CN107001866A - Patch material - Google Patents

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Publication number
CN107001866A
CN107001866A CN201480083859.1A CN201480083859A CN107001866A CN 107001866 A CN107001866 A CN 107001866A CN 201480083859 A CN201480083859 A CN 201480083859A CN 107001866 A CN107001866 A CN 107001866A
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China
Prior art keywords
adhesive
mass
methyl
patch material
alkyl acrylate
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Granted
Application number
CN201480083859.1A
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Chinese (zh)
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CN107001866B (en
Inventor
藤泽博充
南波真广
木幡佳奈子
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Nichiban Co Ltd
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Nichiban Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00—Bandages or dressings; Absorbent pads
    • A61F13/02—Adhesive bandages or dressings
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42—Use of materials characterised by their function or physical properties
    • A61L15/58—Adhesives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Organic Chemistry (AREA)
  • Vascular Medicine (AREA)
  • Hematology (AREA)
  • Heart & Thoracic Surgery (AREA)
  • Materials Engineering (AREA)
  • Epidemiology (AREA)
  • Biomedical Technology (AREA)
  • Medicinal Preparation (AREA)
  • Materials For Medical Uses (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

It is an object of the invention to provide a kind of patch material, it is characterized in that, adhesive phase is formed by (a) adhesive A and (b) adhesive B mixed adhesive being mixed, simultaneously, (i) adhesive A and the adhesive B mixed proportion are 15/85~85/15, meanwhile, (ii) mixed adhesive is cross-linking products, wherein, (a) adhesive A：Acrylic adhesives containing copolymer, the copolymer is made by the mass % of (methyl) alkyl acrylate 65~99.5 of the alkyl with carbon number 8~12, the mass % of vinyl monomer 0.5~8 with functional group, without the hydrophilic mass % of vinyl monomer 0~34.5；(b) adhesive B：Acrylic adhesives containing copolymer, the copolymer is made by the mass % of (methyl) alkyl acrylate 50~90 of the alkyl with carbon number 8~12, the mass % of vinyl monomer 0.5~8 with functional group, with the hydrophilic mass % of vinyl monomer 9.5~49.5.

Description

Patch material
Technical field
The present invention relates to medical field, it is related to patch material, the patch material particularly promotes to hurt, abrade, stab, The treatment of the wounds such as scuffing, foot's mill bubble and mild burn, mitigates pain, keeps moist environment, additionally for protection purpose； In particular, the present invention relates to the patch material suitable for first aid adhesive plaster.In addition, the present invention relates to can be as medical adhesive tape or can The useful patch material of the transdermal formulation of percutaneous dosing.
Background technology
Generally, patch material possess support body layer that plastic foil, woven fabric, non-woven fabrics, looped fabric, paper etc. is made and The Rotating fields of the adhesive phase set at least one side of support body layer.Further, can in order to protect the surface of adhesive phase Separation layer is set, in addition, for example in the case where support body layer is very thin, with the layer knot for possessing carrier layer in support body layer Structure.
As the supporter of patch material, in the case of using woven fabric, non-woven fabrics, looped fabric, paper etc., due to penetrability It is excellent, but water proofing property is poor, in the case of the uses such as wet operation place, there are problems that bonding force reduction,.
In this regard, to ensure water proofing property, film is used in supporter, moisture permeability is reduced by film, risen accordingly, there exist skin The problems such as wrinkling, be also easy to produce fash.It is therefore desirable to while with water proofing property, penetrability and cohesive also excellent adhesive.
Generally, in patch material, it is used as the adhesive for constituting adhesive phase, it is known to rubber-like, acrylic compounds, organosilicon Class and polyurethane binding, wherein, from it is heat-resisting, have excellent weather resistance while bonding force also very excellent viewpoint and from easy From the viewpoint of modification, acrylic adhesives are preferably used.
In the case of acrylic adhesives, the adhesive penetrability being made up of the high copolymer of hydrophilic monomer ratio It is high but bonding force is weak, on the other hand, if the ratio of alkyl acrylate (hydrophobic monomer) increases, bonding force can be made to increase but thoroughly Moist reduction.In order to improve the bonding force and penetrability of acrylic adhesives, change in acrylic adhesives as its master The species of (methyl) acrylate monomer of composition is wanted, can manufacture and sexually revise various hydrophilic monomers and copolymerization to improve moisture-inhibiting The copolymer of property monomer etc., can manufacture the acrylic adhesives with multifrequency nature.But, even predictable bonding force and The aspect of penetrability two all very situations of excellent copolymer, frequently result in bonding force and penetrability either side are all insufficient Adhesive, the adhesive that bonding force and penetrability have both fully is met it is difficult to obtain.It therefore, it can consider the third of different qualities Alkene acrylic binder is used in mixed way.
In patent document 1, it was recently reported that as adhesive phase, the adhesive after being crosslinked containing following (A), (B) and (C), its In, the copolymer that the monomer that (A) contains carboxyl or hydroxyl is made with (methyl) acrylate as neccessary composition copolymerization, (B) side The copolymerization that the monomer and (methyl) acrylate for containing the nitrogen-atoms without salt structure on chain are made as neccessary composition copolymerization Thing, the organic liquid component that (C) mixes with above-mentioned (A) composition and (B) composition.In addition, in patent document 2, it was recently reported that contain (A) Composition and (B) composition, as the copolymer of foregoing (A) composition and from by metallo-chelate, metal oxide and metal hydroxide At least one crosslinking agent selected in the group that thing is constituted by the adhesive after cross-linking reaction, wherein, (A) composition is by having Have a monomer for containing carboxyl and (methyl) acrylate be made as the copolymer of monomeric unit, (B) composition by with containing The monomer and (methyl) acrylate for having pyrrolidone-base are made as the copolymer of monomeric unit.But, in this two documents, Cohesive and the dissolubility of medicine have effect, but do not consider the film for using water proofing property as saturating in the case of supporter It is moist.
In patent document 3, it was recently reported that use the mixture of (A) and (B) two kinds of adhesives, wherein, (A) contains metering system Sour 2- acetoacetoxyethyls and other vinyl monomers as the copolymer of constituent binding property polymer A, (B) with The carbon number of alkyl for (methyl) alkyl acrylate of 4~10 with other vinyl monomers as constituent, contain There is the binding property polymer B of the copolymers different from aforementioned adhesion polymer A.In addition, in patent document 4, it was recently reported that contain Binding property polymer A that weight average molecular weight is 500,000~1,000,000, the binding property polymer that weight average molecular weight is 1,000,000~1,500,000 B and liquid plasticizer medical non-crosslinked adhesive, binding property polymer A are (methyl) alkyl acrylate and N- ethene Polymer that base -2-Pyrrolidone copolymerization is obtained, binding property polymer B (methyl) alkyl acrylate are polymerized alone and obtained Polymer or (methyl) alkyl acrylate and polymerizeing that the comonomer beyond NVP is obtained The medical non-crosslinked adhesive of thing.But, in this two documents, it is contemplated that cohesive and skin irritation, in order that adhesive The intermiscibility in mixing each other is good, using liquid plasticizer, but further consider water proofing property, penetrability and Cohesive.
As described above, when two kinds of different acrylic adhesives of composition are mixed, intermiscibility is deteriorated, it is necessary to add plasticizer Situation increase.In addition, in the case where the film high using water proofing property is used as supporter, it is desirable to improve penetrability and cohesive And the excellent patch material of intermiscibility of two kinds of acrylic adhesives.
Prior art literature
Patent document
Patent document 1：JP 2000-44904 publications
Patent document 2：JP 2006-241179 publications
Patent document 3：No. 2006/64747 publication of International Publication No.
Patent document 4：JP 2005-314251 publications
The content of the invention
The invention technical problem to be solved
The problem of the present invention is provided is used as mixed adhesive by two kinds of acrylic adhesives mixing, even if to improve Water proofing property, use membrane material as supporter in the case of, also without skin corrugation, the situation of fash and water proofing property, penetrability The patch material having both with cohesive.
Solve the means of technical problem
The present inventors are associated as adhesive phase, by with specific to solve the result of above-mentioned problem further investigation Ratio coordinate intermiscibility it is good, specific two kinds of acrylic adhesives and be further crosslinked, even in being used as supporter In the case of using membrane material, the patch material that water proofing property, flexibility, cohesive have both completely can be made.
For acrylic adhesives, usually as monomeric unit, (methyl) alkyl acrylate as mainly into Point.During according to the content of (methyl) alkyl acrylate of the alkyl with carbon number 8~12 more than certain value, by skin The sebum composition of secretion is easily absorbed by adhesive, patch material is difficult to the knowledge peeled off, the present inventors associate with (methyl) alkyl acrylate of the alkyl of carbon number 8~12 is used as main component.
I.e., it is contemplated that can using main component as the alkyl with carbon number 8~12 (methyl) alkyl acrylate Two kinds of acrylic adhesives, by forming mixed adhesive and being further crosslinked, obtain required water proofing property, penetrability and The adhesive that cohesive has both.
The present inventors consider that usual main component is (methyl) alkyl acrylate of the alkyl with carbon number 8~12 The acrylic adhesives of base ester are it may be said that with hydrophobic characteristic, by its acrylic adhesives with hydrophilic characteristic Mix and be further crosslinked, the adhesive that water proofing property, penetrability and cohesive have both can be thus made.
Therefore, the present inventors are based in (methyl) alkyl acrylate, to be crosslinked the cooperation on a small quantity of necessary degree It can be explored for crosslinking purpose with (methyl) alkyl acrylate copolymer, vinyl monomer with functional group adhesive 3rd composition of the hydrophilic characteristic of generation.In this case, in mixing, it is necessary to consider the phase of two kinds of acrylic adhesives Dissolubility is suitable.But, due to reducing the characteristic of adhesive using plasticizer, therefore it is not preferred.
The present inventors are during further investigation, it is considered to intermiscibility, are found to be the acrylic acid for obtaining hydrophilic characteristic Class adhesive, using with hydrophilic vinyl monomer as the 3rd composition be appropriate.That is, present inventors found that passing through the 3rd The presence or absence of composition, adhesive A (without the 3rd composition) acrylic compounds different from adhesive B (containing the 3rd composition) characteristic glue The mixed adhesive of mixture, by the way that the mixed adhesive is crosslinked, can obtain the bonding that water proofing property, penetrability and cohesive have both Agent.
That is, by the present invention, (1) can provide a kind of patch material, it is characterised in that foregoing patch material possesses supporter Layer and adhesive phase, the adhesive phase are formed by (a) adhesive A and (b) adhesive B mixed adhesive being mixed, meanwhile, (i) when aforementioned adhesion agent A and aforementioned adhesion agent B gross mass is 100 mass parts, the adhesive A and adhesive B mixing ratios Example (adhesive A/adhesive B) is 15/85~85/15 (mass ratio), meanwhile, (ii) mixed adhesive is cross-linking products, its In,
(a) adhesive A：Acrylic adhesives containing copolymer, the copolymer is by with carbon number 8~12 The mass % of (methyl) alkyl acrylate 65~99.5 of alkyl, can with (methyl) alkyl acrylate copolymer have function Group the mass % of vinyl monomer 0.5~8 as neccessary composition, and further monomer add up to 100 mass % in the range of, The vinyl monomer different with the vinyl monomer from (methyl) alkyl acrylate and can be with (methyl) alkyl acrylate Base ester copolymerization and it is made without the hydrophilic mass % of vinyl monomer 0~34.5 as residual components；
(b) adhesive B：Acrylic adhesives containing copolymer, the copolymer in monomer by adding up to 100 mass % In the range of, the mass % of (methyl) alkyl acrylate 50~90 of the alkyl with carbon number 8~12, can be with (methyl) The mass % of vinyl monomer 0.5~8 with functional group of alkyl acrylate copolymer, with should (methyl) alkyl acrylate and The different vinyl monomer of the vinyl monomer and can be with (methyl) alkyl acrylate copolymer and with hydrophilic second The mass % of alkenyl monomer 9.5~49.5 is made as neccessary composition.
In addition, by the present invention, (2) can provide the patch material of foregoing (1), wherein, the crosslinking of aforementioned adhesion oxidant layer is led to Cross crosslinking agent progress.
In addition, by the present invention, (3) can provide the patch material of foregoing (1), wherein, aforementioned functional groups are carboxyl or hydroxyl Base.
In addition, by the present invention, (4) can provide the patch material described in any one in foregoing (1)~(3), wherein, It is liquid plasticizer at room temperature that aforementioned adhesion oxidant layer, which is not contained,.
In addition, by the present invention, (5) can provide the patch material described in any one in foregoing (1)~(4), wherein, Foregoing support body layer contains film.
In addition, by the present invention, (6) can provide the patch material described in any one in foregoing (1)~(5), wherein, Foregoing support body layer is the lamination of film and cloth.
In addition, by the present invention, (7) can provide the patch material described in any one in foregoing (1)~(6), wherein, Moisture permeability is 300g/m2More than 24h.
In addition, by the present invention, (8) can provide the patch material described in any one in foregoing (1)~(7), wherein, When aforementioned adhesion agent A and aforementioned adhesion agent B gross mass is 100 mass parts, aforementioned adhesion agent A and aforementioned adhesion agent B's is mixed Composition and division in a proportion (adhesive A/adhesive B) is 35/65~65/35 (mass ratio).
In addition, by the present invention, (9) can provide the patch material described in any one in foregoing (1)~(8), wherein, It is used as adhesive A and (methyl) acrylic acid alkyl of the alkyl with carbon number 8~12 of adhesive B main composition The difference of the solubility parameter (SP) of ester is within 0.50.
In addition, by the present invention, (10) can provide the patch material described in any one in foregoing (1)~(9), its In, foregoing patch material is first aid adhesive plaster.
Invention effect
By the invention it is possible to realize following effect：It is not necessary to using plasticizer, by the hydrophobicity third with intermiscibility The mixed adhesive that alkene acrylic binder is made with hydrophilic acrylic adhesives enters one as the adhesive of patch material The mixed adhesive is crosslinked by step, even if it is possible thereby to provide supporter for the film with water proofing property, will not also occur skin and rise Wrinkle, produce fash, while having both the patch material of water proofing property, penetrability and cohesive.
Above-mentioned patch material can be used as first aid adhesive plaster, medical adhesive tape or transdermal formulation.
Embodiment
The patch material of the present invention is substantially the patch material for possessing support body layer and adhesive phase.
1. support body layer
The support body layer of the patch material of the present invention can enumerate cloth such as film, woven fabric, looped fabric, non-woven fabrics etc., especially, Preferably comprise film, the film there is water proofing property and meanwhile skin can be close to and can follow the such degree of skin movements soft material, And the generation such as fash of skin after long-time is attached can be suppressed.
The film used as the support body layer of the present invention, can enumerate such as polyethylene, polypropylene, poly terephthalic acid second two Alcohol ester (hereinafter also referred to " PET "), polybutylene terephthalate (PBT), PEN, polystyrene, nylon, Cotton, acetic acid artificial silk, artificial silk, artificial silk/polyethylene terephthalate compound, polyacrylonitrile, polyvinyl alcohol, propylene Acids polyurethane, polyester-based polyurethane, polyether polyurethane, styrene-isoprene-styrene copolymer, styrene-fourth two Alkene-styrol copolymer, styrene ethylene-propylene-styrol copolymer, SBR styrene butadiene rubberses, ethane-acetic acid ethyenyl Ester copolymer, glassine paper etc. are used as the monofilm of composition or the layered product of film.In addition, generation in order to suppress skin rash etc., As support body layer, moisture permeability (according to specified in JIS Z0208 B conditions (40 DEG C of temperature, the phase of support body layer is preferably used To humidity 90%) determine) it is 1,000g/m2More than 24h hours, particularly 2,000g/m2More than 24h hours.
In addition, in the present invention, as with water proofing property, further there is the support body layer of flexibility and penetrability, preferably Use elastomer film.As the elastomer for forming elastomer film, such as polyurethane elastomer, 1,2- polybutadienes heat can be enumerated Mixing more than thermoplastic elastic, polystyrene-type thermoplastic elastomers, polyolefins thermoplastic elastomer and above two Thing etc..In above-mentioned elastomer, preferred polyurethane elastomer film.
As the support body layer of the present invention, on the above-mentioned film with water proofing property, in order to further have flexibility and suction It is moist, the support body layer after preferably cloth is laminated.Cloth is in addition to natural fiber, by polyester fiber, polyacrylic fibre, to gather Non-woven fabrics, woven fabric and looped fabric that urethane fiber is made, wherein, from the viewpoint of flexible, by polyurethane fiber system Into non-woven fabrics be preferred.The side for being laminated to coating adhesive of film and cloth can be film, or cloth.
The thickness of support body layer
The thickness for the support body layer that the patch material of the present invention possesses is 10~50 μm of model in the case of only film Enclose, by film and it is fabric into layered product in the case of, can for 20~250 μm, be preferably 70~200 μm.By film and fabric stratification In the case of laminate, the thickness of film is 2~20 μm, is preferably 3~10 μm.Thickness mistake of the thickness of support body layer in support body layer In the case of thin, the intensity of support body layer becomes insufficient, and patch material is attached at skin, when peeling off patch material from skin When, the situation that support body layer is torn can be produced.In addition, when the thickness of support body layer is excessive, the thickness of patch material becomes big, and it is tied Fruit patch material is difficult to be close to the tiny concavo-convex skin surface such as sulci of skin, and attaching state becomes obvious, is easily produced tight The incongruity of weight.
Additive
In attaching, in order that patch material is unobtrusively, i.e. from the so-called viewpoint for easily appearing the skin color under attaching Set out, the film for forming support body layer is preferred to use the excellent plastic foil of the transparency mostly, but is formed in the film of support body layer, according to Need, the various additives such as colouring agent, stabilizer, ultra-violet absorber, the lubricants such as pigment and dyestuff can be contained.Above-mentioned addition The content of agent can select most suitable scope according to the species of additive, relative to the mass parts of resin material 100 for constituting film, on The content for stating additive is generally mostly 0.001~30 mass parts, is preferably 0.01~25 mass parts, is more preferably 0.1 The scope of~20 mass parts.
Embossing processing
When patch material is attached at the skin surface of people, feel, slickness, outward appearance in order to improve patch material etc., Constitute on the back side (surface for representing the support body layer positioned at the opposite side of adhesive phase side) of the support body layer of patch material, it is excellent Form slection is into small concavo-convex situation.That is, processing can be embossed to the surface of the support body layer of the opposite side of adhesive phase side Patch material.By being embossed processing, the coefficient of kinetic friction on support body layer surface can be reduced to less than 1.0.If in addition, in carrier Small bumps can be formed by being embossed processing, support body layer is formed on the small male and fomale(M＆F), by bullet on the surface of layer Property the formation of body film support body layer surface (back side) on can transfer the small bumps.
In addition, for the purpose of improving anchoring with adhesive etc., support body layer also can carry out sandblasting in one or two sides Processing, sided corona treatment etc. are surface-treated.In addition, in order to easily take out patch material from packaging material, also can be in support body layer One or two sides on set concavo-convex by method outside sandblasting.
2. adhesive phase
For the patch material of the present invention, the adhesive of adhesive phase is formed mixed for following two acrylic adhesives Close the mixed adhesive being made.
(a) adhesive A：
Acrylic adhesives containing copolymer, the copolymer by the alkyl with carbon number 8~12 (first Base) 65~99.5 mass % of alkyl acrylate, can be with (methyl) alkyl acrylate copolymer the ethene with functional group The mass % of base monomer 0.5~8 as neccessary composition, and further monomer add up to 100 mass % in the range of, with (the first Base) the alkyl acrylate vinyl monomer different with the vinyl monomer and can be with (methyl) alkyl acrylate copolymer And be made without the hydrophilic mass % of vinyl monomer 0~34.5 as residual components.
(b) adhesive B：
Acrylic adhesives containing copolymer, the copolymer in monomer in the range of adding up to 100 mass %, tool Have the alkyl of carbon number 8~12 the mass % of (methyl) alkyl acrylate 50~90, can be with (methyl) acrylic acid alkyl The mass % of vinyl monomer 0.5~8 with functional group of ester copolymerization and (methyl) alkyl acrylate and the vinyl list The different vinyl monomer of body and can be with (methyl) alkyl acrylate copolymer and with hydrophilic vinyl monomer 9.5 ~49.5 mass % are made as neccessary composition.
Further, for the mixed adhesive, when adhesive A and adhesive B gross mass are 100 mass parts, Adhesive A and adhesive B mixing ratio (adhesive A/adhesive B) is 15/85~85/15 (mass ratio), be preferably 25/75~ 75/25 (mass ratio), more preferably 35/65~65/35, in addition, adhesive A is cross-linking products with adhesive B.
Adhesive A is double component systems or 3 component systems, determine composition than method depend on the amount of adhesive A, so Afterwards, by neccessary composition into being placed in prescribed limit, by all as 100 mass % in the way of, residual components are placed in rule Determine in scope.Adhesive B is 3 component systems, and composition ratio is determined with all 100 mass %.
(1) adhesive A
Adhesive A is hydrophobicity.
Acrylic adhesives A used in the patch material of the present invention is the acrylic adhesive containing copolymer Agent, the copolymer by the alkyl with carbon number 8~12 the mass % of (methyl) alkyl acrylate 65~99.5, preferably For 75~99.3 mass %, more preferably 80~98 mass %, can have with (methyl) alkyl acrylate copolymer The mass % of vinyl monomer 0.5~8 of functional group, preferably 0.7~6 mass %, more preferably 0.9~5 mass % institutes State as neccessary composition, and further monomer add up to 100 mass % in the range of, with (methyl) alkyl acrylate and The different vinyl monomer of the vinyl monomer and can be with (methyl) alkyl acrylate copolymer and without hydrophilic The mass % of vinyl monomer 0~34.5, preferably 0~24.3 mass %, more preferably 0~19.1 mass % are used as residue Composition is made.
(1-1) has (methyl) alkyl acrylate of the alkyl of carbon number 8~12
, can as (methyl) alkyl acrylate of the alkyl with carbon number 8~12 of neccessary composition in adhesive A Enumerate (methyl) n-octyl, (methyl) 2-EHA, (methyl) Isooctyl acrylate monomer, (methyl) acrylic acid Different nonyl ester, the positive last of the ten Heavenly stems ester of (methyl) acrylic acid, (methyl) isodecyl acrylate, (methyl) lauryl acrylate etc..Above-mentioned (methyl) In alkyl acrylate, different nonyl ester of particularly preferred 2-EHA, acrylic acid etc. has the alkyl of carbon number 8~9 Alkyl acrylate.Above-mentioned (methyl) alkyl acrylate can individually using or be used in combination.
(1-2) can be with (methyl) alkyl acrylate copolymer the vinyl monomer with functional group
For functional group, as to make adhesive A be played a role with the adhesive B functional groups being crosslinked, as functional group, Can be carboxyl, hydroxyl, amino, amide groups and epoxy radicals, wherein preferably carboxyl and hydroxyl., can as the monomer containing carboxyl Enumerate (methyl) acrylic acid, itaconic acid, maleic acid, as the monomer containing hydroxyl, can enumerate (methyl) acrylate, (methyl) hydroxy-ethyl acrylate, (methyl) hydroxypropyl acrylate, gather in addition, (methyl) propylene acid diethylene glycol monoesters etc. can be enumerated (methyl) acrylic monoester of aklylene glycol.As the monomer with amino, (methyl) aminoethyl acrylate can be enumerated；As Monomer containing amide groups, can enumerate (methyl) acrylamide；As the monomer containing epoxy radicals, acrylic acid can be enumerated and shrink sweet Grease.Above-mentioned substance can be used in combination.It is preferred that acrylic acid, polyethylene glycol monomethacrylate.
(1-3) can be with (methyl) alkyl acrylate copolymer and without hydrophilic vinyl monomer
The vinyl monomer is the monomers different from foregoing (1-1), (1-2) vinyl monomer, without hydrophily.
I.e., herein, as without hydrophilic vinyl monomer, will as foregoing (1-1) (methyl) alkyl acrylate Base ester and as being foreclosed used in the vinyl monomer of foregoing (1-2) with the vinyl monomer of functional group.
That is, in adhesive A, (methyl) alkyl acrylate or vinyl monomer with functional group with without hydrophily Vinyl monomer do not repeat.
As the different vinyl monomer of (1-1) foregoing from this, (1-2) vinyl monomer, it can enumerate with carbon atom (methyl) alkyl acrylate or vinyl esters of the alkyl of number 1~6 etc..
That is, (methyl) alkyl acrylate of the alkyl with carbon number 1~6 can enumerate (methyl) acrylic acid first Ester, (methyl) ethyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) the just own ester of acrylic acid etc..
In addition, can enumerate：(methyl) acrylate with saturated carbon rings such as cyclohexyl；Vinyl acetate, vinyl propionate The vinyl esters such as ester；The vinyl monomer (unsaturated nitrile) containing cyano group such as acrylonitrile, methacrylonitrile；The vinyl such as styrene Aromatic compound；Acrylamide etc..Above-mentioned substance can be used in combination.It is preferred that vinyl acetate.
(1-4) specifically, can be enumerated for example containing by the different matter of nonyl ester 96 of acrylic acid as adhesive A as described above The adhesive for the copolymer that amount %, the mass % of acrylic acid 4 are made；Containing by the different mass % of nonyl ester 98 of acrylic acid, the matter of acrylic acid 2 The adhesive for the copolymer that amount % is made；Containing by the mass % of 2-EHA 85, the mass % of acrylic acid 4, acetic acid second The adhesive for the copolymer that the mass % of alkene ester 11 is made.
(2) adhesive B
Adhesive B is hydrophily.
Acrylic adhesives B used in the patch material of the present invention is containing copolymer, with hydrophilic Acrylic adhesives, the copolymer in monomer in the range of adding up to 100 mass %, the alkane with carbon number 8~12 The mass % of (methyl) alkyl acrylate 50~90 of base, preferably 51~88 mass %, more preferably 52~86 matter % is measured, can be with the mass % of vinyl monomer 0.5~8 with functional group of (methyl) alkyl acrylate copolymer, preferably 0.7~6 mass %, more preferably 0.9~5 mass %, with (methyl) alkyl acrylate and the vinyl monomer not With vinyl monomer and can with (methyl) alkyl acrylate copolymer and with hydrophilic vinyl monomer 9.5~ 49.5 mass %, preferably 11.3~48.3 mass %, more preferably 13.1~47.1 mass % are used as neccessary composition system Into.
(methyl) alkyl acrylate of (2-1) the adhesive B alkyl with carbon number 8~12 can be from foregoing (1- 1) selected in.
(2-2) adhesive B's can be from the vinyl monomer with functional group of (methyl) alkyl acrylate copolymer Selected in foregoing (1-2).
(2-3) can be with (methyl) alkyl acrylate copolymer and with hydrophilic vinyl monomer
In order to produce hydrophilic characteristic, as the 3rd composition, using with hydrophilic vinyl monomer.
The vinyl monomer be with (methyl) alkyl acrylate of foregoing (2-1), foregoing (2-2) vinyl monomer not Same vinyl monomer, with hydrophily.
I.e., herein, as with hydrophilic vinyl monomer, will as foregoing (2-1) (methyl) acrylic acid alkyl The vinyl monomer with functional group that the vinyl monomer with functional group described in ester, foregoing (2-2) is used forecloses.
That is, in adhesive B, with hydrophilic vinyl monomer and (methyl) alkyl acrylate or with functional group Vinyl monomer is not repeated.
As with hydrophilic vinyl monomer, usually using the vinyl monomer with alkoxy.
As the vinyl monomer with alkoxy, (methyl) acrylic acid 2- methoxy acrylates, (methyl) propylene can be enumerated Sour 2- ethoxy ethyl esters, (methyl) acrylic acid 2- propoxy ethyls, (methyl) acrylic acid 2- butoxyethyls, (methyl) acrylic acid 2- ethyoxyl methyl esters.Further, the alcoxyl of (methyl) acrylate, the methoxyl group diethylene glycol of methoxy ethyl glycol etc. can be enumerated (methyl) acrylate of base (poly-) aklylene glycol.Preferably acrylic acid 2- methoxy acrylates, methoxy poly (ethylene glycol) propylene Acid esters.
(2-4) can be enumerated for example as adhesive B as described above：Containing by the different mass % of nonyl ester 68 of acrylic acid, propylene The adhesive for the copolymer that 2 mass % of acid, the mass % of acrylic acid 2- methoxy acrylates 30 are made；Containing by the different nonyl ester 83 of acrylic acid Quality %, CH2=CHCOO- (CH2CH2O)9Mass %, CH of H 12=CHCOO- (CH2CH2O)9CH3What 16 mass % were made is total to The adhesive of polymers.
The manufacture of acrylic copolymer
The acrylic copolymer of the adhesive A and adhesive B that constitute the adhesive phase for forming the patch material of the present invention can Manufactured by radical polymerization.Be used as the polymerization of acrylic copolymer, it is known that solution polymerization process, emulsion polymerization method, Mass polymerization etc., from being readily available from the viewpoint of good adhesion characteristic, the bonding that patch material of the invention possesses The preferred solution polymerization process of oxidant layer.As to obtain the polymerization initiator of acrylic copolymer, benzoyl peroxide, peroxide can be enumerated Change the organic peroxides such as lauroyl；Azo-initiators such as azodiisobutyronitrile etc..Specifically, relative to formation acrylic acid The foregoing b-1 of copolymer), b-2) and b-3) composition the mass parts of whole monomers 100, add 0.1~3 mass parts radical polymerization Initiator is closed, under nitrogen protection, at a temperature of 40~90 DEG C or so, stirs 30 minutes~30 hours and carries out copolymerization.Solution In polymerization, as solvent, usually using ethyl acetate, acetone, toluene or their mixture.
The weight average molecular weight for constituting adhesive A and adhesive B acrylic copolymer is usually 100,000~1,500, 000th, it is preferably 300,000~1,000,000, more preferably 450,000~650,000 scope.It is common by acrylic acid The weight average molecular weight of polymers within the above range, coherency that can be in balance adhesive layer, bonding force, with the mixing of other compositions Compatibility of processability and other compositions etc..The weight average molecular weight of acrylic copolymer is by gel permeation chromatography (GPC) method The value obtained is used as using standard styrene scaled value.
Intermiscibility
For the adhesive phase of the present invention, when adhesive A and adhesive B gross mass are 100 mass parts, adhesive A and adhesive B is mixed with the ratio of 15/85~85/15 (mass ratio), further the structure with crosslinking.Adhesive A, which has, to be dredged It is aqueous, in addition, adhesive B has hydrophily, in order to which mixed adhesive, as adhesive phase and integration, is had each other Intermiscibility is critically important, in the present invention, is used as the alkyl with carbon number 8~12 of both main compositions (methyl) alkyl acrylate is same substance, even in different situations, preferably using the SP values of solubility parameter Material of the difference within 0.50.Adhesive A and adhesive B preferred mixing ratio are 25/75~75/25 (mass ratio), further Preferably 35/65~65/35 (mass ratio).
Crosslinking and crosslinking agent
In the present invention, by adhesive A and adhesive B mixed processings, it can also be handed under conditions of no crosslinking agent Connection, but be preferably crosslinked by crosslinking agent, as crosslinking agent, polyfunctional isocyanate compound (toluene diisocyanate can be enumerated Acid esters (TDI), 4,4 '-methyl diphenylene diisocyanate (MDI), hexamethylene diisocyanate, the sub- isocyanic acid of dimethylbenzene two Ester, sub- XDI, 1,5- naphthalene diisocyanates, hydrogenated diphenyl methane diisocyanate, hydrogenated toluene two Isocyanates, the sub- XDI of hydrogenation, IPDI etc.), multi-functional epoxy compound, levulinic Ketone metal salt etc., as commercially available product, may be selected the U ロ ネ ー ト (notes of the Japanese Port リ ウ レ タ Application Industrial Co., Ltd manufacture of purchase Volume trade mark) HL, U ロ ネ ー ト L, U ロ ネ ー ト EH, ガ ス KCCs of Mitsubishi manufacture TETRAD-X (registrars Mark), TETRAD-C (registration mark), ナ ー セ system (registration mark) aluminium etc..Relative to the propylene in adhesive A and adhesive B The mass parts of total amount 100 of acid copolymer, the content of crosslinking agent is preferably 0.01~1 mass parts, more preferably 0.03~0.5 Mass parts, particularly preferably 0.04~0.1 mass parts.Crosslinking agent can be used alone or in any combination, and two are added when also can be different More than kind, the method that can be set forth in before the adhesive coating to form adhesive phase or be added in coating.
Additive
In the adhesive phase of the present invention, in addition to aforementioned adhesion agent A, adhesive B and crosslinking agent, as needed, it can contain There are various additives.As additive, medicine, filler, antioxidant (antioxidant, preservative), colouring agent, perfume (or spice) can be contained The additive usually used in the adhesive for the adhesive phase that the formation patch material such as material, tackifier, plasticizer possesses.Example Such as, in order to adjust the adhesion characteristic of adhesive, tackifier can be coordinated.As tackifier, such as terpenes, terpene phenolic can be enumerated The tackifying resins such as class, coumarone-indene, phenylethylene, rosin, xylene, phenol, petroleum-type.
Plasticizer
The adhesive A and adhesive B that adhesive phase is formed in the present invention are to use the adhesive with intermiscibility to go forward side by side one Step carries out crosslinking Treatment, and therefore, adhesive usually not necessity in patch material contains plasticizer.As these plasticizer, It is known such as polyalcohols (glycerine, sorbierite, propane diols, 1,3 butylene glycol, 1,3- tetramethylene glycols, polyethylene glycol)； Phenols (thymol, safrole, isosafrole, Eugenol, isoeugenol etc.)；Higher alcohols (phenmethylol, oleyl alcohol, spermaceti Alcohol, stearyl alcohol, cetostearyl alcohol, octyl dodecanol etc.)；Esters surface active agent (sorbitan sesquioleate, polyoxy second Alkene rilanit special, polyethylene glycol stearate etc.)；Fatty acid ester (isopropyl myristate, myristic acid octyl dodecanol Ester, oleic acid oleic alcohol ester, diethyl phthalate, dibutyl phthalate etc.)；Organic acid (lactic acid, citric acid, winestone Acid, maleic acid, malic acid etc.) etc. at room temperature be liquid plasticizer.
In the present invention, it is liquid plasticizer at room temperature preferably not contain on the contrary.In addition, so-called in the present invention " be free of Have is liquid plasticizer at room temperature ", therefore represent to contain will not influence adhesion characteristic for liquid plasticizer at room temperature Content, generally, relative to the mass parts of acrylic adhesives 100, it is allowed at room temperature for liquid plasticizer content lead to It is at most often below 2 mass parts, below preferably up to 0.5 mass parts.
Medicine etc.
Various medicines contained in the adhesive in usual patch material can be contained in adhesive phase in the present invention.Make For these medicines, pyridoxol dicaprylate, dipotassium glycyrrhizinate, pyridoxine dipalmitate, glycyrrhizic acid, the drawing of hydrochloric acid benzene sea can be enumerated Bright, phellodendron extract, glycyrrhetinic acid stearate, lysozyme chloride, aminocaproic acid, Ganodenna Lucidum P.E, Job's tears, wooden slippers are extracted Thing, peony extract (ボ タ Application エ キ ス), angelica extract, Angelica roots, Rhizoma Chuanxiong extract, geranium thunbergii are extracted The anti-inflammatory agents such as thing, allantoin and arnica extract (ア Le ニ カ エ キ ス)；Alkannin, sabinol, cedrol, benzene prick chlorine The antimicrobial such as ammonium, benzethonium chloride, photosensitive plain No. 201 and adipic acid；Estradiol, vitamin B2, vitamin B6, royal jelly are extracted The sebum secretion inhibitor such as thing, riboflavin；The oil absorption Porous powder such as porous nylon powder and porous cellulose powder；It is high The sebum absorbing agents such as ridge soil, talcum, clay, zinc oxide；The exfoliators such as salicylic acid, sulphur, bentonite, cyclodextrin；Dibutyl Hydroxy-methylbenzene, tocopherol acetate, ascorbic acid, benzoic acids, parabens, benzalkonium chloride and benzethonium chloride Deng antioxidant (preservative)；Arnica extract, licorice, retinol, dipotassium glycyrrhizinate, peony extract, rat-tail The pachylosis improver such as leaf extract, loquat-leaf extract, Rosmarinus officinalis extract；Vitamin and butylated hydroxytoluene etc. Antioxidant；Further, various easing pain and diminishing inflammation agent；Antihistaminic；Corticosteroid agent；NMF；Vitamins；Spices；It is beautiful Rongcheng grades.
In the case that the patch material of the present invention is used as transdermal formulation, respectively according to purpose, pass through skin institute The medicine of absorption can be required for elements addition disease medicine.For example, as analgestic, steroid antalgesic, non-steroid can be enumerated Body class analgesics anti-inflammatory, anesthesia class antalgesic or local anesthetic etc..As other drugs, can enumerate sedative, antidepressants, Insomnia improves medicine, antihypertensive etc..
Further, as needed, the adhesive of the adhesive phase formed in the present invention can contain calcium carbonate, magnesium carbonate, silicon The fillers such as hydrochlorate, zinc oxide, titanium dioxide, magnesium sulfate, calcium sulfate.
It is different according to its different effective content of the species of medicine or filler, when using the gross mass of adhesive phase as During 100 mass %, the content of foregoing pharmaceutical or filler suitably contains 0.001~10 mass %, particularly preferably contains 0.01 ~2 mass %.
The thickness of adhesive phase
The present invention patch material in adhesive phase thickness for 10~200 μm scope, be preferably 15~150 μm, More preferably 20~100 μm of scope.
3. separation layer
The patch material of the present invention is in addition to support body layer, adhesive phase, situation about being used usually as first aid adhesive plaster Under, when adhesive phase is attached at skin, in order to protect adhesive phase, the patch material possess with adhesive phase close to Separation layer.
As the separation layer in the present invention, it is not particularly limited, in the technical field of patch material, generally, can be used It is referred to as the materials such as release liners, mould release membrance, peeling paper, stripping film, release liner.Specifically, such as surface progress can be enumerated Cross the polyethylene terephthalate film of silicon processing, surface and carry out the polyethylene of silicon processing and the layered product of paper etc..As The sheet material more than two panels of same thickness or different-thickness, separation layer can protect adhesive phase.In addition, in order to improve operability (that is, from the fissility of adhesive phase), separation layer may also set up disconnecting unit, form the area big compared with patch material, also can be in week Edge sets grip portions.In addition, for separation layer, for the purpose of improving operability and printing adaptability etc., in isolation On the face towards the face of adhesive phase or adhesive phase opposite side of layer, pass through the settable bumps such as blasting treatment.Further, every Absciss layer may be configured as a piece of big sheet material, thereon, can also arrange and multiple is made up of adhesive phase, support body layer and carrier layer Combination, in this case, separation layer can have in multiple patch materials.
The thickness of separation layer can be appropriately arranged with, and be not particularly limited, usually more than 20 μm, preferably more than 40 μm, its Higher limit is 500 μm or so.
4. carrier layer
Generally, in the case where support body layer is thin, patch material be preferably by carrier layer, support body layer, adhesive phase with And the patch material that separation layer is sequentially laminated.For patch material, by possess with support body layer close to carrier layer, can carry The operability of high patch material, the adhesion to skin, in addition, in the manufacture method of patch material, support body layer can be made Formation easily carry out.That is, when patch material is attached at into skin, fold or patch material hair can be produced in support body layer The situation that raw bending and then adhesive phase are mutually bonded, still, by patch material possess with support body layer close to carrier layer, The conformality of patch material can be improved, thus prevents above mentioned problem.The thickness of carrier layer can be appropriately arranged with, and not limited especially System, usually more than 20 μm, preferably 40 μm, its higher limit is 500 μm or so.
The film that is made up of various thermoplastic resins can be used to be formed for carrier layer, for example, can be used by polyurethane, polyethylene, Polypropylene, ionomer, polyamide, polyvinyl chloride, polyvinylidene chloride, vinyl-vinyl acetate copolymer, thermoplastic polyester, The film that polytetrafluoroethylene (PTFE) etc. is made.In addition, the layered product of above-mentioned film and paper can be used.
Carrier layer is the layer that easily can be peeled off when using (that is, when patch material being attached at into skin) from support body layer. Therefore, carrier layer forms strippable form with support body layer by thermo-compression bonding or bonding.In order to adjust carrier layer and supporter Layer peeling force, can on the surface with support body layer opposite side of carrier layer coating adhesive, liquid plasticizer, releasing agent Deng.
5. patch material
The patch material of the present invention is to possess to assign the supporter of water proofing property and the patch material of adhesive phase, is used as patch The patch material with high moisture-inhibiting and high adhesion of enclosure material.It is used as moisture permeability, it is however preferred to have 300g/m224h with On, in addition, probe tack is preferably 1.0~4.0N/5mm φ.The shape of patch material
The patch material of the present invention is to possess support body layer, the patch material of adhesive phase, further, as long as before possessing Every characteristic is stated, shape is not particularly limited, can be made into and mutually fitted with the characteristic as first aid adhesive plaster, adhesive tape or transdermal formulation The shape answered, such as, as the situation of adhesive tape, can be made into web-like；Can be circle if first aid adhesive plaster or transdermal formulation Shape, ellipse or the shape according to application target.
Moisture permeability
It is 300g/m as moisture permeability for the patch material of the present invention2More than 24h, preferably 600g/m2· More than 24h, more preferably 650g/m2More than 24h, more preferably 700g/m2More than 24h, particularly preferably 750g/ m2More than 24h.The upper limit is 1500g/m224h, preferably 1070g/m2·24h.Because moisture permeability is big, patch material is attached When skin, it can prevent from feeling oppressed, deposit sweat.Moisture permeability is in B conditions specified in JIS Z0208 (40 DEG C of temperature, relative humidity 90%) it is measured under.
Probe tack
For the patch material of the present invention, probe tack is preferably 1.0~4.0N/5mm φ, more preferably 1.95 ~3.70N/5mm φ, more preferably 1.96~3.60N/5mm φ, particularly preferably 1.97~3.57N/5mm φ.Probe tack It is too small, have the situation that the patch material during attaching comes off.In addition, probe tack is excessive, have after patch material attaching The situation of resistance or pain is felt when being peeled off from skin surface.
The manufacture method of patch material
As long as following patch material can be obtained, the manufacture method of patch material of the invention is not just limited, described The feature of patch material is：Possesses the patch material of support body layer and adhesive phase, the adhesive phase is by (a) adhesive A and (b) The mixed adhesive that adhesive B is mixed is formed, meanwhile, (i) is in aforementioned adhesion agent A and aforementioned adhesion agent B gross mass During 100 mass parts, the adhesive A is 15/85~85/15 (mass ratio) with adhesive B mixed proportions, meanwhile, (ii) this mixes Conjunction adhesive is cross-linking products, wherein,
(a) adhesive A：Acrylic adhesives containing copolymer, the copolymer is by with carbon number 8~12 The mass % of (methyl) alkyl acrylate 65~99.5 of alkyl, can with (methyl) alkyl acrylate copolymer have function Group the mass % of vinyl monomer 0.5~8 as neccessary composition, and further monomer add up to 100 mass % in the range of, The vinyl monomer different with the vinyl monomer from (methyl) alkyl acrylate and can be with (methyl) alkyl acrylate Base ester copolymerization and it is made without the mass % of vinyl monomer 0~34.5 of alkoxy as residual components；
(b) adhesive B：Acrylic adhesives containing copolymer, the copolymer in monomer by adding up to 100 mass % In the range of, the mass % of (methyl) alkyl acrylate 50~90 of the alkyl with carbon number 8~12, can be with (methyl) The mass % of vinyl monomer 0.5~8 with functional group of alkyl acrylate copolymer, with should (methyl) alkyl acrylate and The different vinyl monomer of the vinyl monomer and can with (methyl) alkyl acrylate copolymer and with alkoxy second The mass % of alkenyl monomer 9.5~49.5 is made as neccessary composition.
The present invention patch material can be manufactured as the layered product of sheet, also can as web-like layered product system Make.The manufacture method of common adhesive preparation can be used, hot melt, the rolling process of general adhesive preparation manufacture method can be employed as Or the dissolving method of development etc., wherein it is preferred that the dissolving method of development.The so-called dissolving method of development, is that neccessary composition is dissolved in after solvent in branch Deploy on support body, solvent is evaporated off afterwards to be made to fit with supporter, is then cut into the method that suitable shape obtains adhesive preparation.
One of manufacture method of adhesive preparation as the present invention, can add the mixed adhesive of two kinds of acrylic adhesives With crosslinking agent, it is uniformly mixed, is being coated with the process paper of organic silicon remover, is coated with the molten of above-mentioned mixed adhesive After liquid or emulsion formation adhesive phase, by making the adhesive phase be manufactured with the integrated method containing film support.Apply Cloth method is not particularly limited, for example, can be coated with the solution of the adhesive containing each composition using knife type coater, unfilled corner wheel The general coating machine such as machine (U Application マ コ ー タ ー) or reverse coating machine is coated.Obtained adhesive preparation can be rolled into a roll Web-like patch material, can also cut ovalisation, circle, square, shapes and sizes as defined in rectangle etc. according to purposes.
The purposes of patch material
As needed, patch material of the invention can carry carrier layer, separation layer, according to the shape being made using position, It can be used as general first aid adhesive plaster.In addition, can be used directly as medical adhesive tape, specific medicine conduct can be also added Transdermal formulation.
Embodiment
Hereinafter, by shown embodiment and comparative example, it is specifically described for the present invention, but the present invention is not limited only to These embodiments.The characteristic for each layer that the patch material and patch material of the present invention possesses and the measure side of physical property Method is as follows.
Thickness
The thickness of support body layer, adhesive phase and patch material determines (unit with dial type calibrator：μm, n=3's Average value).
Moisture permeability
The moisture permeability of patch material is entered under B conditions specified in JIS Z0208 (40 DEG C of temperature, relative humidity 90%) Row determines (unit：g/m224h, n=3 average value).
Probe tack
The probe tack of adhesive phase is to manufacture probe tack tester using ニ チ バ Application Co., Ltd., as reference, According to the probe tack test method described in JIS Z0237 (version in 1996), diameter 5mm cylindrical needle is determined from adhesive surface Make every effort to (unit required for vertically pulling up：N/5mm φ, n=3 average value).
Practicality is evaluated
Evaluated as the practicality of patch material, after adult 5 subjects of men and women wipe moisture after taking a shower, in finger second Joint attaches adhesive preparation, after attaching 12 hours, takes a shower, and evaluates " tack after shower ".Afterwards, 24 hours since attaching Afterwards, evaluate after " tack after attaching for 24 hours ", peel off patch material, evaluate " corrugation of skin ".Evaluation is 5 tested Person is evaluated with following benchmark 1~5 respectively, and its average value rounds up, and is evaluated according to following standards.In addition, comprehensive Evaluation is, according to evaluating characteristics and the practical result evaluated, to be evaluated by the present inventors.
Tack after shower
5：It is comprehensively well attached
4：Slightly peel off or roll in periphery
3：1/3 or so peels off or rolls
2：More than half is peeled off or rolled
1：Come off
A：Average value is more than 4.0
B：Average value is 3.5~3.9
C：Average value is less than 3.4
Tack after attaching for 24 hours
5：It is comprehensively well attached
4：Slightly peel off or roll in periphery
3：1/3 or so peels off or rolls
2：More than half is peeled off or rolled
1：Come off
A：Average value is more than 3.6
B：Average value is 3.1~3.5
C：Average value is less than 3.0
The corrugation of skin
5：Do not wrinkle
4：Slightly wrinkle but have no problem
3：Because of corrugation generation problem
2：Because corrugation produces big problem
1：Because excessively corrugation can produce blister
A：Average value is more than 4.0
B：Average value is 3.5~3.9
C：Average value is less than 3.4
Overall merit
AA：It is especially excellent for synthesis
A：It is excellent for synthesis
C：It is problematic for synthesis
Adhesive A and adhesive B intermiscibility analysis
Adhesive A 1：In 2-EHA/vinyl acetate/acrylic acid (mass ratio 85/11/4) copolymer 0.05 part of crosslinking of epoxies crosslinking agent (manufacture of TETRAD-X, Mitsubishi ガ ス chemistry society) is added in acrylic adhesives to obtain.
Adhesive B1：In the different nonyl ester of acrylic acid/acrylic acid 2- methoxy acrylates/acrylic acid (mass ratio 68/30/2) copolymerization 0.05 part of crosslinking of epoxies crosslinking agent (manufacture of TETRAD-X, Mitsubishi ガ ス chemistry society) is added in the acrylic adhesives of thing to obtain .
Mixed adhesive C1：In adhesive A (2-EHA/vinyl acetate/acrylic acid (mass ratio 85/ 11/4) acrylic adhesives of copolymer) and adhesive B (the different nonyl esters of acrylic acid/acrylic acid 2- methoxy acrylates/acrylic acid The acrylic adhesives of (mass ratio 68/30/2) copolymer) amount in 100 mass parts, add epoxies crosslinking agent (manufacture of TETRAD-X, Mitsubishi ガ ス chemistry society) 0.05 mass parts crosslinking is obtained.
Measurement of Dynamic Viscoelasticity is carried out to adhesive A 1, adhesive B1 and mixed adhesive C1, respective tan δ are obtained The temperature dependency of the temperature dependency of (loss angle tangent), the temperature dependency of storage modulus (G ') and loss modulus (G "). In addition, the solubility parameter SP values of 2-EHA and the different nonyl ester of acrylic acid are respectively 8.36 and 8.38, its difference exists In the range of 0.50.
As a result
By the tan δ (loss angle tangent) of Measurement of Dynamic Viscoelasticity temperature dependency, vitrifying is obtained by its peak value and turned Temperature (Tg), the glass transition temperature for adhesive A 1 is -33.2 DEG C, adhesive B1 glass transition temperature for - 19.4 DEG C, the glass transition temperature for confirming mixed adhesive C1 is only a peak value in the range of -29.3~-27.6 DEG C.Cause This, mixed adhesive C1 glass transition temperature is in adhesive A 1 and the respective glass transition temperatures of adhesive B1 Value near -26.3 DEG C of point, can confirm intermiscibility.
The temperature dependency change of mixed adhesive C1 storage modulus (G ') and loss modulus (G ") be located at adhesive A 1 with Position between adhesive B1, shows same change, therefore confirm intermiscibility.
Embodiment 1~7 and comparative example 1~4
On the supporter that polyurethane non-woven fabrics is laminated with polyurethane film, by common manufacture method, set There are patch material (170 μm of the thickness of support body layer, the thickness 40 of adhesive phase by the mixed adhesive C1 adhesive phases being made μm).Change adhesive A 1 and adhesive B1 mixing ratio, patch material made by same method, investigate adhesive A 1 with The influence that adhesive B1 mixing ratio is brought.The practical of patch material is carried out respectively to evaluate and evaluating characteristics.As a result such as the institute of table 1 Show.
Embodiment 8
Obtain being provided with the adhesive phase (thickness being made up of mixed adhesive C1 on polyurethane elastomer film (30 μm of thickness) Degree 40 μm) patch material.Under the mixing ratio that adhesive A 1 is 50 mass parts, adhesive B1 is 50 mass parts, carry out practical Evaluate and evaluating characteristics.As a result it is as shown in table 1.
Table 1
Investigate
Shown by table 1, supporter is the situation of the embodiment 1~7 of film/non-woven fabrics, in the case of adhesive A is single, thoroughly Relatively low humidity is 594g/m224h, but the preferable adhesive B of penetrability coordinates 15 matter in the mass parts of mixed adhesive 100 In the case of measuring more than part, moisture permeability is more than 650g/m2·24h.Above-mentioned adhesive A and adhesive B mixing ratio for 35/65~ Best practical evaluation is obtained when 65/35 (mass ratio).
But, adhesive A and adhesive B mixing ratio (adhesive A/adhesive B) are until 15/85~85/15 (quality Than) it is practical evaluate all to be excellent, increase adhesive B, when in the mass parts of mixed adhesive 100, adhesive B ultrasound crosses 85 mass parts When, practicality, which is evaluated, to be deteriorated.
For supporter, in the case of the embodiment 8 of film, moisture permeability declines because supporter is film, but and skin It is in close contact, in practical assessment, the tack after shower is good.It is due to that water can not enter from side to consider this.
Relative to embodiment, there is the problem of also having C in the evaluation for having C in practical evaluate, overall merit in comparative example 1~4.
Industrial applicibility
The patch material of the present invention is applied to skin etc., for example, as medical, it is adaptable to such as medicine and hygiene fieldses or outer With etc. field.Specifically, available for adhesive plaster, medical adhesive tape, cohesive bandage, dressing, the surgical tape of surgical operation, warp Skin absorbable preparation etc..
Because the present invention can provide following patch material, the adhesive phase of the patch material is glued by hydrophobic acrylic compounds The mixed adhesive that mixture is made with hydrophilic acrylic adhesives is formed, even if supporter is the film with water proofing property, Also skin corrugation, fash can be avoided and have both water proofing property, penetrability and cohesive, therefore as suitable for medical adhesive tape or urgency The patch material of adhesive plaster is rescued, practicality industrially is very high.It is particularly suitable for use in first aid adhesive plaster.
Claims (according to the 19th article of modification of treaty)
[1. July 9 (2015.07.09) international affairs bureau accepts within 2015]
(after modification) a kind of patch material, it is characterised in that foregoing patch material possesses support body layer and adhesive phase, this glues Mixture layer is formed by (a) adhesive A and (b) adhesive B mixed adhesive being mixed, meanwhile, (i) the adhesive A with When adhesive B gross mass is 100 mass parts, the adhesive A and adhesive B mixed proportions (adhesive A/adhesive B) For 15/85~85/15 (mass ratio), meanwhile, (ii) mixed adhesive is cross-linking products, wherein,
(a) adhesive A：Acrylic adhesives containing copolymer, the copolymer is by the alkyl with carbon number 8~12 The mass % of (methyl) alkyl acrylate 65~99.5, can with (methyl) alkyl acrylate copolymer and with functional group The mass % of vinyl monomer 0.5~8 as neccessary composition, and further monomer add up to 100 mass % in the range of, with this (methyl) the alkyl acrylate vinyl monomer different with the vinyl monomer and can be with (methyl) alkyl acrylate Copolymerization and it is made without the hydrophilic mass % of vinyl monomer 0~34.5 as residual components,
(b) adhesive B：Acrylic adhesives containing copolymer, the copolymer is by the model in the total 100 mass % of monomer In enclosing, the mass % of (methyl) alkyl acrylate 50~90 of the alkyl with carbon number 8~12, can be with (methyl) propylene Acid alkyl ester copolymerization and the mass % of vinyl monomer 0.5~8 and (methyl) alkyl acrylate and the second with functional group The different vinyl monomer of alkenyl monomer and can be with (methyl) alkyl acrylate copolymer and with hydrophilic vinyl The mass % of monomer 9.5~49.5 is made as neccessary composition,
Herein, aforementioned functional groups be carboxyl, hydroxyl, amino, amide groups or epoxy radicals,
It is foregoing not have (methyl) alkyl acrylate that hydrophilic vinyl monomer is the acrylic with carbon number 1~6 Base ester, (methyl) acrylate, vinyl esters, the vinyl monomer containing cyano group, vinyl aromatic with saturated carbon ring Compound or acrylamide, in addition,
It is foregoing that there is hydrophilic vinyl monomer to be the vinyl monomer with alkoxy.
2. according to patch material described in claim 1, wherein, the crosslinking of aforementioned adhesion oxidant layer is carried out by crosslinking agent.
3. according to patch material described in claim 1, wherein, aforementioned functional groups are carboxyl or hydroxyl.
4. the patch material according to described in any one in claims 1 to 3, wherein, bonding is formed in aforementioned adhesion oxidant layer It is liquid plasticizer at room temperature that the adhesive of oxidant layer, which is not contained,.
5. the patch material according to described in any one in Claims 1-4, wherein, foregoing support body layer contains film.
6. the patch material according to described in any one in claim 1 to 5, wherein, foregoing support body layer is film and cloth Lamination.
7. the patch material according to described in any one in claim 1 to 6, wherein, moisture permeability is 300g/m224h with On.
8. the patch material according to described in any one in claim 1 to 7, wherein, in aforementioned adhesion agent A and aforementioned adhesion When agent B gross mass is 100 mass parts, aforementioned adhesion agent A and aforementioned adhesion agent B mixing ratio (adhesive A/adhesive B) is 35/65~65/35 (mass ratio).
9. the patch material according to described in any one in claim 1 to 8, wherein, aforementioned adhesion agent A's has carbon atom (the first of (methyl) alkyl acrylate of the alkyl of number 8~12 and the aforementioned adhesion agent B alkyl with carbon number 8~12 Base) alkyl acrylate solubility parameter (SP) difference in the range of 0.50.
10. the patch material according to described in any one in claim 1 to 9, wherein, foregoing patch material is first aid rubber Cream.
Illustrate or state (according to the 19th article of modification of treaty)
Modification for claim 1 is indefinite proposed in the written comment for clear and definite international course of the review The record of opinion.
That is, respectively will " the ethene with functional group that can be with (methyl) alkyl acrylate copolymer in claim 1 Base monomer " is clearly " can be with (methyl) alkyl acrylate copolymer " " vinyl monomer with functional group ", by " function Group " is clearly " carboxyl, hydroxyl, amino, amide groups or epoxy radicals ", " will not have hydrophilic vinyl monomer " and clearly be " have (methyl) alkyl acrylate of acrylic of carbon number 1~6, (methyl) acrylate with saturated carbon ring, Vinyl esters, the vinyl monomer containing cyano group, vinyl aromatic compounds or acrylamide ", in addition, " will have hydrophilic Property vinyl monomer " be clearly the vinyl monomer of alkoxy " have ".

Claims (10)

1. a kind of patch material, it is characterised in that foregoing patch material possesses support body layer and adhesive phase, the adhesive phase by (a) mixed adhesive that adhesive A and (b) adhesive B are mixed is formed, meanwhile, (i) glues in aforementioned adhesion agent A with foregoing When the gross mass of mixture B is 100 mass parts, the adhesive A is 15/ with adhesive B mixed proportions (adhesive A/adhesive B) 85~85/15 (mass ratioes), meanwhile, (ii) mixed adhesive is cross-linking products, wherein,
(a) adhesive A：Acrylic adhesives containing copolymer, the copolymer is by the alkyl with carbon number 8~12 (methyl) alkyl acrylate 65~99.5 mass %, can have a functional group with (methyl) alkyl acrylate copolymer The mass % of vinyl monomer 0.5~8 as neccessary composition, and further monomer add up to 100 mass % in the range of, with this (methyl) the alkyl acrylate vinyl monomer different with the vinyl monomer and can be with (methyl) alkyl acrylate Copolymerization and it is made without the hydrophilic mass % of vinyl monomer 0~34.5 as residual components,
(b) adhesive B：Acrylic adhesives containing copolymer, the copolymer is by the model in the total 100 mass % of monomer In enclosing, the mass % of (methyl) alkyl acrylate 50~90 of the alkyl with carbon number 8~12, can be with (methyl) propylene The mass % of vinyl monomer 0.5~8 with functional group of acid alkyl ester copolymerization and (methyl) alkyl acrylate and the second The different vinyl monomer of alkenyl monomer and can be with (methyl) alkyl acrylate copolymer and with hydrophilic vinyl The mass % of monomer 9.5~49.5 is made as neccessary composition.
2. according to patch material described in claim 1, wherein, the crosslinking of aforementioned adhesion oxidant layer is carried out by crosslinking agent.
3. according to patch material described in claim 1, wherein, aforementioned functional groups are carboxyl or hydroxyl.
4. the patch material according to described in any one in claims 1 to 3, wherein, bonding is formed in aforementioned adhesion oxidant layer It is liquid plasticizer at room temperature that the adhesive of oxidant layer, which is not contained,.
5. the patch material according to described in any one in Claims 1-4, wherein, foregoing support body layer contains film.
6. the patch material according to described in any one in claim 1 to 5, wherein, foregoing support body layer is film and cloth Lamination.
7. the patch material according to described in any one in claim 1 to 6, wherein, moisture permeability is 300g/m224h with On.
8. the patch material according to described in any one in claim 1 to 7, wherein, in aforementioned adhesion agent A and aforementioned adhesion When agent B gross mass is 100 mass parts, aforementioned adhesion agent A and aforementioned adhesion agent B mixing ratio (adhesive A/adhesive B) is 35/65~65/35 (mass ratio).
9. the patch material according to described in any one in claim 1 to 8, wherein, aforementioned adhesion agent A's has carbon atom (the first of (methyl) alkyl acrylate of the alkyl of number 8~12 and the aforementioned adhesion agent B alkyl with carbon number 8~12 Base) alkyl acrylate solubility parameter (SP) difference in the range of 0.50.
10. the patch material according to described in any one in claim 1 to 9, wherein, foregoing patch material is first aid rubber Cream.
CN201480083859.1A 2014-12-26 2014-12-26 Adhesive material Active CN107001866B (en)

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KR20170102225A (en) 2017-09-08
KR102264107B1 (en) 2021-06-10

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