WO2014148582A1

WO2014148582A1 - Solventless polyurethane-based adhesive

Info

Publication number: WO2014148582A1
Application number: PCT/JP2014/057618
Authority: WO
Inventors: 律絵子足立
Original assignee: ニチバン株式会社
Priority date: 2013-03-21
Filing date: 2014-03-19
Publication date: 2014-09-25
Also published as: JPWO2014148582A1; JP6270818B2

Abstract

The purpose of the present invention is to provide a polyurethane-based adhesive which can be produced without the use of a solvent and which exhibits excellent adhesion to the skin even if the thickness of an adhesive layer is a thickness whereby moisture permeability can be satisfactorily achieved, for example 100 μm or lower. The present invention relates to a solventless polyurethane-based adhesive, which is obtained by reacting (A) an active hydrogen compound having an average molecular weight of 1.2 × 10⁴ or higher and having an average of three functional groups, (B) an active hydrogen compound having an average molecular weight of 0.1 × 10⁴ or higher and having an average of two functional groups, and (C) an organic polyisocyanate having an average of two functional groups (here, if the total quantity of active hydrogen compounds in the adhesive is 100 parts by weight, the quantity of the active hydrogen compound (A) is 40-90 parts by weight).

Description

Solvent-free polyurethane adhesive

The present invention relates to a solventless polyurethane pressure-sensitive adhesive mainly used for a patch applied to the skin.

Medical patch materials, especially dressing materials, must have the flexibility and followability to prevent the entry of water, bacteria, viruses, etc. from the outside into the body and to follow the curved surface and movement of the skin. It is. Therefore, a thin elastomer film having a low elastic modulus similar to that of the skin is generally used as a support for such a patch.

Also, the adhesive material is required to have excellent moisture permeability so that moisture generated by sweating from the skin is evaporated to the outside of the adhesive material. If the moisture permeability is poor, moisture generated from the skin is stored between the skin and the adhesive layer, causing a decrease in adhesive strength, weakening the adhesive fixing function and facilitating peeling, and resident bacteria due to water storage Skin damage is likely to occur due to the growth of the skin. For medical patches, imparting high moisture permeability is also an important requirement.

In addition to the thin-layer elastomer film, polyurethane adhesive is also used for the adhesive. For example, Patent Document 1 discloses a patch using a polyurethane-based pressure-sensitive adhesive for the purpose of providing a patch having both excellent adhesive properties and moisture permeability. Patent Document 2 also describes their absorbency and / or permeability, except for the loss of water and / or other body fluids that come into contact with the adhesive through the epithelium from the application site, and polyurethane aggregation and adhesion. A pressure sensitive adhesive comprising a polyurethane polymer having a pure balance is disclosed. Furthermore, Patent Document 3 discloses a polyurethane resin adhesive having a high initial adhesive strength, capable of stably maintaining the adhesive strength for a long period of time, excellent in heat resistance and cold resistance of the adhesive force, and does not exude low molecular components. It is disclosed.

International Publication No. 2010/137699 JP-A-7-310066 JP 9-324170 A

The polyurethane-based pressure-sensitive adhesive can be produced by a method such as a bulk polymerization (solid reaction) method or a solution polymerization method in which the reaction is performed in a molten state. However, since an organic solvent is used in the solution polymerization method, a step for drying the pressure-sensitive adhesive and recovering the organic solvent is required, and in addition, a step for preparing a pressure-sensitive adhesive solution by polymerizing the raw materials in the organic solvent. Therefore, there is a problem that the manufacturing process increases and costs increase. In addition, as an environmental measure, a method for producing a patch without using an organic solvent has been desired.

On the other hand, in addition to Patent Document 2, several documents disclose a patch using a polyurethane-based adhesive that can be produced without a solvent. However, these pressure-sensitive adhesives show only the pressure-sensitive adhesive properties when the thickness of the pressure-sensitive adhesive is relatively thick, such as 100 μm to several mm, which is one of the important characteristics when using polyurethane-based pressure-sensitive adhesives on the skin. It is difficult to obtain moisture permeability, and since it becomes a thick patch, it may be difficult to peel off when applied to the skin, or may cause physical irritation. . In addition, there is a case where a process for preparing a prepolymer is required. In this case, there is a problem that the number of manufacturing processes is increased even in the case of a solvent-free system as in the case of a solvent-based adhesive.

Therefore, the present invention does not include a step of preparing a pressure-sensitive adhesive solution or a prepolymer, can be manufactured without using a solvent, and the thickness of the pressure-sensitive adhesive layer can sufficiently exhibit moisture permeability, for example, 100 μm. Even if it is below, it aims at providing the polyurethane-type adhesive which has the adhesive characteristic outstanding with respect to skin.

The present inventors have intensively studied in order to solve the above-mentioned problems, and as a result, the present invention has been completed.

That is, the present invention
A solventless polyurethane pressure-sensitive adhesive that can be produced without a step of preparing a pressure-sensitive adhesive solution or prepolymer,
(A) an active hydrogen compound having an average molecular weight of 1.2 × 10 ⁴ or more and an average functional group number of 3;
(B) an active hydrogen compound having an average molecular weight of 0.1 × 10 ⁴ or more and an average functional group number of 2;
(C) A pressure-sensitive adhesive obtained by reacting with an organic polyisocyanate having an average functional group number of 2 (where, in the pressure-sensitive adhesive, when the total active hydrogen compound is 100 parts by weight, the active hydrogen compound of (A) Is 40 to 90 parts by weight).
The present invention also relates to a patch having a pressure-sensitive adhesive layer containing the pressure-sensitive adhesive.

According to Patent Document 3, when the average molecular weight of the polyether polyol exceeds 0.5 × 10 ⁴ , the reactivity becomes low and the cohesive force is insufficient. However, since the pressure-sensitive adhesive of the present invention is produced without using a solvent, the reaction proceeds faster than in the case of using a solvent, and a decrease in reactivity does not become a problem. In addition, since the gel content increases even in the same composition when the reaction proceeds immediately at high temperature, the adhesive of the present invention produced without using a solvent has insufficient cohesive force even when a high molecular weight active hydrogen compound is used. Rather, it has an appropriate tack and can be suitable for the skin.

In order to form a three-dimensional crosslinked structure, the average number of functional groups of at least one of the active hydrogen compound and the organic polyisocyanate needs to be larger than 2, but if these average functional groups are too large, the network is clogged. It becomes a polymer having a different structure and lacks flexibility and becomes a pressure-sensitive adhesive with a tack too low. Moreover, even if the molecular weights of the active hydrogen compound and the organic polyisocyanate are too small, the cross-linked portions are clogged and the flexibility of the polymer is insufficient. In the present invention, an active hydrogen compound having an average molecular weight of 1.2 × 10 ⁴ or more and an average functional group number of 3 and an organic polyisocyanate having an average functional group number of 2 are used, and further an average molecular weight of 0.1 × 10 ⁴ or more and an average functional group number By using two active hydrogen compounds in combination, a more flexible pressure-sensitive adhesive having a structure similar to that obtained when a higher molecular weight active hydrogen compound is used can be provided.

From the above, the pressure-sensitive adhesive of the present invention has sufficient adhesive properties to the skin even when a thin pressure-sensitive adhesive layer of 100 μm or less is formed, and therefore sufficiently exhibits the high moisture permeability of the urethane-based pressure-sensitive adhesive. can do. If the adhesive of this invention is used, the patch which has sufficient moisture permeability and the outstanding adhesive characteristic can be provided.
In addition, since the pressure-sensitive adhesive of the present invention is produced without using a solvent, a solvent recovery device or the like is not required when drying the pressure-sensitive adhesive, and the preparation of the pressure-sensitive adhesive raw material solution or prepolymer is not required. Therefore, the manufacturing process is simplified and the manufacturing cost can be reduced. Moreover, since no organic solvent is used, it is excellent in environmental measures.

It is a schematic diagram of a sectional view of an example of a patch of the present invention.

In the present invention, the solventless polyurethane-based pressure-sensitive adhesive means a polyurethane-based pressure-sensitive adhesive manufactured without using a solvent, and is manufactured using, for example, a bulk polymerization (solid reaction) method in which a reaction is performed in a molten state. It is a thing.

The average molecular weight of the active hydrogen compound (A) of the present invention is a polymer having a flexible structure in which the cross-linked portions have an appropriate distance between them, and the mixture at the time of coating becomes low in viscosity and the coating property is lowered. In order to prevent this, it is 1.2 × 10 ⁴ or more, preferably 1.3 × 10 ⁴ or more, and more preferably 1.4 × 10 ⁴ or more. The upper limit of the average molecular weight of the active hydrogen compound (A) is not particularly limited, but prevents a decrease in cohesive force, and prevents the coating property from being lowered due to the high viscosity of the mixture during coating. Therefore, 3.0 × 10 ⁴ or less, particularly 2.0 × 10 ⁴ or less, and particularly 1.8 × 10 ⁴ or less are preferable.
For example, the average molecular weight of the active hydrogen compound (A) is 1.2 × 10 ⁴ to 3.0 × 10 ⁴ , preferably 1.3 × 10 ⁴ to 2.0 × 10 ⁴ , more preferably 1.4. × 10 ⁴ to 1.8 × 10 ⁴ .

In the present invention, the average molecular weight of the active hydrogen compound is represented by the following formula based on the hydroxyl value (OHv, unit is mgKOH / g) of the active hydrogen compound.
Average molecular weight = (56100 / OHv) × Calculated using the average number of hydroxyl groups per molecule. Here, the hydroxyl value is a value measured according to JIS K1557-1 (2007 edition) B method (phthalation method). The average number of hydroxyl groups per molecule refers to the number of active hydrogen atoms per molecule of initiator used as a raw material when producing an active hydrogen compound. For example, ethylene glycol and propylene glycol are 2, Glycerin and trimethylolpropane are three.

The average molecular weight of the active hydrogen compound (B) of the present invention is 0 in order to prevent the cross-linked portions from having an appropriate distance between each other, and to prevent the mixture at the time of coating from becoming low viscosity and lowering the coating property. and a .1 × 10 ⁴ or more, preferably 0.2 × 10 ⁴ or more, more preferably 0.4 × 10 ⁴ or more. The upper limit of the average molecular weight of the active hydrogen compound (B) is not particularly limited, but is preferably 3.0 × 10 ⁴ or less, particularly 2.0 × 10 ⁴ or less, and particularly preferably 1.5 × 10 ⁴ or less.
For example, the average molecular weight of the active hydrogen compound (B) is 0.1 × 10 ⁴ to 3.0 × 10 ⁴ , preferably 0.2 × 10 ⁴ to 2.0 × 10 ⁴ , more preferably 0.4. × 10 ⁴ to 1.5 × 10 ⁴ .
In addition, if the difference in molecular weight between the active hydrogen compound (A) and the active hydrogen compound (B) is too large, the difference in reactivity becomes too large and the reaction of the low molecular weight active hydrogen compound proceeds excessively. It becomes. From the viewpoint of preventing this, the average molecular weight of the active hydrogen compounds (A) and (B) is preferably within the above-mentioned range.

In particular, the active hydrogen compound (A) having an average molecular weight of 1.2 × 10 ⁴ or more, particularly 1.2 × 10 ⁴ to 1.5 × 10 ⁴ , and the active hydrogen compound (B), preferably 0. The polyurethane pressure-sensitive adhesive of the present invention obtained by combining 4 × 10 ⁴ to 1.0 × 10 ⁴ of the active hydrogen compound (B) has a suitable cohesive force and becomes a polymer having a flexible structure. Is preferable. The polyurethane pressure-sensitive adhesive thus obtained has an appropriate viscosity at the time of coating, which is advantageous in terms of coating properties.

Examples of the active hydrogen compounds (A) and (B) include polyether polyols, ether ester polyols obtained by partially modifying polyether polyols, and polyalkylenes having amino groups (for example, ethylene and propylene) oxide diamines. And polyether polyols are preferred.

Examples of the polyether polyol include, as an initiator, an active hydrogen compound (A) having an average functional group number of 3 having three active hydrogen groups such as glycerin and trimethylolpropane, ethylene oxide, propylene oxide, A polyether polyol obtained by ring-opening polymerization of tetrahydrofuran or the like, or a mixture of two or more of these polyols having an average number of functional groups of 3 is preferable.

Examples of the polyether polyol include polyethylene glycol, polypropylene glycol, polytetramethylene obtained by ring-opening polymerization of ethylene oxide, propylene oxide, tetrahydrofuran, or the like as the active hydrogen compound (B) having an average functional group number of 2. Mixtures of two or more of ether glycols and polyether glycols such as polyether glycols copolymerized with these and / or polyols having an average number of these two functional groups are preferred.

Specifically, Sanyo Chemical's Sanniks series, Mitsui Chemicals Polyurethane's Act Call series, Asahi Denka's Adeka polyether series, Lyondell's Acclaim series, Asahi Glass's Exenol series, Preminol series, etc. Can be used.

In the present invention, the active hydrogen compounds of (A) and (B) can be used alone, for example, using a mixture of two or more different in terms of average molecular weight, average number of functional groups, types of monomer units, etc. Also good.

The active hydrogen compound used in the production of the polyurethane pressure-sensitive adhesive of the present invention is preferably composed only of the active hydrogen compounds of the above (A) and (B), but other active hydrogen compounds such as monools and polyols are used. As long as the effect of the present invention is not impaired, it can be contained. As such active hydrogen compounds such as monools and polyols, general compounds such as acrylic monools, ester polyols, and polycarbonate polyols can be used.

In the production of the polyurethane pressure-sensitive adhesive of the present invention, from the viewpoint of obtaining a polymer having an appropriate flexibility, when the total active hydrogen compound is 100 parts by weight, the active hydrogen compound of (A) has a lower limit, 40 parts by weight or more, preferably 42 parts by weight or more, more preferably 45 parts by weight or more, while the upper limit is 90 parts by weight or less, preferably 80 parts by weight or less, more preferably 70 parts by weight or less, still more preferably 60 parts by weight or less, particularly preferably 50 parts by weight or less.
For example, when the total active hydrogen compound is 100 parts by weight, the active hydrogen compound (A) is 40 to 90 parts by weight, preferably 42 to 80 parts by weight, more preferably 45 to 70 parts by weight, still more preferably It is 45 to 60 parts by weight or more, particularly preferably 45 to 50 parts by weight or less.
Further, when the total active hydrogen compound is 100 parts by weight, the active hydrogen compound (A) may be 50 to 90 parts by weight, preferably 55 to 80 parts by weight, more preferably 60 to 70 parts by weight. Good.

In the present invention, the total active hydrogen compound means all active hydrogen compounds reacted with the organic polyisocyanate (C), including the active hydrogen compounds (A) and (B). .

It has been confirmed that the alkylene oxide which is a constituent molecule of the polyurethane-based pressure-sensitive adhesive of the present invention, that is, the active hydrogen compounds (A) and (B) containing a polyoxyalkylene structure are generally highly safe to the human body. ing. Similarly, polyurethane having this as a segment is also highly safe and is practically used as a medical polymer material. In addition, by selecting the type of active hydrogen compound of (A) and (B) above, the balance between the hydrophilicity and hydrophobicity of the segment can be adjusted, the flexibility of the molecule due to the urethane bond is added, the transparency is high and the skin Good adhesion, soft and familiar, and a low-irritant adhesive. Therefore, it is suitable for an application to be applied to a human body, and is suitable as an adhesive for a medical patch. In this case, the pressure-sensitive adhesive can be a new pressure-sensitive adhesive satisfying all of the adhesiveness, safety, stability as a material, and economy.

As the (C) organic polyisocyanate having an average functional group number of 2 of the present invention, any organic polyisocyanate that can be generally used for producing a polyurethane resin can be used. Specifically, fragrances such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,2'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, etc. Diisocyanates, aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, or alicyclic diisocyanates such as isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, etc. Organic diisocyanates such as a mixture of these are preferred, but polyisocyanates obtained by modifying a part of these by urethanization, uretdioneization, carbodiimidization, or the like can also be used. It is also possible to use an isocyanate prepolymer prepolymerized with a polyol.

In particular, the above aliphatic diisocyanates or alicyclic diisocyanates, polyisocyanates modified from these, and isocyanate prepolymers obtained by prepolymerizing them are desirable in terms of preventing yellowing of the pressure-sensitive adhesive.

The NCO / OH molar ratio between the active hydrogen compound and the organic polyisocyanate is preferably 0.7 / 1 to 1/1 in order to increase the adhesive strength. If the amount of residual NCO is low, the stability over time will be good, so a ratio of 1.05 / 1 or less, particularly 1/1 or less is preferred. On the other hand, when the ratio is 0.7 / 1 or more, the amount of residual active hydrogen compound is decreased, so that the possibility of bleed-out is reduced, which is preferable.

The polyurethane-based pressure-sensitive adhesive in the present invention is not particularly limited unless a solvent is used, and can be produced by a conventional method, for example, a bulk polymerization (solid reaction) method in which the reaction is performed in a molten state. Since this method does not use a solvent, the process of removing the solvent or preparing a raw material solution is not necessary, so the polyurethane-based pressure-sensitive adhesive of the present invention can be easily produced, and is an environmental measure. Is also excellent.

When producing the polyurethane-based pressure-sensitive adhesive in the present invention, a catalyst, an additive and the like can be used as necessary. Examples of the catalyst include general urethanization catalysts such as nitrogen-containing compounds and organometallic catalysts. Examples of nitrogen-containing compounds include triethylamine and triethylenediamine. Examples of organometallic catalysts include dialkyltin compounds {eg, dibutyltin dilaurate, dibutyltin di (2-ethylhexoate)}, carboxylic acid metal catalysts (eg, octylic acid). Tin, tin stearate) and the like. Examples of the additive include ultraviolet absorbers such as substituted benzotriazoles, antioxidants such as phenol derivatives, and hydrolysis inhibitors.

The polyurethane pressure-sensitive adhesive of the present invention may be used in a pressure-sensitive adhesive layer of a patch, particularly a medical patch such as a dressing. The present invention also relates to a patch having an adhesive layer containing the polyurethane adhesive of the present invention. The patch of the present invention can be obtained, for example, by providing the pressure-sensitive adhesive layer of the present invention on a support using a conventional technique.

Moreover, the patch of the present invention may include a carrier and / or a peeler. The carrier is provided in a peelable state on the surface of the support opposite to the surface on which the pressure-sensitive adhesive layer is provided. The peelable body is provided in a peelable state on the surface opposite to the surface on which the support of the pressure-sensitive adhesive layer is provided. That is, the patch of the present invention may include a carrier, a support, a pressure-sensitive adhesive layer, and a release body in this order (FIG. 1). In the present invention, one or more other layers may be interposed between the support and the support, between the support and the pressure-sensitive adhesive layer, and / or between the pressure-sensitive adhesive layer and the release body. . For example, an undercoat layer, an adhesive layer, or a release agent layer may be provided in order to improve adhesiveness and peelability, or a film, a nonwoven fabric, a woven fabric, or a laminate thereof may be interposed.

The pressure-sensitive adhesive layer of the present invention may be provided by coating the support with a pattern coating, for example, in the form of a lattice or diamond, but the pressure-sensitive adhesive layer is supported to improve the fixation to the skin. It is preferably in a state of essentially covering the entire surface of the body. In addition, from the point that the amount of exfoliation when the patch is peeled from the skin is reduced, and the deterioration of fixability due to moisture stored between the skin and the adhesive layer is suppressed, the moisture permeability of the patch of the present invention is 1,000g / ^m 2 · 24hr or more and preferably 2,000g / ^m 2 · 24hr or more. The upper limit value of the moisture permeability of the patch may be 8,000 g / m ² · 24 hr or less, but the higher the moisture permeability, the better, and the upper limit value is not particularly limited.

In the present invention, the moisture permeability is measured according to JIS Z-0208. It can be said that the higher the moisture permeability, the less the stuffiness is. In particular, the term “highly moisture permeable” may be used in the present invention, but in the test according to JIS Z-0208, 1,000 g / m ² · 24 hr or more is meant.

The pressure-sensitive adhesive layer of the present invention preferably has a water vapor transmission rate of 3,000 g / m ² · 24 hr or more, more preferably 4,000 g in order to provide a patch having both excellent adhesive properties and high moisture permeability. / m ² · 24 hr or more. The upper limit value of the moisture permeability of the pressure-sensitive adhesive layer may be 8,000 g / m ² · 24 hr or less, but the higher the moisture permeability, the better, and the upper limit value is not particularly limited.
In the present invention, the moisture permeability of the pressure-sensitive adhesive can be adjusted by a known method (for example, see JP-A-7-231910 and JP-A-2005-58288). Generally, high moisture permeability can be obtained by increasing the number of ethylene oxide (sometimes abbreviated as EO) units in the polyurethane-based pressure-sensitive adhesive. However, if there are too many EO units, swelling occurs during moisture absorption. Stickiness and deterioration of physical properties occur. In addition, moisture permeability and adhesive operations can be performed by adding a plasticizer. However, the addition of a plasticizer causes insufficient internal cohesive strength of the polyurethane-based adhesive, resulting in a decrease in adhesive strength, or when the skin is peeled off. It may cause adhesive residue on the surface. Furthermore, it has been reported that irritation by chemical components of these plasticizers causes rashes and skin irritation.

The pressure-sensitive adhesive of the present invention can impart higher moisture permeability by including an EO unit in the active hydrogen compound in the polyurethane-based pressure-sensitive adhesive. If the amount of the EO unit is excessive, the flexibility of the pressure-sensitive adhesive is lowered and the pressure-sensitive adhesive properties are lowered. Therefore, the EO unit content of all active hydrogen compounds in the polyurethane-based pressure-sensitive adhesive according to the present invention is the whole polyurethane-based pressure-sensitive adhesive. The content is preferably 0 to 8% by weight, particularly preferably 0 to 4% by weight.

Further, the pressure-sensitive adhesive layer of the present invention has a urethane support when the pressure-sensitive adhesive layer has a thickness of 27 μm and the support has a thickness of 18 μm even if the moisture permeability is 3,000 g / m ² · day or more. In the case of the body, the adhesive strength to bakelite by the test method described later may be 0.3 to 2 N / 12 mm, preferably 0.5 to 1.6 N / 12 mm, more preferably 0.7 to 1 N / 12 mm. The probe tack according to the test method described later can be 0.5 to 1.2 N / 5 mmφ, preferably 0.5 to 1 N / 5 mmφ, more preferably 0.6 to 0.9 N / 5 mmφ. The ball tack by the test method of No. 15 is preferably No. 15 or more, more preferably No. 20 or more, and the holding power to glass (deviation length) by the test method described later is preferably 0.1 to 1mm, more preferably .1 ~ 0.5 mm, more preferably it may be 0.2 ~ 0.3 mm. The adhesive force can be adjusted by the method described in this document or a conventional method, but can also be adjusted by the thickness of the pressure-sensitive adhesive layer or the support. That is, when the thickness of the adhesive is increased, the adhesive strength tends to increase, and when the thickness is decreased, the adhesive strength tends to decrease. When the support is thickened, the adhesive strength tends to be high and the adhesive strength tends to be high, and when the support is thin, the adhesive strength tends to be low. Moreover, since it is influenced by the bending resistance of the support itself, it cannot be generally stated. For example, in the case of a non-woven fabric or a woven fabric, the adhesive force has almost the same tendency as that of urethane.

The thickness of the pressure-sensitive adhesive layer of the patch of the present invention is not particularly limited, but it secures fixation to the skin and is preferably 5 μm or more, particularly preferably 10 μm or more from the viewpoint of balance with the support thickness. When the thickness is too thick, the moisture permeability and followability to the skin are lowered, and the thickness is preferably 100 μm or less, particularly 40 μm or less.
For example, the thickness of the pressure-sensitive adhesive layer is preferably 5 μm to 100 μm, particularly preferably 10 μm to 40 μm.

Also, in applications where the skin is covered, when the thickness of the adhesive layer of the patch is about 3 to 7 μm, effects such as followability to the skin as a patch and difficulty in conspicuousness are given to the patch. Can do.

The support of the present invention is not particularly limited as long as it has appropriate stretchability, flexibility, strength, and the like for application to the skin, but in order to obtain an application material that takes advantage of the moisture permeability of the adhesive, A wet substrate is suitable. The moisture permeability of the support is preferably 3,000 g / m ² · 24 hr or more, particularly preferably 4,000 g / m ² · 24 hr or more. The upper limit of the moisture permeability of the support is not particularly limited, but is usually about 10,000 g / m ² · 24 hr or less, preferably about 8,000 g / m ² · 24 hr or less. For example, 3,000 g / m ² · 24 hr to about 10,000 g / m ² · 24 hr, particularly 4,000 g / m ² · 24 hr to about 8,000 g / m ² · 24 hr is preferable. Such a moisture-permeable support can be easily achieved with a nonwoven fabric or a knitted fabric, but a urethane resin support particularly useful as a dressing material is known per se (for example, JP-A-7-231910). ) And are commercially available.

When the patch of the present invention is used for a medical tape, the support preferably has a moisture permeability of 3,000 g / m ² · 24 hr or more, particularly 4,000 g / m ² · 24 hr or more. A stretchable material can also be used. For example, a woven fabric, a non-woven fabric, a knitted fabric, a film, etc., which can be selected from polyurethane, polyester, polyvinyl acetate, polyvinylidene chloride, polyethylene, polyethylene terephthalate, aluminum sheet, or a composite material thereof, and is laminated. You can also As it is, a film having low moisture permeability can be used by processing a porous film containing calcium carbonate or the like after perforation. Nonwoven fabrics, woven fabrics, knitted fabrics and the like are preferable as the support in that a patch having high moisture permeability can be obtained.

As the support of the present invention, particularly as a support for a dressing material, a support produced from a urethane resin, for example, a film or the like is suitable, has a flexible and appropriate strength, and in particular, has a fixing property to the skin. From the viewpoint of increasing or reducing the uncomfortable feeling during application, those having low water swellability are preferably used.

In the present invention, when the support is produced from a urethane resin, it is not particularly limited as long as it has the above-mentioned moisture permeability, and examples thereof include ether-based urethane resins and ester-based urethane resins. An ether urethane resin is preferably selected because of its low point.
These ether-based urethane resins having a predetermined moisture permeability are available from BASF Corporation. In order to produce an ether-based urethane resin, for example, polymerization can be performed using a conventionally used one-shot method or prepolymer method. Moreover, even if it is bulk polymerization which does not use a solvent, you may superpose | polymerize in a solution for viscosity reduction. Films produced by these polymerization methods include DINTEX FT1080-PE, DINTEX FT1881-PE (manufactured by Unipolymer), and Samprene HMP-17A (manufactured by Sanyo Kasei), which are available.

In the support of the present invention, additives usually used, for example, an ultraviolet absorber, an anti-aging agent, a filler, a pigment, a colorant, a flame retardant, an antistatic agent and the like can be added as necessary. These additives are used in normal amounts depending on the type.

The thickness of the support of the present invention is preferably 10 μm or more, particularly preferably 15 μm or more from the viewpoint of improving the handleability as a patch, and it becomes easy to produce a highly moisture-permeable support, and the effects of the present invention are easily achieved. From this point, it is preferably 50 μm or less, particularly preferably 40 μm or less. When the thickness is 10 μm or less, especially 5 to 10 μm, the support is very thin and difficult to handle. Therefore, the support should be devised, for example, the support must be made more rigid than the support, or a mouth piece may be provided. Is required.

The carrier of the present invention plays a role of reinforcing the support and improving the manufacturability and operability of the patch of the present invention. In addition, it is desirable that this carrier is transparent or translucent in view of visibility so that the application site can be confirmed at the time of application. Further, it is preferable that the carrier has a relatively high elastic modulus with respect to the support and has an elastic modulus of about 3 to 20 times that of the support. Moreover, since it is necessary to laminate | stack the support body on the surface which laminates | stacks a support body with a moderate adhesiveness with a support body, it is appropriate to perform various processes. Examples of such treatment include corona treatment, plasma treatment, ultraviolet treatment, and mat treatment.

If the carrier is difficult to peel from the support, a cut may be provided near the center of the carrier, or two carriers may be provided with a gap between the carriers. Further, a tape or a film may be laminated on the upper part of the cut of the carrier, and a mouth portion may be provided as a gripping piece. The mouth portion may be a film, non-woven fabric, woven fabric, or a laminate thereof, may be an adhesive tape, and may be colored. The end portion of the carrier film may be in a state of being corrugated or a plurality of cuts, or may be formed larger than the support. These are effective for making the carrier film easy to peel off and improving the handleability even when the patch is made into a roll.

Examples of the carrier used include polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate, polyamides such as nylon, polyvinyl chloride, and polyvinylidene chloride. In addition to these single carriers, it may be a composite carrier laminated with paper, non-woven fabric, woven fabric, knitted fabric, or metal foil. From the viewpoints of cost and cost, polyolefin and polyester films are preferably used.

The adhesive material of the present invention can be provided with a release body for ease of handling, but the release body is also useful in the production of the adhesive material. That is, in both cases of transfer coating and direct coating, since there is a possibility of contact with the mold release treatment agent before the reaction of the isocyanate of the pressure-sensitive adhesive, a treatment agent that does not react with isocyanate such as silicone is used. The exfoliated body is convenient.

As the release body of the present invention, those conventionally used in the field of patch materials can be used. For example, a paper substrate such as high-quality paper or glassine paper subjected to silicone release treatment, a polyester film, or the like can be used. Also, the basis weight of the release body, but are not limited to, usually, preferably about 50 ~ 150g / ^{m 2,} and more preferably about 60 ~ 100g / ^{m 2.} By providing one or more linear release liner dividing portions for dividing the outer shape at the substantially central portion of the release body, even if one of the release bodies is peeled off, the other release body remains, and the adhesive surface remains on the adhesive surface. Attaching work can be performed without touching, and workability is improved. In the case where the patch is made into a roll, it is particularly effective for making it easy to peel off the peeled body and improving the handleability. Moreover, even if it arrange | positions so that two or more exfoliation bodies may peel off from an adhesive so that a exfoliation body may be covered or folded up, it is effective in improving handleability.

The patch of the present invention can use a pad. As the pad, a non-woven fabric of gauze, rayon, polyethylene, polyester, polypropylene or the like having a basis weight of about 2 to 100 g / m ² can be used, and it can be preferably placed at the center of the adhesive-coated surface.

The numerical range indicated by the upper limit value and the lower limit value shown in the present specification may be partially removed by arbitrarily narrowing it (and one point or several points in the range may be excluded). In the range after the removal, the same effects as before the removal are obtained.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto. In the following synthesis examples, examples and comparative examples, parts and% are in principle parts by weight and% by weight, respectively.

1. Preparation of Patch Material 1.0% by weight of urethane curing catalyst was added to polyether polyol and stirred to obtain a mixture. This mixture and the isocyanate were mixed with a planetary stirrer at 2,000 rpm for 1 minute, and then immediately coated on the release paper so that the thickness of the adhesive was 27 ± 3 μm. In order to accelerate the curing of the pressure-sensitive adhesive, it was heated in an oven at 130 ° C. for 1 minute, then laminated with a urethane film (thickness: 18 μm), and aged in a 23 ° C. atmosphere for 1 week to prepare a patch.

Tables 1 to 3 show the raw materials such as polyether polyol used in the above production and the amounts used. The amount used is expressed in parts. The isocyanate is hexamethylene diisocyanate prepolymer (average molecular weight of about 0.07 × 10 ⁴ , average number of functional groups (F) = 2, manufactured by Asahi Kasei Chemicals, Duranate AE700-100), and the NCO / OH molar ratio is 0.00. 9 was used.

The raw materials shown in Tables 1 to 3 are as follows.
A1: Polyether polyol, polymer of propylene oxide (PO) unit using glycerol as an initiator, average molecular weight 1.5 × 10 ⁴ , average number of functional groups (F) = 3, manufactured by Asahi Glass Co., Ltd., trade name Preminol S3015;
A2: Polyether polyol, PO unit polymer with glycerin as an initiator, average molecular weight 1.2 × 10 ⁴ , F = 3, manufactured by Asahi Glass Co., Ltd., trade name Preminol 3012;
A3: Polyether polyol, PO unit polymer using glycerin as an initiator, average molecular weight 1.0 × 10 ⁴ , F = 3, manufactured by Asahi Glass Co., Ltd., trade name Preminol S3011;
A4: Polyether polyol, copolymer of EO units and PO units using glycerin as an initiator, average molecular weight 1.0 × 10 ⁴ , F = 3, EO unit content = 10%, manufactured by Asahi Glass Co., Ltd., trade name Preminol 7012 ;
B1: Polyether polyol, PO unit polymer starting with propylene glycol, average molecular weight 1.5 × 10 ⁴ , F = 2, manufactured by Asahi Glass Co., Ltd., trade name Preminol S4015;
B2: Polyether polyol, PO unit polymer with propylene glycol as an initiator, average molecular weight 1.0 × 10 ⁴ , F = 2, manufactured by Asahi Glass Co., Ltd., trade name Preminol S4011;
B3: Polyether polyol, PO unit polymer with propylene glycol as an initiator, average molecular weight 0.55 × 10 ⁴ , F = 2, manufactured by Asahi Glass Co., Ltd., trade name Preminol S4006;
B4: Polyether polyol, copolymer of EO units and PO units using propylene glycol as an initiator, average molecular weight 0.4 × 10 ⁴ , F = 2, EO unit content = 25%, manufactured by Asahi Glass Co., Ltd., trade name Preminol 5005;
B5: Polyether polyol, PO unit polymer with propylene glycol as an initiator, average molecular weight 0.2 × 10 ⁴ , F = 2, manufactured by Asahi Glass Co., Ltd., trade name Preminol S4001;
C: Polyether monool, polymer of PO unit with methanol as an initiator, average molecular weight 0.33 × 10 ⁴ , F = 1, manufactured by Asahi Glass Co., Ltd., trade name Preminol S1004F;
Catalyst: Curing catalyst for urethane, zinc carboxylate, manufactured by King Industries, trade name K-KAT XK-627

2. Measurement of Adhesive Properties The adhesive properties and the like of the patch materials of Examples 1 to 20 and Comparative Examples 1 to 10 produced above were measured by the following tests. The results are shown in Tables 1-3.

(1) Preparation of test piece For measurement of adhesive strength against bakelite, probe tack, holding force, and skin adhesive strength, the width of the substrate is 12 mm x 75 mm long so that the MD direction of the substrate is the long side of the sample. Cut.
For ball tack measurement, the substrate was cut into a width of 25 mm and a length of 225 mm so that the MD direction of the substrate was the long side of the sample.

(2) Adhesive strength against bakelite According to JIS Z-0237, a 12 mm wide test piece was attached to a bakelite panel (phenol resin plate, manufactured by Sumitomo Bakelite Co., Ltd.) at 23 ° C. and 50% RH atmosphere, and 2 kg One reciprocal pressure bonding was performed with a rubber roll at a speed of 300 mm / min, and after standing for 20 minutes, a 180 ° peeling force was measured at a peeling speed of 300 mm / min (average value of three specimens).

(3) Probe tack According to ASTM D-2979, using an NS probe tack tester (manufactured by Nichiban Co., Ltd.) in an atmosphere of 23 ° C. and 50% RH, a probe having a diameter of 5 mm, a pressure of 0.98 N / cm ² , The measurement was performed under the conditions of a contact time of 1 second and a peeling speed of 10 mm / sec (average value of 3 samples).

(4) Ball tack According to JIS Z-0237, measurement was performed using an inclined ball tack tester in an atmosphere of 23 ° C. and 50% RH. A test piece having a width of 25 mm was fixed with a double-sided tape (manufactured by Nichiban Co., Ltd.) so that the inclination angle was 30 °, the runway was 100 mm, and the measurement part (adhesive surface of the test piece) was 100 mm. Rolled 32 types of bearing balls with a diameter of 1/32 to 1 inch, and the maximum number of balls that remained on the adhesive surface for 30 seconds or more. Was measured.

(5) Holding strength against glass plate In accordance with JIS Z-0237, a test piece having a width of 12 mm, covered with a suitable adhesive tape to prevent the test piece from being stretched at 23 ° C. and 50% RH, It was pasted to an area of 12 mm × 20 mm, and was subjected to one reciprocal pressure bonding with a 2 kg rubber roll at a speed of 300 mm / min. After leaving for 20 minutes, the pressure-sensitive adhesive sheet was hung so as to hang vertically, a load of 200 g was applied, and the shift length after 1 hour was measured (average value of 3 samples).

(6) Adhesion state, pain when peeling off, adhesive residue A test piece of 12 mm width was affixed to the inner side of the forearm of 5 adult men and women in an atmosphere of 23 ° C and 50% RH. Then, it was observed whether or not the adhesive remained on the skin after peeling (glue residue), and “adhesion state”, “pain”, and “glue residue” were evaluated according to the following criteria.
Adhesion state: The adhesion state 1 hour after application was evaluated according to the following criteria.
AA: 4 to 5 people adhered well over the entire surface of the test piece.
A: Three people adhered well over the entire surface of the test piece.
B: Two people adhered well over the entire specimen surface.
C: 1 person adhered well over the whole test piece.
Pain; Pain at the time of peeling was evaluated according to the following criteria.
AA: 4-5 people felt no pain.
A: Three people felt no pain.
B: Two people felt no pain.
C: One person felt no pain.
Adhesive residue: The degree of the adhesive remaining on the skin after peeling off the test piece was evaluated according to the following criteria.
AA: No adhesive residue was seen in 4 to 5 people.
A: No glue residue was seen in 3 people.
B: Adhesive residue was not seen in 2 persons.
C: No glue residue was seen in one person.

(7) Coating property As an evaluation of coating property, the mixture was coated on release paper, heated in an oven at 130 ° C for 1 minute, and the area where the mixture repelled against the coated area was scored according to the following criteria. .
AA: The repelled area is 5% or less of the coated surface. A: The repelled area is about 5% to 20% of the coated surface. B: The repelled area is 20 to 40% of the coated surface.
C: The area that repels is 40% or more of the coated surface

3. Moisture Permeability Moisture permeability was evaluated as the amount of water vapor passing through a test piece of a unit area for a certain time. Specifically, in a 40 ° C. atmosphere, when the relative humidity of the space on one side separated by the test piece is 90% and the other side space is kept dry by the hygroscopic agent, the test piece passes through for 24 hours. The mass (g) of water vapor was measured and converted per 1 m ^{2 of} the test material. The measurement is performed according to JIS Z-0208. A round test piece with a diameter about 10 mm larger than the inner diameter of the cup is put on a cup containing about 8 g of calcium chloride moisture absorbent, and a rubber packing is used to prevent the test piece from shifting. The ring was put on and screwed. When measuring the moisture permeability of the pressure-sensitive adhesive layer, a test piece was prepared by supporting the pressure-sensitive adhesive layer to be measured with a rough nylon net that does not affect the moisture permeability of the pressure-sensitive adhesive layer, and measured in the same manner as described above. . After measuring the total mass of the test piece, it was placed in a constant temperature and humidity chamber under a 40 ° C., 90% RH atmosphere, and the change in mass per fixed time was measured. The moisture permeability was determined according to the following formula:
Moisture permeability (g / m ² · 24hr) = W x 24000 / S
[In the formula, S represents a moisture permeable area (cm ² ), and W represents an increase in mass per hour (g / hr). ]

When the total polyether polyol is 100 parts, the patch of Examples 1 to 20 having an average molecular weight of 1.2 × 10 ⁴ or more and an average functional group of 3 polyether polyol of 40 parts or more has a ball tack of 15 or more. The glass plate holding force (holding force deviation) was within 1 mm.

On the other hand, when the total polyether polyol is 100 parts, the patch of Comparative Example 1 in which the polyether polyol having an average molecular weight of 1.5 × 10 ⁴ and an average functional group number of 3 is less than 40 parts has a ball tack of 15 or more. As shown, the holding force deviation exceeded 1 mm.

Further, Comparative Examples 2 and 3 not containing a polyether polyol having an average molecular weight of 1.2 × 10 ⁴ or more and an average functional group number of 3 showed a ball tack of 24 or more, but the evaluation was based on a holding force deviation of 1 mm or more, or insufficient cohesive force. It became impossible.

In Comparative Examples ^{4, 5,} and 10, which did not contain a polyether polyol having an average molecular weight of 0.1 × 10 ⁴ or more and an average functional group number of 2, the deviation in holding force was within 1 mm, but the ball tack was 13 or less.

In addition, the adhesive materials of Comparative Examples 6 to 9 in which the polyether polyol having an average molecular weight of 1.0 × 10 ⁴ or less and an average functional group number of 3 was 40 parts or more showed repelling when applied to release paper. There was a problem with sex. If the coating properties are poor, even if the adhesive properties are good, it is not suitable for actual production, and the adhesive thickness of the obtained patch will vary, resulting in variations in adhesive properties and good adhesive properties. It is not possible to obtain a patch having

In Examples 1 to 20, the state of application to the skin 1 hour after application was good and adhered well over the entire surface of the test piece, and almost no adhesive residue remained on the skin after peeling.

From the above, 40 to 90 parts by weight of a polyether polyol having an average molecular weight of 1.2 × 10 ⁴ or more and an average functional group number of 3 and a polyether polyol having an average molecular weight of 0.1 × 10 ⁴ or more and an average functional group number of 2 When used, it was confirmed that an adhesive having good adhesive properties and coatability could be obtained.

The patch material using the pressure-sensitive adhesive of the present invention is applied to skin and the like, and is suitably used for medical purposes, for example, in the fields of medical hygiene and external use. Specifically, it can be used for adhesive bandages, adhesive bandages, dressing materials, surgical surgical tapes, percutaneous absorption preparations, and the like. The patch of the present invention can take any form such as a film, a sheet, a plate, a strip, and a tape according to the usage. Moreover, it may be stored in a roll and may be used after being appropriately cut at the time of use.

DESCRIPTION OF SYMBOLS 1 Support body 2 Support body 3 Adhesive layer 4 Stripping body

Claims

Solvent-free polyurethane adhesive,
(A) an active hydrogen compound having an average molecular weight of 1.2 × 10 4 or more and an average functional group number of 3;
(B) an active hydrogen compound having an average molecular weight of 0.1 × 10 4 or more and an average functional group number of 2;
(C) A pressure-sensitive adhesive obtained by reacting with an organic polyisocyanate having an average functional group number of 2 (where, in the pressure-sensitive adhesive, when the total active hydrogen compound is 100 parts by weight, the active hydrogen compound of (A) Is 40 to 90 parts by weight).
The polyurethane adhesive according to claim 1, wherein the active hydrogen compound of (A) is 45 to 70 parts by weight when the total active hydrogen compound is 100 parts by weight in the adhesive.
The polyurethane pressure-sensitive adhesive according to claim 1 or 2, wherein the average molecular weight of the active hydrogen compound activity of (A) is 1.4 × 10 4 or more.
4. The polyurethane-based pressure-sensitive adhesive according to claim 1, wherein the active hydrogen compound is a polyether polyol.
A patch comprising an adhesive layer comprising the adhesive according to any one of claims 1 to 4.
6. The patch according to claim 5, wherein the pressure-sensitive adhesive layer has a thickness of 5 to 100 μm.
The patch according to claim 5 or 6, wherein the moisture permeability of the patch is 1,000 g / m 2 · 24 hr or more.