CN109642141A - Bonding agent, blister package laminated body and the blister package using it - Google Patents
Bonding agent, blister package laminated body and the blister package using it Download PDFInfo
- Publication number
- CN109642141A CN109642141A CN201780051060.8A CN201780051060A CN109642141A CN 109642141 A CN109642141 A CN 109642141A CN 201780051060 A CN201780051060 A CN 201780051060A CN 109642141 A CN109642141 A CN 109642141A
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- China
- Prior art keywords
- blister package
- bonding agent
- laminated body
- agent
- acid
- Prior art date
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/088—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/092—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising epoxy resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/40—Applications of laminates for particular packaging purposes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D75/00—Packages comprising articles or materials partially or wholly enclosed in strips, sheets, blanks, tubes, or webs of flexible sheet material, e.g. in folded wrappers
- B65D75/28—Articles or materials wholly enclosed in composite wrappers, i.e. wrappers formed by associating or interconnecting two or more sheets or blanks
- B65D75/30—Articles or materials enclosed between two opposed sheets or blanks having their margins united, e.g. by pressure-sensitive adhesive, crimping, heat-sealing, or welding
- B65D75/32—Articles or materials enclosed between two opposed sheets or blanks having their margins united, e.g. by pressure-sensitive adhesive, crimping, heat-sealing, or welding one or both sheets or blanks being recessed to accommodate contents
- B65D75/36—Articles or materials enclosed between two opposed sheets or blanks having their margins united, e.g. by pressure-sensitive adhesive, crimping, heat-sealing, or welding one or both sheets or blanks being recessed to accommodate contents one sheet or blank being recessed and the other formed of relatively stiff flat sheet material, e.g. blister packages, the recess or recesses being preformed
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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
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- 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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Composite Materials (AREA)
- Laminated Bodies (AREA)
- Packages (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Blister package laminated body made of layer stackup of bonding agent, substrate layer and the metal foil that solid component mass ratio with polyalcohol and epoxide in the host agent containing polyalcohol and epoxide and the curing agent containing isocyanate compound and aforementioned host agent is 100/20~100/60 by the bonding agent of foregoing description and the blister package using aforementioned blister package laminated body.The solid component mass ratio of aforementioned isocyanates compound and foregoing polyols is preferably 1~30 range.
Description
Technical field
The present invention relates to the blister package laminated body of the medical packaging purposes for being suitable for carrying out forming etc., wherein
The bonding agent used.
Background technique
In the past, the container as storage items such as the drugs such as package troche, capsule preparations, food, it is known to blister package
For the container for implementing forming of representative.Blister package (otherwise referred to as aluminium-plastic bubble plate packing (press through
package),PTP.) using the single side and tool of the resin film by making to be formed with multiple concave parts for accommodating storage item
The lid material engagement of the metal foils such as standby aluminium foil is sealed as the composition of sealing state to each concave part, passes through the anti-of pressing concave part
Face, the storage item in concave part puncture metal foil and content can be taken out (referring for example to patent document 1,2) from concave part.
The high light-proofness and moisture resistance having using metal, storage item is other than the aforementioned drug of expectation long-term preservation, food, also
Use the various articles such as the feed of cat and dog, cosmetics, medical instrument, electronic component.In addition, recently in addition to it has been known that there is concave parts
Other than blister package transparent, with visuality, it is also known that have and expect higher light-proofness and moisture resistance in concave part
Blister package with metal foil (referring for example to patent document 3).
In addition, blister package referred to laminated body film used in the forming of the blister package before storage item is enclosed or
Sheet material.
The blister package that concave part also has metal foil is to be laminated to by substrates such as metal foil and plastic films with bonding agent
Made of obtained from processing is formed with laminated body in blister package.But when the forming, sometimes in metal foil
It is peeling-off between layer, laminated body and adhesive layer, laminated body fracture.
As the laminated body for needing forming made of the substrates such as metal foil and plastic film are laminated with bonding agent,
Know to have and describe a kind of laminated body in battery laminated body, such as patent document 4, is that substrate layer and barrier layer and sealant are borrowed
Made of helping adhesive layer to stack gradually, aforementioned barrier layer includes metal foil, the bonding agent between aforementioned barrier layer and sealant
Layer is by the carbamate comprising the pure and mild epoxide of polyester polyols as host agent and comprising polyisocyanates as curing agent
It is that bonding agent is formed, the ratio of aforementioned host agent and aforementioned curing agent is calculated as 10:1.269~10:2.885 with solid component mass ratio,
Package body used in the packing container that the laminated body is used to be suitable for packing the liquid material for containing alcohol with high concentration.
In addition, the battery use packing material polyurethane adhesive containing host agent and curing agent is described in patent document 5,
Wherein, aforementioned host agent includes the acrylic acid that number-average molecular weight is 10,000~100,000 and hydroxyl value is 1~100mgKOH/g
Class polyalcohol (A) is originated from the isocyanate group of aromatic polyisocyanate (B) contained in curing agent relative to from aforementioned third
Equivalent proportion [NCO]/[OH] of the hydroxyl of alkene acrylic polyol (A) is 10~30, which can be used as the bonding of PTP packaging
Agent.
It is outer layer side resin thin film layer, outer layer in addition, describing following battery use packing material in patent document 6
Battery use packing material made of side bonds oxidant layer, metal foil layer, internal layer side bonds oxidant layer and hot sealing layer stack gradually, wherein
Aforementioned outer layer side adhesive layer is by having the host agent containing polyol component (A) and containing the solidification of polyisocyanate component (B)
The polyurethane adhesive of agent is formed, foregoing polyols ingredient (A) contain polyester polyol (A1): 85~99 weight %, 3 functions with
On alcohol component (A2): aforementioned (A1) and the total of (A2) (wherein, are set as 100 weight %) by 1~15 weight %, aforementioned polyester
Polyalcohol (A1) is the polyester polyols that the number-average molecular weight being made of polyacid constituent and polyol component is 5000~50000
Alcohol includes 45~95 moles of % of aromatic polyvalent sour component in 100 moles of % of aforementioned polybasic acids ingredient, contained in curing agent
Isocyanate group relative to be originated from aforementioned host agent contained in polyalcohol (A) hydroxyl and carboxyl total equivalent proportion [NCO]/
([OH]+[COOH]) is 0.5~10, and describes the bonding agent and may be used as the bonding agent of PTP packaging.
But do not carry out specifically evaluating PTP i.e. blister package, it is poly- especially with regard to being used as plastic film
The application of blister package laminated body when amide there is no any opinion.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2013-199283 bulletin
Patent document 2: Japanese Unexamined Patent Application Publication 2009-526715 bulletin
Patent document 3: Japanese Unexamined Patent Application Publication 2008-535746 bulletin
Patent document 4: Japanese Unexamined Patent Publication 2015-157363 bulletin
Patent document 5: Japanese Unexamined Patent Publication 2014-185317 bulletin
Patent document 6: Japanese Unexamined Patent Publication 2015-82354 bulletin
Summary of the invention
Problems to be solved by the invention
Problem of the present invention is that providing as the blister package laminated body that can be used as blister package, in processing and forming
When can reduce the fracture of metal foil layer, the bonding agent with specific composition of substrate layer floated layer laminated body.
The solution to the problem
The inventors of the present invention's discovery, by having the host agent containing polyalcohol and epoxide and with containing isocyanates
The solid component mass ratio of polyalcohol and epoxide in aforementioned host agent is set as specific model by the curing agent of compound
It encloses, is able to solve the above subject.
I.e. the present invention provides a kind of bonding agent, includes the host agent containing polyalcohol and epoxide and contains isocyanide
The curing agent of ester compound, the solid component mass ratio of polyalcohol and epoxide in aforementioned host agent is 100/20~
100/60。
In addition, the present invention provides a kind of blister package laminated body, it is substrate layer and metal foil by foregoing description
Made of the layer stackup of bonding agent.
In addition, the present invention provides a kind of medical blister package, it uses the blister package laminated bodies of foregoing description.
The effect of invention
By the way that bonding agent of the invention to be used as to the bonding agent of blister package laminated body, it is capable of providing in processing and forming
When reduce the blister package floated of the fracture of metal foil layer, substrate layer.
Detailed description of the invention
Fig. 1 is the schematic diagram for showing the composition of blister package laminated body of the invention.
Specific embodiment
(definition of term)
In the present invention, " blister package " refers to such main disclosed in Patent Documents 1 to 3 as shown in background technique
Container for storage items such as the drugs such as package troche, capsule preparations, food (herein regardless of the presence or absence of visuality).It needs to illustrate
, otherwise referred to as aluminium-plastic bubble plate packing, PTP, but referred to as blister package in the present invention.
(host agent)
Host agent used in the present invention contains polyalcohol and epoxide.
(polyalcohol)
Polyalcohol used in the present invention is not particularly limited, and polyalcohol used in bonding agent field can be used.
It is more that the polyalkylene polyols such as polyethylene glycol, polypropylene glycol, polyether polyol, polyester polyol, polyurethane can be used for example
The mixture etc. of first alcohol, polyester polyurethane polyol, polyether-polyurethane polyalcohol and polyalcohol above-mentioned etc..
As polyether polyol, such as the rings such as ethylene oxide of sening as an envoy to, propylene oxide, epoxy butane, tetrahydrofuran can be enumerated
Siloxane compound using the low molecular weight polyols such as such as water, ethylene glycol, propylene glycol, trimethylolpropane, glycerol as initiator into
Polyether polyol obtained from row polymerization.
Polyester polyol is as obtained from making polyacid and polyol reaction.As long as aforementioned polybasic acids are well known,
Any raw material can be used.Dimeric dibasic acid can be used for example.Dimeric dibasic acid is the unsaturated lipid based on C18 such as oleic acid, linoleic acid
The diels of fat acid-Alder type dimerization product, it is commercially available have in unsaturated bond plus hydrogen be saturated it made of object
The various substances such as matter.Representative substance is the dimeric dibasic acid 70~98% and C54 of 0~5 weight %, C36 of monocarboxylic acid comprising C18
0~30 weight % person of trimer acid.In addition, two polyalcohols (dimer diol) are the dimeric dibasic acid that will illustrate among the above also members and obtain
Person.Furthermore it is possible to individually or in the form of two or more mixtures use following substances: such as succinic acid, adipic acid, nonyl two
Acid, decanedioic acid, dodecanedicarboxylic acid, maleic anhydride, fumaric acid, 1,3- cyclopentane dicarboxylic acid, 1,4- cyclohexane dicarboxylic acid, to benzene
Dioctyl phthalate, M-phthalic acid, phthalic acid, 1,4- naphthalene dicarboxylic acids, 2,5- naphthalene dicarboxylic acids, 2,6 naphthalene dicarboxylic acid, naphthalenedicarboxylic acid,
The acid anhydrides or ester formative derivative of bis- (phenoxy group) ethane-p, p '-dicarboxylic acids of diphenyl dicarboxylic acid, 1,2- and the dicarboxylic acids；
P-hydroxybenzoic acid, to the ester formative derivatives of (2- hydroxyl-oxethyl) benzoic acid and the dihydroxy carboxylic acids, dimeric dibasic acid etc.
Polyacid.
As long as in addition, foregoing polyols be it is well known, any raw material can be used.It can be individually or with two or more
The form of mixture use following substances: for example ethylene glycol, propylene glycol, 1,3- propylene glycol, 1,4- butanediol, 1,5- pentanediol,
3- methyl-1,5- pentanediol, 1,6-HD, neopentyl glycol, methyl pentanediol, dimethylbutadio, butyl ethyl propylene glycol,
Diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, double hydroxyl-oxethyl benzene, 1,4- cyclohexanediol, 1,4-
The glycols such as cyclohexanedimethanol, triethylene glycol, polycaprolactone glycol, two polyalcohols, bisphenol-A, hydrogenated bisphenol A, by propiolactone,
The ring-opening polymerization of the cyclic ester compounds such as butyrolactone, 6-caprolactone, δ-valerolactone, Beta-methyl-δ-valerolactone obtains poly-
Esters, by ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene, 1,3 butylene glycol, 1,4- butanediol, 1,
There is the one kind or two or more of the compound of 2 active hydrogen atoms to be used as initiator for 6- hexylene glycol, neopentyl glycol etc., make epoxy second
1 kind of the monomers such as alkane, propylene oxide, epoxy butane, Styryl oxide, epoxychloropropane, tetrahydrofuran, cyclohexylidene or 2 kinds
Above by polyol components such as polyethers obtained from conventional method addition polymerization.
Polyurethane polyol is obtained from reacting foregoing polyols with isocyanates.It is carbamate as reaction
Isocyanates used in change, can enumerating aromatic diisocyanate, (methyl diphenylene diisocyanate, xyxylene two are different
Cyanate, tetramethyl xylylene diisocyanate, two isocyanide of toluene di-isocyanate(TDI), low-molecular-weight diol class and aforementioned fragrance race
The prepolymer etc. of acid esters)；Aliphatic diisocyanate (1,6- hexamethylene diisocyanate, 2,2,4- tri-methyl hexamethylene
The low-molecular-weight diols such as diisocyanate, lysine diisocyanate, ethylene glycol, propylene glycol class and aforementioned aliphatic diisocyanate
Prepolymer etc.)；Alicyclic diisocyanate (isophorone diisocyanate, 4,4 '-diphenylmethane diisocyanates of hydrogenation
Ester, methylcyclohexylidene diisocyanate, isopropylidene dicyclohexyl -4,4 '-diisocyanate, low-molecular-weight diol class with it is aforementioned
The prepolymer etc. of alicyclic diisocyanate)；And their two or more mixtures.Furthermore it is possible to poly- alkylene above-mentioned
Polylol, polyether polyol, polyester polyol reaction, can be applied in combination in this case with foregoing polyols, can also not
It is applied in combination.Substance obtained from being reacted is also referred to as polyester polyurethane polyol, polyether-polyurethane polyalcohol.
Wherein, from the excellent aspect of flexibility, mouldability, it is preferable to use polyester polyol, polyester-polyurethane are polynary
Alcohol etc. has the polyalcohol of ester skeleton.
(epoxide)
Epoxide used in the present invention, can enumerate usual commercially available epi-bis type, phenolic varnish type,
Beta-methyl epichlorohydrin type (β-methylepichloro-type), cyclic annular alkylene oxide type, diglycidyl ether type, ethylene oxidic ester
Type, polyglycols ether type, glycol ether type, epoxidized fatty acid ester type, polybasic carboxylic acid ester type, aminoglycidyl type, isophthalic two
The various epoxy resin such as phenolic.
As epoxy resin, usual commercially available bisphenol-type epoxy resin, phenolic resin varnish type epoxy resin, ring-type can be enumerated
Alkylene oxide type resin, diglycidyl ether type resin, glycidyl ester type resin, polyglycols ether type epoxy, glycol ethers type ring
Oxygen resin, epoxidized fatty acid ester type resin, polybasic carboxylic acid ester type epoxy resin, glycidyl amine type resin, resorcinol
The various epoxy resin such as type epoxy resin.Wherein, from the excellent aspect of mouldability, it is preferable to use bisphenol-type epoxy resin.
Feature are as follows: in the aforementioned host agent containing polyalcohol and epoxide, the solid of polyalcohol and epoxide at
Dividing mass ratio is 100/20~100/60.In this range, it can obtain being not susceptible to the disconnected of metal foil layer in processing and forming
It splits, the laminated body for the layer with bonding agent of substrate layer floated.For aforesaid solid composition quality ratio, wherein preferably 100/
20~100/40, most preferably 100/20~100/30.
(curing agent containing isocyanate compound)
Known usual isocyanate compound can be used in isocyanate compound used in the present invention.
For example, can enumerate toluene di-isocyanate(TDI), xylylene diisocyanate, methyl diphenylene diisocyanate,
1,6- hexamethylene diisocyanate, 4,4 '-di-2-ethylhexylphosphine oxides (cyclohexyl isocyanate), relies ammonia at isophorone diisocyanate
Sour diisocyanate, trimethyl hexamethylene diisocyanate, 1,3- (isocyanatomethyl) hexamethylene, two isocyanide of 1,5- naphthalene
The polyisocyanates such as acid esters, triphenylmethane triisocyanate；The adduction body of the polyisocyanates, the polyisocyanates
Derivatives (modifier) of polyisocyanates such as the isocyanuric acid ester body of biuret body or the polyisocyanates etc..
It is not limited to polyisocyanates, compared with fatty family, aromatic system is more preferable in terms of peel strength, formability
Achievement.
In the present invention, to the hydroxyl (OH) and the isocyanate group for being originated from polyisocyanate compound for being originated from polyalcohol
(NCO) equivalent proportion (NCO/OH) is not particularly limited, and preferably uses in 1~30 range.When within the scope of this, wet-heat resisting
Property (65 DEG C -90%/72 small not float at present, near the boundary portion of depth 6.5mm shaped flange portion and sidewall portion), heat-sealing
The balance of property (not floating near the boundary portion of depth 6.5mm shaped flange portion and sidewall portion under 190 DEG C/3 seconds) is best.Separately
On the one hand, in the case where less than 1, the worry for having peel strength, humidity resistance to be deteriorated when more than 30, there is peel strength, heat sealability
The worry of variation.
Further preferably 2~10, it is most preferred for being more preferably 4~10,4~7 range.
In addition, bonding agent of the invention can also contain ketone resin.
Ketone resin used in the present invention can enumerate known usual ketone resin, can be suitably used formaldehyde resin,
Cyclohexanone formaldehyde resin and keto-aldehyde condensation resin etc..
Bonding agent of the invention can be any form in solvent type or no-solvent type.In solvent type situation, solvent
It is used as reaction medium in the manufacture of host agent and curing agent, and then is used as diluent in coating.As what be can be used
Solvent, such as the esters such as ethyl acetate, butyl acetate, cellosolve acetate, acetone, methyl ethyl ketone, isobutyl ketone, hexamethylene can be enumerated
The halogen such as the ethers such as the ketones such as ketone, tetrahydrofuran, dioxanes, toluene, dimethylbenzene etc. is aromatic hydrocarbon, methylene chloride, dichloroethanes
For hydro carbons, dimethyl sulfoxide, dimethyl sulfonamide etc..In these, it is usually preferred to ethyl acetate or first be used alone or as a mixture
Ethyl ketone.On the other hand, in the present invention, no-solvent type is situated between when can enumerate the manufacture in host agent above-mentioned and curing agent as reaction
Matter uses so as being used in coating as diluent, such as ethyl acetate, butyl acetate, cellosolve acetate
The virtues such as the ethers such as the ketones such as esters, acetone, methyl ethyl ketone, isobutyl ketone, cyclohexanone, tetrahydrofuran, dioxanes, toluene, dimethylbenzene
Halogenated hydrocarbons, dimethyl sulfoxide, the dimethyl sulfonamides such as fragrant race's hydro carbons, methylene chloride, dichloroethanes etc..In these, usually
Refer to the form without ethyl acetate or methyl ethyl ketone.
For bonding agent of the invention, as another good mode, well known phosphoric acid class can be applied in combination or it spreads out
Biology.The problems such as initial cementability of bonding agent further increases as a result, can eliminate tunnel-effect (tunneling).
As phosphoric acid class used herein or derivatives thereof, such as ortho phosphorous acid, phosphorous acid, orthophosphoric acid, secondary can be enumerated
The phosphoric acid such as phosphoric acid class, condensed phosphoric acid class, such as orthophosphoric acid such as metaphosphoric acid, pyrophosphoric acid, tripolyphosphate, polyphosphoric acid, peroxophosphoric acid
Mono-methyl, orthophosphoric acid mono ethyl ester, orthophosphoric acid list propyl ester, orthophosphoric acid mono-n-butylester, the mono- 2- ethylhexyl of orthophosphoric acid, orthophosphoric acid list benzene
Base ester, phosphorous acid mono-methyl, phosphorous acid mono ethyl ester, phosphorous acid list propyl ester, phosphorous acid mono-n-butylester, the mono- 2- ethylhexyl of phosphorous acid,
Phosphorous acid list phenylester, two -2- ethylhexyl of orthophosphoric acid, orthophosphoric acid diphenyl dimethylphosphite, diethyl phosphite, phosphorous
The monoesters such as sour dipropyl, dibutyl phosphite, two -2- ethylhexyl of phosphorous acid, phosphorous acid diphenyl, diester compound, condensation phosphorus
Monoesters, diester compound, the epoxide such as making phosphoric acid class above-mentioned and such as ethylene oxide, propylene oxide of acid and alcohols
Substance obtained from addition for example makes obtained from aliphatic or aromatic diglycidyl ether and phosphoric acid class addition above-mentioned
Epoxy phosphate esters etc..
One or more can be used in above-mentioned phosphoric acid class or derivatives thereof.As be allowed to containing method, can be with
Simply it is mixed into.
In addition, adhesion promoters also can be used in bonding agent of the invention.Adhesion promoters can enumerate silane coupled
Coupling agent, the epoxy resin etc. of agent, titanate esters system coupling agent, aluminium system etc..
As silane coupling agent, for example, γ aminopropyltriethoxy silane, gamma-amino propyl trimethoxy can be enumerated
Base silane, N- β (amino-ethyl)-gamma-amino propyl trimethoxy silicane, N- β (amino-ethyl)-gamma-amino oxypropyl trimethyl
The amino silanes such as dimethoxysilane, N- phenyl-gamma-amino propyl trimethoxy silicane；β-(3,4- epoxycyclohexyl) ethyl
The rings such as trimethoxy silane, γ-glycidoxypropyltrime,hoxysilane, γ-epoxy propoxy propyl triethoxysilane
Oxosilane；Vinyl three ('beta '-methoxy ethyoxyl) silane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-
The vinyl silanes such as methacryloxypropyl trimethoxy silane；Hexamethyldisilazane, γ-mercaptopropyi trimethoxy
Silane etc..
As titanate esters system coupling agent, for example, tetraisopropoxy titanium, four titanium n-butoxides, butyltitanate can be enumerated
Dimer, four stearyl titanate esters, titanium acetylacetone, lactic acid titanium, four octamethylenes, two alcohol titanate, lactic acid titanium, four stearic oxygroups
Titanium etc..
In addition, as aluminium system coupling agent, for example, acetyl aluminum alkoxide diisopropanol compound etc. can be enumerated.
As long as bonding agent of the invention be it is well known, can be coated by any coating method, usually pass through gravure
Roller coating mode for cloth is coated with.For the coating weight of this bonding agent, 1.5~5g/m is being calculated as with solid component2, preferably 2~4g/m2
Application conditions under use.In general, solvent type is with about 1.0~4.0g/m2Coating weight, no-solvent type is with about 0.5~3.0g/m2
The coating weight use of left and right is advisable.
Blister package of the invention has the feature that substrate layer and metal foil by the layer of aforementioned bonding agent with laminated body
Stacking.As previously mentioned, in the application, blister package is used in the forming of blister package before storage item is enclosed with laminated body
Film or sheet material, the substrate used at this time can enumerate blister package (aluminium-plastic bubble plate packing, PTP), food packaging, bait
The usually used plastic basis material in packing of material.
In addition, can be substrate layer for the composition of blister package laminated body of the invention and be only adhered to metal foil
Single side is also possible to the two sides that substrate layer is adhered to metal foil.In addition, substrate layer can be the fitting of multilayer.
As aforementioned metal foil, preferably pure aluminum foil or alloy foil.In addition, the preferred semi-hard material of metal foil or soft material
Material.
In addition, for the plastic basis material used as substrate layer, such as polyamide, polyester, polyolefin can be enumerated etc..
As foregoing polyamides, such as polyamide homopolymer or copolymer can be enumerated.As polyamide homopolymer, can arrange
Enumerate poly- (4-Aminobutanoicacid) (nylon 4), poly- (6-aminocaprolc acid) (nylon 6, in addition, poly- (caprolactam)), poly- (7- amino heptan
Acid) (nylon 7), poly- (8- aminocaprylic acid) (nylon 8), poly- (9 aminononanoic acid) (nylon 9), poly- (10- aminocapric acid) (nylon
10), poly- (11- amino undecanoic acid) (nylon 11), poly- (12 amino dodecanoic acid) (nylon 12) etc..As copolyamide
Object can enumerate nylon 4,6, poly- (hexamethylene adipamide) (nylon 6,6), poly- (hexamethylene sebacamide) (nylon 6,10), poly- (heptan
Two acyl heptamethylene diamines) (nylon 7,7), poly- (suberoyl octamethylenediamine) (nylon 8,8), poly- (hexamethylene azelamide) (nylon 6,9), poly-
(nonanedioyl nonamethylene diamine) (nylon 9,9), poly- (nonanedioyl decamethylene diamine) (nylon 10,9), poly- (tetra-methylenedimine -co- ethanedioic acid)
Polyamide (nylon 6,12), the ten dimethylene diamines and positive ten of (nylon 4,2), two ketone acid of n-dodecane and hexamethylene diamine
Polyamide (nylon 12,12) of two ketone acid of dioxane etc..The polyamide copolymer useful as other, can enumerate caprolactam/
Hexamethylene adipamide copolymer (nylon 6,6/6), hexamethylene adipamide/caprolactam copolymer (nylon 6/6,6), trimethylene
Adipamide/hexamethylene diazelaamide copolymer (nylon trimethyl 6,2/6,2), hexamethylene adipamide-hexa-methylene-nonyl
Diamides caprolactam copolymer (nylon 6,6/6,9/6), poly- (tetra-methylenedimine -co- M-phthalic acid) (nylon 4, I),
Polyhexamethylene isophtalamide (nylon 6,1), hexamethylene adipamide/hexa-methylene-isophtalamide (nylon 6,6/
6I), hexamethylene adipamide/hexa-methylene terephthalamide (nylon 6,6/6T), poly- (2,2,2- tri-methyl hexamethylene is to benzene
Diformamide), poly- (xyxylene adipamide) (MXD6), poly- (terephthaldehyde's base adipamide), poly- (hexa-methylene
Terephthalamide), poly- (ten dimethylene terephthalamides), polyamide 6 T/6I, polyamide 6/MXDT/I, polyamide
MXDI etc..
Furthermore it is possible to illustrate in other polyamide and this specification to be not particularly illustrated in this specification poly-
The combination of amide.In these, as polyamide, more preferable nylon 6, nylon 6,6, nylon 6/6, or mixtures thereof 6, further
It is preferred that nylon 6.
As aforementioned polyester, polyethylene terephthalate (PET), glycol modification poly terephthalic acid second can be enumerated
Diol ester (PETG).The copolymer of cyclic olefin copolymer (COC) optimal ethylene and norbornene.
As aforementioned polyolefins, preferably comprises and be selected from by polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), gather partially
The material in group that vinyl chloride (PVdC), cyclic olefin copolymer (COC), polystyrene (PS), acrylic resin form, it is excellent
Select polyethylene (PE), polyester, polyvinyl chloride (PVC).As aforementioned polyethylene, low density polyethylene (LDPE) (LDPE), line can be enumerated
Property low density polyethylene (LDPE) (LLDPE), linear density polyethylene (LMDPE), the linear and low-down polyethylene of density
(VLDPE), linear ultra low density polyethylene (ULDPE), high density polyethylene (HDPE) (HDPE), preferably low density polyethylene (LDPE).
(blister package)
Blister package of the invention has lid material in blister package laminated body of the invention, can be such as manufacture of getting off:
Blister package of the invention on laminated body (ground) shape stated number recess portion, then by the contents such as tablet accommodate at
In each recess portion of shape, lid material is heat-sealed in the blister pack as ground by the form fill seal machine being packed for using blister package
The dress flange part of laminated body, thus manufactures.
Preferably there is heat-sealing from the aspect that the content of receiving can be sealed by heat-sealing as aforementioned cover material
Property resin layer.For heat sealability resin layer, as long as the layer in heat-sealing with the surface welding for the ground for containing content,
It does not limit, for example, can enumerate comprising low density polyethylene (LDPE) (LDPE), medium density polyethylene (MDPE), high-density polyethylene
Alkene (HDPE), linear low density polyethylene (LLDPE), ethylene vinyl acetate copolymer (EVA), polypropylene (PP), ethylene-the third
Olefin(e) acid copolymer (EAA), ethylene-methacrylic acid copolymer (EMA), ethylene-methyl acrylate copolymer (EMAA), second
Alkene-ethyl acrylate copolymer (EEA), ethylene methyl methacrylate copolymer (EMMA), ionomer (IO) etc.
In one kind or two or more layer.In addition, from the good aspect of low water vapo(u)r transmission, lid material preferably comprises the gold such as aluminium layer
Belong to the metal layers such as vapor deposition film layer, metal foil layer, more preferably includes aluminium foil layer.
In turn, the aspect excellent from light-proofness and moisture resistance particularly preferably has blister package layer of the invention
Stack and lid material through being bonded all have the composition of the two sides metal foil layer (aluminium foil layer) of metal foil layer.
For blister package laminated body of the invention and blister package, it is medical needless to say, can also be used as food
With or pet bait with packing use.In addition, after long-duration experiments, the also not reduction of the adhesive strength of interlayer, not
The bad orders such as float of interlayer are generated, therefore can be efficiently used for as battery electrolyte sealing film or battery electrode portion
It battery that protective film uses and is used as secondary cell electrolyte sealing film or electrode for secondary battery portion protective film
Secondary cell.
Embodiment
Hereinafter, by embodiment, the present invention will be described in more detail.Stating " part " indicates mass parts.
The production of (Production Example 1) bonding agent (1)
By DICDRY LX-906 (polyester polyol, Dainippon Ink Chemicals's system) and EPICLON-1050 (epoxide,
Dainippon Ink Chemicals's system) it is mixed with solid component mass ratio for 100/40 (polyalcohol/epoxide), use ethyl acetate
It is diluted, thus prepares the host agent A of solid component 60%.With host agent/catalyst ratio=10:1.6 (conversion in host agent A
It is 5.2 for NCO/OH ratio (mol/mol)) mixed curing agent KW-75 (polyisocyanates, Dainippon Ink Chemicals's system), uses ethyl acetate
It is diluted, compounding liquid is thus made, obtain the bonding agent (1) of solid component 35%.
The production of (Production Example 2) bonding agent (2)
By DICDRY LX-906 (polyester polyol, Dainippon Ink Chemicals's system) and EPICLON-1050 (epoxide,
Dainippon Ink Chemicals's system) it is mixed with solid component mass ratio for 100/25 (polyalcohol/epoxide), use ethyl acetate
It is diluted, thus prepares the host agent A of solid component 60%.With host agent/catalyst ratio=10:1.6 (conversion in host agent A
It is 4.6 for NCO/OH ratio (mol/mol)) mixed curing agent KW-75 (polyisocyanates, Dainippon Ink Chemicals's system), uses ethyl acetate
It is diluted, compounding liquid is thus made, obtain the bonding agent (2) of solid component 35%.
The production of (Production Example 3) bonding agent (3)
By DICDRY LX-906 (polyester polyol, Dainippon Ink Chemicals's system) and EPICLON-1050 (epoxide,
Dainippon Ink Chemicals's system) it is mixed with solid component mass ratio for 100/60 (polyalcohol/epoxide), use ethyl acetate
It is diluted, thus prepares the host agent A of solid component 60%.With host agent/catalyst ratio=10:1.6 (conversion in host agent A
It is 5.9 for NCO/OH ratio (mol/mol)) mixed curing agent KW-75 (polyisocyanates, Dainippon Ink Chemicals's system), uses ethyl acetate
It is diluted, compounding liquid is thus made, obtain the bonding agent (3) of solid component 35%.
The production of (Production Example 4) bonding agent (4)
By DICDRY LX-906 (polyester polyol, Dainippon Ink Chemicals's system) and EPICLON-1050 (epoxide,
Dainippon Ink Chemicals's system) it is mixed with solid component mass ratio for 100/40 (polyalcohol/epoxide), use ethyl acetate
It is diluted, thus prepares the host agent A of solid component 60%.With host agent/catalyst ratio=10:1.4 (conversion in host agent A
It is 4.5 for NCO/OH ratio (mol/mol)) mixed curing agent KW-75 (polyisocyanates, Dainippon Ink Chemicals's system), uses ethyl acetate
It is diluted, compounding liquid is thus made, obtain the bonding agent (4) of solid component 35%.
The production of (Production Example 5) bonding agent (5)
By DICDRY LX-906 (polyester polyol, Dainippon Ink Chemicals's system) and EPICLON-1050 (epoxide,
Dainippon Ink Chemicals's system) it is mixed with solid component mass ratio for 100/40 (polyalcohol/epoxide), use ethyl acetate
It is diluted, thus prepares the host agent A of solid component 60%.With host agent/catalyst ratio=10:1.8 (conversion in host agent A
It is 5.8 for NCO/OH ratio (mol/mol)) mixed curing agent KW-75 (polyisocyanates, Dainippon Ink Chemicals's system), uses ethyl acetate
It is diluted, compounding liquid is thus made, obtain the bonding agent (5) of solid component 35%.
The production of (Production Example 6) bonding agent (6)
By DICDRY LX-906 (polyester polyol, Dainippon Ink Chemicals's system) and EPICLON-1050 (epoxide,
Dainippon Ink Chemicals's system) it is mixed with solid component mass ratio for 100/40 (polyalcohol/epoxide), use ethyl acetate
It is diluted, thus prepares the host agent A of solid component 60%.With host agent/catalyst ratio=10:2.0 (conversion in host agent A
It is 6.5 for NCO/OH ratio (mol/mol)) mixed curing agent KW-75 (polyisocyanates, Dainippon Ink Chemicals's system), uses ethyl acetate
It is diluted, compounding liquid is thus made, obtain the bonding agent (6) of solid component 35%.
The production of (Production Example H1) bonding agent (H1)
By DICDRY LX-906 (polyester polyol, Dainippon Ink Chemicals's system) and EPICLON-1050 (epoxide,
Dainippon Ink Chemicals's system) it is mixed with solid component mass ratio for 100/10 (polyalcohol/epoxide), use ethyl acetate
It is diluted, thus prepares the host agent A of solid component 60%.With host agent/catalyst ratio=10:1.6 (conversion in host agent A
It is 4.1 for NCO/OH ratio (mol/mol)) mixed curing agent KW-75 (polyisocyanates, Dainippon Ink Chemicals's system), uses ethyl acetate
It is diluted, compounding liquid is thus made, obtain the bonding agent (H1) of solid component 35%.
The production of (Production Example H2) bonding agent (H2)
By DICDRY LX-906 (polyester polyol, Dainippon Ink Chemicals's system) and EPICLON-1050 (epoxide,
Dainippon Ink Chemicals's system) it is mixed with solid component mass ratio for 100/70 (polyalcohol/epoxide), use ethyl acetate
It is diluted, thus prepares the host agent A of solid component 60%.With host agent/catalyst ratio=10:1.6 (conversion in host agent A
It is 6.3 for NCO/OH ratio (mol/mol)) mixed curing agent KW-75 (polyisocyanates, Dainippon Ink Chemicals's system), uses ethyl acetate
It is diluted, compounding liquid is thus made, obtain the bonding agent (H2) of solid component 35%.
(embodiment 1) has used the production of blister package laminated body (1) of bonding agent (1)
Bonding agent (1) is coated on soft aluminium foil (45 μ of thickness with the coating weight of solid component 3.0g using dry laminating machine
M), it after being vaporized solvent, is bonded with PVC (60 μm of thickness), obtains laminated body.Then, using dry laminating machine by bonding agent (1)
It is coated on Biaxially oriented polyamide film (25 μm of thickness) with the coating weight of solid component 3.0g, it is and aforementioned after being vaporized solvent
The aluminium face paste of laminated body is closed, and is kept the temperature 96 hours at 40 DEG C to make bonding agent solidify, is obtained blister package laminated body (1).
(embodiment 2~6)
Instead of bonding agent (1), is operated similarly with example 1, steeped in addition to this using bonding agent (2)~(6)
Cover is packed for laminated body (2)~(6).
(comparative example 1) has used the production of blister package laminated body (2) of bonding agent (H1)
It is in addition to this, same as laminated body (1) using the bonding agent (H1) made in Production Example 2 instead of bonding agent (1)
Ground operation makes blister package with laminated body (H1).
(comparative example 2) has used the production of the blister package laminated body of bonding agent (H2)
It is in addition to this, same as laminated body (1) using the bonding agent (H2) made in Production Example 3 instead of bonding agent (1)
Ground operation makes blister package with laminated body (H2).
(production of ground (1))
Blister package obtained in embodiment (1) is cut into 60mm in length and breadth with laminated body (1).It is used into each 30mm in length and breadth
Square mold, with accurate press in the direction compression moulding vertical with laminate be depth 6.0mm, obtain ground (1).
It should be noted that the punch shape of the mold used are as follows: square, corner R 2mm, the formed punch shoulder of one side 30mm
Portion R1mm.The mold hole shape of the mold used are as follows: square, die hole corner R 2mm, the die hole shoulder R of one side 34mm:
The gap of 1mm, formed punch and die hole is unilateral side 0.3mm.Using aforementioned interspace, the inclination for meeting forming height is generated.
(ground (2)~(6), ground (H1)~(H2) production)
This is removed using blister package laminated body (2)~(6), (H1)~(H2) with laminated body (1) instead of blister package
In addition, it is operated in the same way with (production of ground (1)), obtains ground (2)~(6), ground (H1)~(H2).
<evaluation of mouldability>
3cm square, depth are carried out with press with polyamide side for convex side to ground (1)~(6), ground (H1)~(H2)
The processing and forming for spending 6mm, obtains molding (1)~(6), molding (H1)~(H2).
(floating area)
Angle part to obtained molding, the number and area at the position floated to polyamide from aluminium face are compared and comment
Valence.
Polyamide floats area less than 5mm: small
It is 5mm or more and less than 10mm that polyamide, which floats area: in
It is 10mm or more that polyamide, which floats area: big.
(number of metal fracture)
To obtained molding, evaluation is compared to the number at the position of aluminium fracture.
Show the result in table 1.
[table 1]
<evaluation of heat resistance>
(production of blister package)
Storage item is filled in molding (1)~(6), molding (H1)~(H2), the aluminium foil for being coated with heat sealing agent is (thick
25 μm of degree) it is used as lid material, it is bonded by 180 DEG C of heating in 2 seconds, thus makes blister package.To the heat-sealing in fitting lid material
The number and area at the position that the polyamide of the angle part of molding floats from aluminium face after process are compared evaluation.
[table 2]
As a result, after having used the blister package laminated body of the bonding agent of embodiment after forming or blister package manufacture
It also is good without floating between polyamide and aluminium face.And the blister package laminated body of the bonding agent of comparative example is used
It produces and floats.
Description of symbols
A:OP coating
B: ink
C: aluminium foil
D: heat sealability resin layer
E: polyvinyl chloride (or tensionless winkler foundation polypropylene)
F: bonding agent
G: aluminium foil
H: bonding agent
I: polyamide (or polyethylene terephthalate)
J: content
K: Gai Cai
L: ground
Claims (8)
1. a kind of bonding agent is comprising: the host agent containing polyalcohol and epoxide and contain isocyanates
The curing agent of compound, the solid component mass ratio of polyalcohol and epoxide in the host agent are 100/20~100/
60。
2. bonding agent according to claim 1, wherein the solid component of the isocyanate compound and the polyalcohol
The range that mass ratio is 1~30.
3. bonding agent according to claim 1 or 2, wherein the epoxide is bisphenol A type epoxy compound.
4. bonding agent described in any one of claim 1 to 3 is used for blister package laminated body.
5. a kind of blister package laminated body is substrate layer and metal foil by according to any one of claims 1 to 4 viscous
It connects made of the layer stackup of agent.
6. blister package laminated body according to claim 5, wherein the substrate layer is polyamide.
7. blister package laminated body according to claim 5 or 6, wherein metal foil is aluminium foil.
8. a kind of blister package, it uses the blister package laminated bodies described in any one of claim 5~7.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016-173657 | 2016-09-06 | ||
| JP2016173657 | 2016-09-06 | ||
| PCT/JP2017/030887 WO2018047672A1 (en) | 2016-09-06 | 2017-08-29 | Adhesive, blister pack laminate and blister pack using same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109642141A true CN109642141A (en) | 2019-04-16 |
Family
ID=61562276
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201780051060.8A Withdrawn CN109642141A (en) | 2016-09-06 | 2017-08-29 | Bonding agent, blister package laminated body and the blister package using it |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP6308413B1 (en) |
| CN (1) | CN109642141A (en) |
| WO (1) | WO2018047672A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102246481B1 (en) * | 2020-10-08 | 2021-05-03 | 디아이씨 주식회사 | Plastic Sheet for Blister Packaging of Drugs and Process of Manufacturing the Sheet |
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| CN109476909A (en) * | 2016-07-26 | 2019-03-15 | Dic株式会社 | Resin combination and laminated body |
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2017
- 2017-08-29 WO PCT/JP2017/030887 patent/WO2018047672A1/en active Application Filing
- 2017-08-29 CN CN201780051060.8A patent/CN109642141A/en not_active Withdrawn
- 2017-08-29 JP JP2017561023A patent/JP6308413B1/en active Active
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| JPS58122977A (en) * | 1982-01-18 | 1983-07-21 | Takeda Chem Ind Ltd | Composition for polyurethane adhesive |
| JPH0711225A (en) * | 1993-04-26 | 1995-01-13 | Takeda Chem Ind Ltd | Polyurethane adhesive composition |
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Also Published As
| Publication number | Publication date |
|---|---|
| WO2018047672A1 (en) | 2018-03-15 |
| JP6308413B1 (en) | 2018-04-11 |
| JPWO2018047672A1 (en) | 2018-09-06 |
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Application publication date: 20190416 |