD739D (5) COSMOL 13 (40) 1762 Example 14 Comparative oil gel absent absent 495 Example 15

[0042] The urethane-based adhesive to which the hydrophilic plasticizing agent was added had a significantly high water vapor transmission amount compared to the oil gel-based adhesive and the acrylic adhesive.