CN105705601B - Reactive two component adhesive system - Google Patents
Reactive two component adhesive system Download PDFInfo
- Publication number
- CN105705601B CN105705601B CN201480060886.7A CN201480060886A CN105705601B CN 105705601 B CN105705601 B CN 105705601B CN 201480060886 A CN201480060886 A CN 201480060886A CN 105705601 B CN105705601 B CN 105705601B
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- Prior art keywords
- reactive
- adhesive
- weight
- component
- adhesive system
- Prior art date
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Abstract
The present invention relates to new, reactive two component adhesive system, preferably with form membrane, for being bonded multiple material, such as such as metal, timber, glass and/or plastics.
Description
Technical field
It is such as example golden for being bonded a variety of materials preferably with form membrane the present invention relates to two component adhesive system
Category, timber, glass and/or plastic material.The two component adhesive system includes two kinds of reactive adhesives component A and B, preferably
Ground each includes at least one reactive monomer or reaction resin (a), wherein first adhesive components with form membrane
Additionally include at least one radical initiator (c) and second adhesive components additionally include at least one activation
Agent (b).Alternatively, which may include two kinds of reactive adhesives component A and B, preferably with form membrane,
Wherein the first adhesive includes (a) at least one reactive monomer and at least one radical initiator (c) and the second gluing
Agent component B includes activator (b).According to the present invention, providing each has selected from manganese (II) of the following compound as ligand
Complex compound, iron (II) complex compound or cobalt (II) complex compound are as activator：Porphyrin, porphyrazine or one of phthalocyanine or these compounds
Derivative.
Two component adhesive system according to the present invention can be used with adhesive compound or preferably with form membrane.If
In membrane form using two component adhesive system, then by polymer film-forming agent matrix (polymere Filmbildner-
Matrix two reactive adhesives component A and B as described above) are added to.
Additionally, the method for being used to prepare reactive adhesive system according to the present invention as described above is provided and is used
In the kitting material for preparing reactive adhesive system according to the present invention, the adhesive system includes as described above first
With the second reactive adhesive component.
Conventional prior
Two component adhesive system has been widely known for many years and has been described in detail in technical literature.Such
In system, the adhesive system being made of two components is applied to part to be bonded, wherein usually using two liquid groups
Point.For example, for the bi-component polymeric adhesives system of chemically reactive, a component includes monomer to be polymerized and activator
And another component includes free yl induction matter (also referred to as curing agent or initiator) and monomer to be polymerized.In two groups
Divide and mixed or at least contacted simultaneously (in most cases in a manner of heating) after activation, free yl induction matter
It is activated that agent is cracked into two free radicals and polymerisation monomer to be polymerized starts.Then, the free radical chain of monomer gathers
It closes until chain termination generation, and adhesive compound cures, so as to fulfill the permanent adhesive of bonding portion is treated.
The shortcomings that such liquid bi-component polymeric adhesives system is：Their use is often sordid, because
Two components must in most cases be applied with liquid to part to be bonded to paste.Especially glued in large area
There is this problem in the case of connecing and/or wherein in the application of uneven surface (such as inclination).In addition, the adhesive body
The activation of system usually carries out at elevated temperatures, this can be problematic for sensibility substrate such as anodized aluminum.This kind of body
The another shortcoming of system is that it can be vital that long hardening time, which can limit application and the bin stability of two components,.
Moreover, after they fully cure, conventional bi-component polymeric adhesives system often involves only in the case of vibrations
The problem of being exposed.Accordingly, for the system of the prior art, can occur due to fiercely vibrating in bonding region crack or
It is damaged.
Goal of the invention
Therefore, it is an object of the invention to provide improved reactive two component adhesive systems.In this context, this hair
Bright proposition is for being bonded the reactive two component adhesive system of a variety of materials, to avoid known liquid two component adhesive body
The above problem of system.
Particularly, reactive two component adhesive system is provided, be easily manipulated and adherence has ideally been presented,
So as to be not in slide when it is applied to substrate to be bonded, and cause double with liquid known in the prior art
Component polymeric adhesives system is possibly realized compared to more accurate bonding.
The content of the invention
The present invention relates to the reactive adhesive system for including at least two reactive adhesive component A and B, wherein first
Adhesive components A includes at least one reactive monomer or reaction resin (a) and radical initiator (c) and the second gluing
Agent component B includes at least one reactive monomer or reaction resin (a) and activator (b), and wherein activator (b) includes respective
With selected from manganese (II) complex compound, iron (II) complex compound or cobalt (II) complex compound of following compound as ligand：Porphyrin, purple
The derivative of one of dish piperazine or phthalocyanine or this compound.
Alternatively, providing includes the reactive adhesive system of at least two reactive adhesive component A and B, wherein
First adhesive components A includes at least one reactive monomer or reaction resin (a) and radical initiator (c) and second
Adhesive components B only includes activator (b), and wherein activator (b) includes each having selected from following compound as ligand
Manganese (II) complex compound, iron (II) complex compound or cobalt (II) complex compound：One of porphyrin, porphyrazine or phthalocyanine or these compounds
Derivative.
Preferably, the reactive adhesive system according to the present invention of form membrane is provided.This is anti-by including at least two
What the reactive adhesive system of answering property adhesive components (or adhesive film) A and B was achieved, wherein the first adhesive components
A includes at least one reactive monomer or reaction resin (a), and radical initiator (c) and polymer film-forming agent matrix (d) are simultaneously
And second adhesive components B include at least one reactive monomer or reaction resin (a), activator (b) and polymer film forming
Agent matrix (d), wherein activator (b) include each having selected from manganese (II) complex compound, iron of the following compound as ligand
(II) complex compound or cobalt (II) complex compound：The derivative of one of porphyrin, porphyrazine or phthalocyanine or these compounds.
According to the present invention, manganese (II) phthalocyanine, iron (II) phthalocyanine or cobalt (II) phthalocyanine are particularly preferably above-described anti-
It is used as activator (b) in answering property adhesive system.
The reactive adhesive system is properly as bi-component polymeric adhesives system, preferably with form membrane, for each
The improved bonding of kind material.
Specific embodiment
According to the present invention, above-mentioned purpose is by including two kinds of reactive adhesive components, preferably two kinds reactive gluings
The reactive adhesive system of agent film is achieved, it is characterised in that：The activator (b) of handling characteristics each has and is selected from
Manganese (II) complex compound, iron (II) complex compound or cobalt (II) complex compound of following compound as ligand：Porphyrin, porphyrazine or phthalein
The derivative of one of cyanines or these compounds.Particularly preferably use manganese (II) phthalocyanine, iron (II) phthalocyanine or cobalt (II) phthalocyanine.
In an embodiment according to the present invention, reactive adhesive system includes at least two reactive adhesives
Component A and B, wherein the first adhesive components A includes at least one reactive monomer or reaction resin (a) and free radical triggers
Agent (c) and the second adhesive components include at least one reactive monomer or reaction resin (a) and activator (b) and wherein
Activator (b) includes each having selected from manganese (II) complex compound, iron (II) complex compound or cobalt of the following compound as ligand
(II) complex compound：The derivative of one of porphyrin, porphyrazine or phthalocyanine or these compounds.
In the embodiment of replacement according to the present invention, reactive adhesive system includes at least two reactive gluings
Agent component A and B, wherein the first reactive adhesive component A is including at least one reactive monomer or reaction resin (a) and certainly
By base initiator (c) and the second adhesive components include activator (b) and wherein activator (b) include each having be selected from
Under manganese (II) complex compound, iron (II) complex compound or cobalt (II) complex compound as ligand of compound：Porphyrin, porphyrazine or phthalocyanine
Or the derivative of one of these compounds.
The reactive adhesive system of the present invention is provided in preferred embodiments with form membrane：
This adhesive film system in one embodiment includes at least two reactive adhesive components or gluing
Agent film A and B, wherein the first adhesive components A includes at least one reactive monomer or reaction resin (a), free radical trigger
Agent (c) and polymer film-forming agent matrix (d) and the second adhesive components include at least one reactive monomer or reactivity tree
Fat (a), activator (b) and polymer film-forming agent matrix (d) and wherein activator (b) include each having selected from following chemical combination
Manganese (II) complex compound, iron (II) complex compound or cobalt (II) complex compound of object as ligand：Porphyrin, porphyrazine or phthalocyanine or these changes
Close the derivative of one of object.
Alternatively, the reactive adhesive system of form membrane includes at least two reactive gluings in another embodiment
Agent component or adhesive film A and B, wherein the first adhesive components A includes activator (b) and optionally polymer film-forming agent matrix
(d) and the second adhesive components include at least one reactive monomer or reaction resin (a), radical initiator (c) and
Polymer film-forming agent matrix (d) and wherein activator (b) include each having selected from manganese of the following compound as ligand
(II) complex compound, iron (II) complex compound or cobalt (II) complex compound：The derivative of one of porphyrin, porphyrazine or phthalocyanine or these compounds
Object.
Therefore, in an embodiment according to the present invention, provide including at least one reactive monomer or reactivity
The reactive adhesive component of resin (a) and activator (b), wherein activator (b) include each having selected from following chemical combination
Manganese (II) complex compound, iron (II) complex compound or cobalt (II) complex compound of object as ligand：Porphyrin, porphyrazine or phthalocyanine or these changes
Close one of object derivative.
In the embodiment of replacement according to the present invention, the reactive adhesive component including activator (b) is provided,
Middle activator (b) include each have selected from following compound as manganese (II) complex compound of ligand, iron (II) complex compound or
Cobalt (II) complex compound：The derivative of one of porphyrin, porphyrazine or phthalocyanine or these compounds.
In above-described embodiment according to the present invention, particularly preferably use manganese (II) phthalocyanine, iron (II) phthalein
Cyanines or cobalt (II) phthalocyanine are as activator (b).
According to other embodiments of the present invention, the reactive gluing according to the present invention for preparing form membrane is disclosed
The method of agent system, wherein this method comprise the following steps：
1. by ingredient dissolving and/or Fine distribution in one or more solvents and/or water；
2. mixed dissolution or Fine distribution ingredient；
3. with the mixture of the dissolving according to step 2 or the ingredient of distribution be coated with peeling liner or peeling paper, back lining materials or
Pressure-sensitive adhesive；
4. the evaporation solvent and/or water；With
5. optionally the reactive adhesive component is wound into a roll；
Wherein ingredient includes
(A) at least one reactive monomer (a), radical initiator (b) and polymer film-forming agent matrix (d)；Or
(B) at least one reactive monomer (a), activator (b) and polymer film-forming agent matrix (d)；
Optionally other additive and/or auxiliary substance.
In another embodiment according to the present invention, provide and be used to prepare two component adhesive system according to the present invention
Kitting material.
In another embodiment according to the present invention, complex is disclosed, utilizes reactive glue according to the present invention
Stick system is bonded using reagent according to the present invention.
Adhesive components, the preferably component of adhesive film or adhesive system according to the present invention according to the present invention
It will be described below.
Reactive monomer or reaction resin (a)
As used in this article, refer to being capable of particularly radical chain polymerization for reactive monomer or reaction resin (a)
Monomer or resin.
According to the present invention, suitable reactive monomer is selected from：Acrylic acid, acrylate, methacrylic acid, methacrylic acid
Ester, diacrylate, dimethylacrylate, triacrylate, trimethyl acrylic ester, higher functionality acrylate,
Methacrylate, vinyl compound and/or the oligomeric or polymerizable compound with carbon-carbon double bond of higher functionality.
In preferred embodiments, reactive monomer is selected from following one or more representatives：Methyl methacrylate
Ester (CAS 80-62-6), methacrylic acid (CAS 79-41-4), cyclohexyl methacrylate (CAS 101-43-9),
Methacrylic acid tetrahydro furfuryl ester (CAS 2455-24-5), methacrylic acid 2- phenoxyethyl acrylates (CAS 10595-06-
9), haloalkylacrylates, particularly methacrylic acid 2- hydroxyethyls ester (CAS 868-77-9), metering system
Sour 2- hydroxy-propyl esters (CAS 923-26-2 and 27813-02-1), methacrylic acid 4- hydroxybutyls ester (CAS 29008-
35-3 and 997-46-6), two (ethylene glycol) methyl ether methacrylates (CAS 45103-58-0) and/or dimethyl allene
Sour glycol ester (CAS 97-90-5).
In another preferred embodiment according to the present invention, reactive adhesive component includes methacrylic acid cyclohexyl
Ester, methacrylic acid tetrahydro furfuryl ester, the mixture of methacrylic acid and ethylene glycol dimethacrylate are as to be polymerized
Reactive monomer.
In another preferred embodiment according to the present invention, reactive adhesive component includes methacrylic acid 2- benzene oxygen
Base ethyl ester, methacrylic acid 2- hydroxyethyls ester, methacrylic acid 2- hydroxy-propyl esters and ethylene glycol dimethacrylate
Mixture as reactive monomer to be polymerized.
In another preferred embodiment according to the present invention, reactive adhesive component includes methacrylic acid 2- benzene oxygen
The mixture of base ethyl ester, 2-hydroxyethyl methacrylate and ethylene glycol dimethacrylate is as reactivity to be polymerized
Monomer.
In another preferred embodiment according to the present invention, reactive adhesive component includes methacrylic acid 2- benzene oxygen
Base ethyl ester is as reactive monomer to be polymerized.
In another preferred embodiment according to the present invention, reactive adhesive component include methyl methacrylate,
Methacrylic acid and the mixture of ethylene glycol dimethacrylate are as reactive monomer to be polymerized.
In another preferred embodiment according to the present invention, reactive adhesive component includes methacrylic acid 2- benzene oxygen
Base ethyl ester and the mixture of ethylene glycol dimethacrylate are as reactive monomer to be polymerized.
In another preferred embodiment according to the present invention, reactive adhesive component includes two (ethylene glycol) methyl ethers
Methacrylate and the mixture of ethylene glycol dimethacrylate are as reactive monomer to be polymerized.
May be selected oligomeric mono-, di-, three and higher functionality (mono-, di-, tri-and higher-
Functionalized) (methyl) acrylate is as reaction resin.Very advantageously, these are reacted at least one
It is used in the mixture of property monomer.
According to the present invention, each in these preferred embodiments can with as polymer film-forming agent matrix (d)
Thermoplastic polyurethane is (for example, Desmomelt) combination, as described below.
According to the present invention, a kind of reactive monomer/a variety of reactive monomers/a kind of reaction resin/a variety of reactivity tree
The amount of fat is in the range of about 20-80 weight %, preferably about 40-60 weight %, each group based on reactive adhesive component
The total mixture divided.It is most preferably anti-using a kind of reactive monomer/a variety of reactive monomer/one kind of about 40-50 weight %
Answering property resin/a variety of reaction resins, the total mixture of each component based on reactive adhesive component.Reactive adhesive group
The total mixture of each component divided refers herein to the total amount of used component, including reactive monomer or reactivity tree
Fat (a), activator (b), radical initiator (c), polymer film-forming agent matrix (d) and/or the other components being optionally present,
It is obtained (in terms of weight %) as sum.
Activator (b)
As used in this article, term activator refers to such compound, even also first in low-down concentration
First allow or promote the progress of polymerization.Activator can be also known as to accelerating agent or accelerator.
In the present invention, activator is added to reactive adhesive component B, be added in preferred embodiments anti-
Answering property adhesive film B, the activator include having manganese, iron or cobalt ions as central atom and the compound containing carbon-to-nitrogen double bon
Complex compounds as ligand.In this case, the compound containing carbon-to-nitrogen double bon in the complex compounds with the moon
Ionic species exists.Manganese, iron or cobalt ions two positive charges of band in the complex compounds, and the chemical combination containing carbon-to-nitrogen double bon
Two negative electrical charges of object band.Manganese, iron or cobalt ions each replace ligand reacting into the complex compound in the complex compounds
Before compound on nitrogen-atoms with two hydrogen atoms.
In preferred embodiments, ligand has cyclic structure, preferably porphyrin, porphyrazine or phthalocyanine ring structure.This
A little structures should be understood frame structure.Ligand carries substitution optionally on the position of hydrogen atom for being bonded to carbon atom
Base.In this case, they are referred to as the derivative of these compounds.Suitable substituent group is selected from：Fluorine, chlorine, bromine, iodine, methyl,
Ethyl, propyl, isopropyl, butyl, tertiary butyl ,-OH ,-NH2-、-NO2。
Particularly suitable activator includes iron (II) phthalocyanine (CAS 132-16-1).
According to the present invention, the amount of activator more than 0 to the scope of about 10 weight %, preferably about 0.1-5.0 weight %.
Most preferably using about 0.2-3.0 weight %, the activator of even more preferably 0.5-2.0 weight %, based on reactive gluing
The total mixture of each component of agent component.The total mixture of each component of reactive adhesive component refers herein to be used
Component total amount, including reactive monomer or reaction resin (a), activator (b), radical initiator (c), polymer
Film forming agent matrix (d) and/or the other components being optionally present, obtain (in terms of weight %) as sum.
Radical initiator (K)
As used in this article, term initiator, particularly radical initiator or free yl induction matter (or are also solid
Agent) refer to trigger the polymerisation of adhesive or crosslinked compound.However, (particularly free radical draws initiator
Hair agent) with the polymers compositions occurred and therefore do not form decision bond property of very small share (content) participation reaction.
In the present invention, initiator (particularly radical initiator) is added into at least one first of adhesive system
In reactive adhesive component.
Radical initiator is preferred.All radical initiators known in the art can be used.Preferred free radical
Initiator is peroxide, hydroperoxides and azo-compound.
In particularly preferred embodiment according to the present invention, radical initiator is organic peroxide or hydrogen peroxide
Compound.Alpha, alpha-dimethylbenzyl hydroperoxides are particularly preferred, are also known as cumene hydroperoxide (CAS 80-15-
9).Further preferably it is diisopropyl phenyl hydroperoxides (CAS 26762-93-6), to terpane hydroperoxides (No. CAS
26762-92-5) and 1,1,3,3- tetramethyl butyls hydroperoxides (CAS 5809-08-5).
According to the present invention, the amount of radical initiator is in the range of about 3-30 weight %, preferably about 8-15 weight %,
The total mixture of each component based on reactive adhesive component.Most preferably triggered using the free radical of about 9-11 weight %
Agent, the total mixture of each component based on reactive adhesive component.The total mixture of each component of reactive adhesive component
The total amount of component used in herein referring to, including reactive monomer or reaction resin (a), activator (b), free radical
Initiator (c), polymer film-forming agent matrix (d) and/or the other components being optionally present, obtain as sum (with weight %
Meter).
Polymer film-forming agent matrix (d)
Adhesive film component according to the present invention is alternately made of matrix, hereinafter referred to as polymer film-forming agent base
Matter, wherein containing reactive monomer and/or reaction resin to be polymerized.Such adhesive components are present as a film simultaneously
Therefore also referred to as adhesive film.The purpose of the matrix is to form the inertia foundation structure (master of reactive monomer and/or tackifying resin
Chain, Grundger ü st), thus thus they cause in the form of liquid and described problem unlike in the prior art, and
It is incorporated in film or paper tinsel.Therefore ensure that easier manipulation.
In this case, inertia means the reactive monomer and/or reaction resin at properly chosen conditions
(such as in sufficiently low temperature) substantially not with the polymer film-forming agent substrate reaction.
It is suitable for the invention film forming agent matrix and is preferably chosen from following list：Thermoplastic polymer, such as polyester or common
Polyester, polyamide or copolyamide, polyacrylate, acrylate copolymer, polymethacrylates, methacrylate are common
The substance chemically or physically of polymers, thermoplastic polyurethane and above-claimed cpd.In addition, different thermoplastics also can be used
The blend of property polymer.
In addition, as polymer film-forming agent matrix, elastomer and thermoplastic elastomer (TPE) are also (in itself or in the mixture)
It is contemplated that.Thermoplastic polymer, particularly hemicrystalline thermoplastic polymer is preferred.
Thermoplastic polymer of the softening temperature less than 100 DEG C is particularly preferred.In this respect, term softening point refers to
It is that thermoplastic granulates start the temperature bonded with itself.If the component of polymer film-forming agent matrix is hemicrystalline thermoplastic poly
Close object, then in addition to its softening temperature (it is related with the fusing of crystal), it is much preferred that its glass transition
Temperature is no more than 25 DEG C, preferably no more than 0 DEG C.
According to a preferred embodiment of the invention, thermoplastic polyurethane is used.Thermoplastic polyurethane is preferably
Softening temperature with less than 100 DEG C, particularly less than 80 DEG C.
In a particularly preferred embodiment according to the present invention, Desmomelt(it can be from Bayer
Material Science AG, 51358Leverkusen, Germany commercially available from) be used as polymer film-forming agent matrix.DesmomeltFor it is hydroxy-end capped, be substantially linear, highly crystalline thermoplastic polyurethane elastomer.
According to the present invention, the amount of polymer film-forming agent matrix is about 20-80 weight %, preferably about 30-50 weight %'s
In the range of, the total mixture of each component based on reactive adhesive component.Most preferably use 35-45 weight %, preferably
The polymer film-forming agent matrix of about 40 weight %, the total mixture of each component based on reactive adhesive component.Reactive glue
The total mixture of each component of stick component herein refers to the total amount of used component, including reactive monomer or reaction
Property resin (a), activator (b), radical initiator (c), polymer film-forming agent matrix (d) and/or be optionally present other groups
Point, it is obtained (in terms of weight %) as sum.
Crosslinking agent
As used in this article, term crosslinking agent refers to such chemical compound：It is capable of providing with reactive official
The linear molecule chain that can be rolled into a ball, thus three-dimensional crosslinking structure can be formed by two-dimensional structure by the formation of intermolecular bridge.
The representative instance of crosslinking agent is such chemical compound：There are two it has in the molecule or in two molecular ends
Or more identical or different functional group, and therefore the molecule of identical or different structure can be made to be cross-linked to each other.In addition, crosslinking
Agent can be with reactive monomer as defined above or reaction resin reaction without polymerizeing truly.Because with such as
The upper activator is different, and crosslinking agent can be combined into polymer network.
In particularly preferred embodiment according to the present invention, by ethylene glycol dimethacrylate (CAS 97-90-
5) it is used as crosslinking agent and/or reactive monomer (see above).
It is preferred that crosslinking agent also has diacrylate, dimethylacrylate, triacrylate, trimethyl acrylic ester, more
The acrylate of high functionality and/or the methacrylate of higher functionality.
Other components of reactive adhesive component A and/or B
The reactive adhesive film of the present invention can be optionally included in other additive well known in the prior art and/or auxiliary
Help substance.Here examples which may be mentioned include filler, dyestuff, pigment, nucleating agent, rheologic additive, foaming agent, bonding enhancings to add
Agent (adhesion promotor, tackifying resin, adhesive, pressure-sensitive adhesive), mixed agent, plasticizer and/or age resister, light is added to stablize
Agent and ultraviolet screener (UV-Schutzmittel), such as with auxiliary antioxidant of advocating peace (primary and secondary
Antioxidants form).
Reactive adhesive component A and B
According to a preferred embodiment of the invention, the first adhesive components A of at least one includes following component
Mixture：Thermoplastic polyurethane, particularly DesmomeltMethacrylic acid 2- phenoxyethyl acrylates, metering system
Sour 2- hydroxyethyls ester, methacrylic acid 2- hydroxy-propyl esters, ethylene glycol dimethacrylate and cumene hydroperoxide.
In another preferred embodiment according to the present invention, at least one first adhesive components include following component
Mixture：Thermoplastic polyurethane, particularly DesmomeltMethacrylic acid 2- phenoxyethyl acrylates, methacrylic acid
2- hydroxyethyls ester, ethylene glycol dimethacrylate and cumene hydroperoxide.
In another preferred embodiment according to the present invention, the first adhesive components A of at least one includes following component
Mixture：Phenoxyethyl methacrylate and cumene hydroperoxide.
In preferred embodiments, the first adhesive components A includes at least one reactivity of (i) 20-80 weight %
At least one of the radical initiator (c), preferably 40-60 weight % of monomer or reaction resin (a) and 2-30 weight %
The radical initiator (c) or (ii) 20-80 weight % of reactive monomer or reaction resin (a) and 8-15 weight % gather
Close object film forming agent matrix (d), at least one reactive monomer or reaction resin (a) of 20-80 weight % and 2-30 weight %
Radical initiator (c), preferably 30-50 weight % polymer film-forming agent matrix (d), at least the one of 40-60 weight %
The radical initiator (c) of kind reactive monomer or reaction resin (a) and 8-15 weight %, based on reactive adhesive component
Each component total mixture.Here the total mixture of each component of reactive adhesive component represents the total of the component used
Amount, including reactive monomer or reaction resin (a), activator (b), radical initiator (c), polymer film-forming agent matrix
(d) and/or other components for being optionally present, obtained (in terms of weight %) as sum.
According to a preferred embodiment of the invention, the second adhesive components B of at least one includes following component
Mixture：Thermoplastic polyurethane, particularly DesmomeltMethacrylic acid 2- phenoxyethyl acrylates, metering system
Sour 2- hydroxyethyls ester, methacrylic acid 2- hydroxy-propyl esters, ethylene glycol dimethacrylate and iron (II) phthalocyanine.
In another preferred embodiment according to the present invention, the second adhesive components B of at least one includes following component
Mixture：Thermoplastic polyurethane, particularly DesmomeltMethacrylic acid 2- phenoxyethyl acrylates, metering system
Sour 2- hydroxyethyls ester, ethylene glycol dimethacrylate and iron (II) phthalocyanine.
In another preferred embodiment according to the present invention, the second adhesive components B of at least one includes following component：
Iron (II) phthalocyanine.
In preferred embodiments, the second adhesive components include the activator (b) of (i) 0.1-5 weight %, preferably
The activator (b) of 0.5-2 weight % or at least one reactive monomer or reaction resin (a) of (ii) 20-80 weight % and
At least one reactive monomer or reaction resin (a) of the activator (b) of 0.1-5 weight %, preferably 40-60 weight % and
The activator (b) of 0.5-2 weight % or the polymer film-forming agent matrix (d) of (iii) 20-80 weight %, 20-80 weight %'s
The activator (b) of at least one reactive monomer or reaction resin (a) and 0.1-5 weight %, preferably 30-50 weight %'s
Polymeric membrane forming agent (d), at least one reactive monomer or reaction resin (a) of 40-60 weight % are with 0.5-2 weight %'s
Activator (b), the total mixture of each component based on reactive adhesive component.Here each component of reactive adhesive component
The total amount of component that uses of total mixture expression, include reactive monomer or reaction resin (a), activator (b), freedom
Base initiator (c), polymer film-forming agent matrix (d) and/or the other components being optionally present are obtained as sum (with weight
Measure % meters).
In general, reactive adhesive the component A and/or B according to the present invention of form membrane have about 20-200 μm, preferably
About 30-100 μm, about more preferably 40-60 μm and particularly preferably about 50 μm of layer thickness.In order to generate larger layer thickness,
Advantageously multiple adhesive films are pressed together layer by layer.
In addition, reactive adhesive component A and B according to the present invention are characterized in that they preferably have pressure-sensitive adhesive
Property.According to(Online 2013, file identification RD-08-00162) by pressure sensitive glueyness Material Definitions
For such viscoelastic adhesive, the film of cured drying is at room temperature permanent gluing and keeps adhesivity.Pass through
Using mild pressure, pressure-sensitive adhesive is realized in almost all of substrate at once.Herein, mild pressure refers to be more than 0
Bar pressure, apply more than 0 second.
Reactive adhesive system
According to the present invention, the first and second reactive adhesives component as described above is used for reactive adhesive system,
It is characterized in that：First reactive adhesive component A includes at least one reactive monomer or reaction resin (a) and free radical
Initiator (c) and the second adhesive components B include at least one reactive monomer or reaction resin (a) and activator (b) and
Wherein activator (b) includes each having selected from manganese (II) complex compound, iron (II) complex compound of following compound as ligand
Or cobalt (II) complex compound：The derivative of one of porphyrin, porphyrazine or phthalocyanine or these compounds.
Alternatively, reactive adhesive architectural feature according to the present invention is：It includes at least two reactive gluings
Agent component A and B, wherein the first adhesive components A includes at least one reactive monomer or reaction resin (a) and free radical draws
It sends out agent (c) and the second adhesive components include activator (b) and wherein activator (b) includes each having selected from following chemical combination
Manganese (II) complex compound, iron (II) complex compound or cobalt (II) complex compound of object as ligand：Porphyrin, porphyrazine or phthalocyanine or these changes
Close the derivative of one of object.
In preferred embodiments, the reactive adhesive system of the present invention is provided with form membrane：
The adhesive film architectural feature is：It includes at least two reactive adhesive components or adhesive film A and B,
Wherein the first adhesive components A includes at least one reactive monomer or reaction resin (a), radical initiator (c) and poly-
It closes object film forming agent matrix (d) and the second adhesive components includes at least one reactive monomer or reaction resin (a), activation
Agent (b) and polymer film-forming agent matrix (d) and wherein activator (b) include each having selected from following compound as ligand
Manganese (II) complex compound, iron (II) complex compound or cobalt (II) complex compound：One of porphyrin, porphyrazine or phthalocyanine or these compounds
Derivative.
Alternatively, the reactive adhesive architectural feature of form membrane is according to the present invention：It includes at least two reactions
Property adhesive components or adhesive film A and B, wherein the first adhesive components A includes at least one reactive monomer or reactivity
Resin (a), radical initiator (c) and polymer film-forming agent matrix (d) and the second adhesive components include activator (b) and appoint
Selection of land polymer film-forming agent matrix (d) and wherein activator (b) include each having selected from following compound as ligand
Manganese (II) complex compound, iron (II) complex compound or cobalt (II) complex compound：One of porphyrin, porphyrazine or phthalocyanine or these compounds are spread out
Biology.
According to the present invention, additionally provide including two or more as defined above first adhesive components A or the
The reactive adhesive system of two adhesive components B and optionally other backing, peeling paper and/or peeling liner,
Two of which or more kind the first adhesive components A or the second adhesive components B each alternately exists.
Once (particularly 0.5-3 bars, at room temperature (23 DEG C)) is by the first and second reactive gluings under suitable pressure
Agent component A and B are contacted, they are just crosslinked and are cured.Optionally, higher or lower temperature is also possible.The conjunction mentioned
Suitable pressure should be especially achievable.According to the present invention, time of contact at room temperature is several seconds to a few minutes, preferably 10-
60 seconds.Mechanically or manually apply pressure.
Two kinds of reactive adhesive components A and B are applied in advance if as described above treats bonding substrates, then above-mentioned
It is crosslinked the result is that occur substrate permanent bonding.Alternatively, it is to be bonded that adhesive components A to first can also be applied first
Substrate and apply adhesive components B to adhesive components A.Then, the second substrate to be bonded is applied to adhesive components
B。
In addition, reactive adhesive system according to the present invention can further comprise film, layer, adhesive and permanent or face
When backing.
Suitable back lining materials are known to the skilled in the art.For example, film (polyester, PET, PE, PP, BOPP, PVC,
Polyimides), non-woven fabrics, foams, woven fabric and/or fabric paillon can be used as permanent backing.Interim backing should be equipped with stripping
Absciss layer, wherein the peeling layer is usually made of the release coating of silicone release coating or fluorination or is essentially polyolefin
(HDPE, LDPE).
It can be required to pre-process the surface to be bonded connect using physics, chemistry and/or physical-chemical method.At this
In the case of, it is favourable using such as priming paint or adhesion promoter composition.
Substrate
The suitable substrate for fitting through reactive adhesive system according to the present invention bonding is metal, glass, timber,
Concrete, stone material, ceramics, textile and/or plastic material.Matrix to be bonded may be the same or different.
In preferred embodiments, reactive adhesive system according to the present invention is used for bonded metal, glass and modeling
Expect material.In particularly preferred embodiment according to the present invention, makrolon and anodized aluminum are glued.
Metallic substrates to be bonded can usually be manufactured by any common metal and metal alloy.Preferably, using metal such as
Aluminium, stainless steel, steel, magnesium, zinc, nickel, brass, copper, titanium, ferrous metal and alloy.It part to be bonded can be additionally by different gold
Belong to and forming.
Suitable plastic matrix is such as acrylonitrile-butadiene-styrene copolymer (ABS), makrolon (PC), ABS/
PC blends, PMMA, polyamide, the polyamide of glass fiber reinforcement, polyvinyl chloride, Kynoar
(Polyvinylenfluorid), cellulose acetate, cyclic olefine copolymer, liquid crystal polymer (LCP), polyactide, polyether-ketone, poly-
Etherimide, polyether sulfone, polymethacryl methyl imide (Polymethacrylmethylimid), polymethylpentene,
It is polyphenylene oxide, polyphenylene sulfide, poly- phthalimide, polyurethane, polyvinyl acetate, styrene-acrylonitrile copolymer, poly-
Acrylate and polymethacrylates, polyformaldehyde, Acrylate-styrene bipolymer-acrylonitrile copolymer, polyethylene, polystyrene,
Polypropylene and/or polyester, such as polybutylene terephthalate (PBT) (PBT) and/or polyethylene terephthalate (PET).
Japanning, printing, vapor deposition or spraying plating can be carried out to substrate.
The matrix to be bonded connect can be with the complex obtained using required any desired form.Simplest
In form, substrate is flat.In addition, it is possible to use reactive adhesive system according to the present invention is bonded three-dimensional substrates (its example
As for oblique).Base to be bonded is low can also to have multiple functions, for example, shell, form, hardening component etc..
It is used to prepare in the method for the reactive adhesive component of form membrane
Reactive adhesive film according to the present invention is prepared by following methods (adhesive components are with form membrane)：
In the first step, by ingredient dissolving or Fine distribution in one or more solvents and/or water.Alternatively, no
Solvent and/or water are needed, because the ingredient has all been dissolved in one another (optionally under the action of heat and/or shearing).
Suitable solvent is known in the art, wherein it is preferable to use at least one of described ingredients wherein to have good dissolving
The solvent of property.Acetone is particularly preferred.
As used in this application, term ingredient includes at least one reactive monomer (a), radical initiator (b) and gathers
Close object film forming agent matrix (d) or at least one reactive monomer (a), activator (b) and polymer film-forming agent matrix (d) and on
Optionally other additive and/or auxiliary substance defined in face.
Then the ingredient of mixed dissolution or Fine distribution in the second step.Mixture is prepared with convention stir device.Separately
Other places, solution are optionally heated.Optionally, ingredient is made while dissolving or Fine distribution and mixing.
First step and second step can also carry out in one step, that is to say, that make ingredient and meanwhile dissolving and/or
Fine distribution.
Then, in third step, it is coated with and is removed with the mixture of the dissolving according to step 2 or the ingredient of Fine distribution
Paper, back lining materials or pressure-sensitive adhesive.The coating is implemented by routine techniques known in the art.
After coating, evaporation of solvent is passed through in four steps.
Optionally, reactive adhesive film can be wound into a roll in other steps.
In order to store, reactive adhesive film peeling liner according to the present invention or peeling paper are covered.
Alternately, reactive adhesive film according to the present invention passes through extrusion, heat fusing mouth pattern coating (hot melt
Die coating) or calendering prepared in a manner of solvent-free and is anhydrous.
It is used to prepare the kitting material of two component adhesive system according to the present invention
According to the present invention, kitting material is additionally provided with, is used to provide the double groups of reactivity preferably in membrane form
Divide adhesive system.The kitting material includes first reactive adhesive A of at least one as described above, and it includes initiations
Agent, particularly radical initiator；With at least one second reactive adhesive B as described above, it includes activators.
Kitting material according to the present invention is generally as follows use：
At least one first adhesive components A is applied to the surface of substrate to be bonded.In addition, at least one second glue
Stick component B applies to the surface of the second substrate to be bonded.Adhesive components A and adhesive components B is made to contact and in room temperature
Contact is kept under (23 DEG C) within pressing time of the several seconds to several minutes, thus polymerisation starts and adhesive cures.It replaces
The second adhesive film B of at least one can also be applied to the first adhesive film A, and only apply at this moment to second and treat by Dai Di
The surface of the substrate of bonding.
Optionally, repeat the above method be achieved in layer substrate-A-B-A-B- substrates or substrate-B-A-B- substrates or
The bonding of substrate-A-B-A- substrates etc..Advantageously, the pressure between bonding substrates and the first and second adhesive film A and B is treated
The property of quick gluing is different.
Compound
Finally, according to the present invention, complex is provided, utilizes reactive adhesive according to the present invention as defined above
System is bonded by kitting material according to the present invention as defined above.
Experimental section
The following examples should not be construed as limiting protection domain in any way for illustrating the present invention.
The preparation of the solution of film former polymer
PU solution：
Pass through the Desmomelt for the 120g that weighs first in screw top jarDescribed in the acetone of 480g and closing
Screw top jar prepares the 20% of film former polymer acetone soln solution.By rotating the spiral mouth on a roller bench
Bottle a couple of days makes DesmomeltIt is completely dissolved.Depending on rolling speed, operation lasts about one to seven day.Alternatively, utilize
Commercial laboratory stirrer is by stirring the Desmomelt in acetoneParticle can also prepare the acetone soln.
The preparation of reactive component A and B
Component A1：
Using commercial laboratory stirrer by the methacrylic acid 2- phenoxyethyl acrylates of 100.0g and the hydrogen peroxide of 10.0g
Change cumene to mix 10 minutes, thereby produce homogeneous mixture.
Component B1：
Component B1 is iron (II) phthalocyanine (grade of powder type：Sigma-Aldrich, purity is about 90%).
Component B2：
Iron (II) phthalocyanine of 5.0g is stirred 10 minutes in the acetone of 50.0g using commercial laboratory stirrer, thus
Generate the mixture with dissolving part.
The preparation of reactive component A and B and film former polymer：Component A-P and B-P
Component A-P1：
Using commercial laboratory stirrer by 150.0gDesmomelt20% acetone soln (PU solution) with
The methacrylic acid 2- phenoxyethyl acrylates of 25.3g, methacrylic acid 2- hydroxyethyls ester, the metering system of 12.7g of 19.0g
The cumene hydroperoxide mixing of sour 2- hydroxy-propyl esters, the ethylene glycol dimethacrylate of 3.0g and 10.0g 10 minutes, thus
Generate homogeneous mixture.
The percentage composition for giving component A-P1 in following table together is weighed with described：
Herein, solid * is interpreted as all substances of non-solvent.Herein, solvent is only acetone.
Component A-P2：
Using commercial laboratory stirrer by 200.0gDesmomelt20% acetone soln (PU solution) with
The methacrylic acid 2- phenoxyethyl acrylates of 20.9g, methacrylic acid 2- hydroxyethyls ester, the dimethyl propylene of 3.0g of 26.2g
The cumene hydroperoxide of olefin(e) acid glycol ester and 10.0g mix 10 minutes, thus generate homogeneous mixture.
The percentage composition for giving component A-P2 in following table together is weighed with described：
Herein, solid * is interpreted as all substances of non-solvent.Herein, solvent is only acetone.
Component B-P1：
Using commercial laboratory stirrer by 150.0g Desmomelt20% acetone soln (PU solution) with
The methacrylic acid 2- phenoxyethyl acrylates of 29.3g, methacrylic acid 2- hydroxyethyls ester, the metering system of 14.3g of 22.4g
Iron (II) phthalocyanine of sour 2- hydroxy-propyl esters, the ethylene glycol dimethacrylate of 3.0g and 1.0g mixes 10 minutes, thus produces
The raw mixture with dissolving part.
The percentage composition for giving component B-P1 in following table together is weighed with described：
Herein, solid * is interpreted as all substances of non-solvent.Herein, solvent is only acetone.
Component B-P2：
Using commercial laboratory stirrer by 200.0g Desmomelt20% acetone soln (PU solution) with
The methacrylic acid 2- phenoxyethyl acrylates of 24.9g, methacrylic acid 2- hydroxyethyls ester, the dimethyl propylene of 3.0g of 31.1g
The iron of olefin(e) acid glycol ester and 1.0g (II) phthalocyanine mixes 10 minutes, thus generates the mixture with dissolving part.
The percentage composition for giving component B-P2 in following table together is weighed with described：
Herein, solid * is interpreted as all substances of non-solvent.Herein, solvent is only acetone.
Component B-P3：
Using commercial laboratory stirrer by 150.0gDesmomelt20% acetone soln (PU solution) with
The methacrylic acid 2- phenoxyethyl acrylates of 29.3g, methacrylic acid 2- hydroxyethyls ester, the metering system of 14.3g of 22.4g
Manganese (II) phthalocyanine of sour 2- hydroxy-propyl esters, the ethylene glycol dimethacrylate of 3.0g and 1.0g mixes 10 minutes, thus produces
The raw mixture with dissolving part.
The percentage composition for giving component B-P3 in following table together is weighed with described：
Herein, solid * is interpreted as all substances of non-solvent.Herein, solvent is only acetone.
Component B-P4：
Using commercial laboratory stirrer by 150.0g Desmomelt20% acetone soln (PU solution) with
The methacrylic acid 2- phenoxyethyl acrylates of 29.3g, methacrylic acid 2- hydroxyethyls ester, the metering system of 14.3g of 22.4g
Cobalt (II) phthalocyanine of sour 2- hydroxy-propyl esters, the ethylene glycol dimethacrylate of 3.0g and 1.0g mixes 10 minutes, thus produces
The raw mixture with dissolving part.
The percentage composition for giving component B-P4 in following table together is weighed with described：
Herein, solid * is interpreted as all substances of non-solvent.Herein, solvent is only acetone.
The production of reactive adhesive film KF-A-P and KF-B-P
Adhesive film KF-A-P1：
Table is coated with (such as from SMO (Sondermaschinen Oschersleben using commercial laboratory with painting cloth-knife
GmbH)) component A-P1 is applied to the polyester film (stripping film) of silication.Then acetone is made in 60 DEG C in drying by circulating air cabinet
Evaporation 10 minutes.The wide film for being adjusted to obtain 50 μ m-thicks after the solvent evaporates of gap during coating.With the polyester of the second silication
The reactive adhesive film KF-A-P1 for the adhesivity that film covers is until bonding and being stored.
Adhesive film KF-A-P2：
Table is coated with (such as from SMO (Sondermaschinen Oschersleben using commercial laboratory with painting cloth-knife
GmbH)) component A-P2 is applied to the polyester film (stripping film) of silication.Then acetone is made in 60 DEG C in drying by circulating air cabinet
Evaporation 10 minutes.The wide film for being adjusted to obtain 50 μ m-thicks after the solvent evaporates of gap during coating.With the polyester of the second silication
The reactive adhesive film KF-A-P2 for the adhesivity that film covers is until bonding and being stored.
Adhesive film KF-B-P1：
Table is coated with (such as from SMO (Sondermaschinen Oschersleben using commercial laboratory with painting cloth-knife
GmbH)) component B-P1 is applied to the polyester film (stripping film) of silication.Then acetone is made in 60 DEG C in drying by circulating air cabinet
Evaporation 10 minutes.The wide film for being adjusted to obtain 50 μ m-thicks after the solvent evaporates of gap during coating.With the polyester of the second silication
The reactive adhesive film KF-B-P1 for the adhesivity that film covers is until bonding and being stored.
Adhesive film KF-B-P2：
Table is coated with (such as from SMO (Sondermaschinen Oschersleben using commercial laboratory with painting cloth-knife
GmbH)) component B-P2 is applied to the polyester film (stripping film) of silication.Then acetone is made in 60 DEG C in drying by circulating air cabinet
Evaporation 10 minutes.The wide film for being adjusted to obtain 50 μ m-thicks after the solvent evaporates of gap during coating.With the polyester of the second silication
The reactive adhesive film KF-B-P2 for the adhesivity that film covers is until bonding and being stored.
Adhesive film KF-B-P3：
Table is coated with (such as from SMO (Sondermaschinen Oschersleben using commercial laboratory with painting cloth-knife
GmbH)) component B-P3 is applied to the polyester film (stripping film) of silication.Then acetone is made in 60 DEG C in drying by circulating air cabinet
Evaporation 10 minutes.The wide film for being adjusted to obtain 50 μ m-thicks after the solvent evaporates of gap during coating.With the polyester of the second silication
The reactive adhesive film KF-B-P3 for the adhesivity that film covers is until bonding and being stored.
Adhesive film KF-B-P4：
Table is coated with (such as from SMO (Sondermaschinen Oschersleben using commercial laboratory with painting cloth-knife
GmbH)) component B-P4 is applied to the polyester film (stripping film) of silication.Then acetone is made in 60 DEG C in drying by circulating air cabinet
Evaporation 10 minutes.The wide film for being adjusted to obtain 50 μ m-thicks after the solvent evaporates of gap during coating.With the polyester of the second silication
The reactive adhesive film KF-B-P4 for the adhesivity that film covers is until bonding and being stored.
The preparation of reactivity plastic (knetbar) adhesive KM-A-P and KM-B-P
Adhesive KM-A-P1：
Adhesive KM-A-P1 is obtained by mediating adhesive film KF-A-P1.Kneading is carried out by hand.It also can be in commercialization
(such as laboratory kneader from Haake) is carried out in kneader.Alternatively, adhesive KM-A-P1 also can be by elder generation from group
Divide after removing solvent, obtained by component A-P1 by extrusion method, such as in vented extruder.It is used to prepare adhesive KM-
All operations of A-P1 carry out within the temperature range of room temperature (23 DEG C) to 50 DEG C of highest.
Adhesive KM-B-P1：
Adhesive KF-B-P1 is obtained by mediating adhesive film KM-B-P1.Kneading is carried out by hand.It also can be in commercialization
(such as laboratory kneader from Haake) is carried out in kneader.Alternatively, adhesive KM-B-P1 also can be by elder generation from group
Divide after removing solvent, obtained by component B-P1 by extrusion method, such as in vented extruder.It is used to prepare adhesive KM-
All operations of B-P1 carry out within the temperature range of room temperature (23 DEG C) to 50 DEG C of highest.
Prepare the sample for push out test
Stamp out from adhesive film KF-A-P1, KF-A-P2, KF-B-P1 and KF-B-P2 to be tested with 21mm diameters
Circle die cutting, covered with peeling liner on each comfortable both sides of the adhesive film.Then by the peeling liner respectively since die cutting
One side on remove.Die cutting KF-A-P1 and KF-A-P2 are each properly placed on the similary circle sample with 21mm diameters
On disk (" disk ", the first substrate, the first test sample).Die cutting KF-A-P1 and KF-A-P2 are each bonded to " disk " at this time.With
Identical mode prepares those test specimens of the test sample of the sample disc with makrolon, glass and the sample disc with steel
Product (are shown in Table lattice).Then the peeling paper being still retained on die cutting KF-A-P1 and KF-A-P2 is removed.It provides as a result, at this time
Disk with KF-A-P1 or with KF-A-P2.
Die cutting KF-B-P1 is individually placed upon with not covering side on the die cutting KF-A-P1 for being bonded to disk, is thus punched
Part KF-B-P1 is each bonded to die cutting KF-A-P1.In the same manner, die cutting KF-B-P2 is each placed with not covering side
On the die cutting KF-A-P2 of disk is bonded to, thus die cutting KF-B-P2 is each bonded to die cutting KF-A-P2.In KF-A-
After P1 is contacted with KF-B-P1 or KF-A-P2 with KF-B-P2, it must then be carried out in most one hours and the second substrate
Bonding.
For the preparation further bonded, each will still be retained in last on die cutting KF-B-P1 and KF-B-P2
Peeling liner removes, and thus each makes to expose die cutting KF-B-P1 and KF-B-P2.In modification is tested, no peeling liner rushes
Cut piece KF-A-P1 is placed on again on exposed die cutting KF-B-P1, thus obtains die cutting sequence KF-A-P1/KF-B-
P1/KF-A-P1.Remaining peeling liner from die cutting KF-A-P1 is removed again at this time, thus makes die cutting KF-A-P1 sudden and violent
Reveal and bonding test sample/KF-A-P1/KF-B-P1/KF-A-P1/ test samples (being shown in Table lattice) can be produced.
For the bonding of push out test
Second substrate (the second test sample) be the square perforation plate made of makrolon (PC), glass or steel (see
Form)；The length of side is 40mm in every case, has the circular hole (bore dia 9mm) for being arranged in square plate center.
It is provided with the circle test sample of the die cutting KF-A-P1 and KF-B-P1 that bond together and is provided with and be bonded in one
The die cutting KF-A-P2 and KF-B-P2 risen justifies test sample and the die cutting to bond together is provided in modification is tested
The circle test sample of KF-A-P1, KF-B-P1 and KF-A-P1 and each exposed side of die cutting are placed in this way
On perforated plate so that justify the center of test sample and be stacked at the hole center of perforated plate.Then, kept by the adhesivity of die cutting
Compound together is made up of：Square perforation plate, die cutting KF-A-P1, die cutting KF-B-P1 and disk or pros
Shape perforated plate, die cutting KF-A-P2, die cutting KF-B-P2 and disk or in modification is tested by square perforation plate, punching
Part KF-A-P1, die cutting KF-B-P1, die cutting KF-A-P1 and disk composition, are so placed on desk so that square
Perforated plate is located at bottom.The weight of 2kg is placed on disk.At room temperature, the compound is exposed to the weight forever
Each self-sustaining a) 10 seconds and b) 60 seconds (pressing time) in the second test series under long pressure.Then the weight is removed.With
Afterwards by the compound 23 DEG C and 50% relative humidity under storage 24 it is small when.During this period, occur in die cutting progressively into
Between capable curing reaction and die cutting the adhesion strength gradually enhanced is generated between substrate (test sample).Therefore, bond with
Time gradually enhances, due to pressure sensitive adhesion effect substantially beyond green strength.Then push out test is carried out.
Push out test
Push out test provides adhesive strength of the gluing product on the direction of the normal of adhesive layer on two-sided gluing
Information.For this purpose, it will be pressed with the constant rate of speed of 10mm/ minutes by the hole in perforated plate using the mandrel in stretching testing machine is clipped in
Power be vertically applied to on circular test sample (" disk ") (that is, parallel to the normal vector in test sample plane；
Concentrated in the center in hole), loosen enough until bonding, thus 50% pressure drop is recorded.The pressure of instant effect before pressure drop
Power is maximum pressure PIt is maximum.The value corresponds to the release value [N/mm shown in table2].All measurements are in the room of controlled temperature
In 23 DEG C and 50% relative humidity under carry out.
It prepares to measure the sample of tensile shear strength
It is rushed from adhesive film KF-A-P1, KF-A-P2, KF-B-P1, KF-B-P2, KF-B-P3 and KF-B-P4 to be tested
The rectangle die cut part that size is 25.0mm × 12.5mm is extruded, each personal peeling paper of adhesive film is covered on both sides.So
The peeling paper is respectively removed since on the one side of each die cutting afterwards.
Die cutting KF-A-P1 and KF-A-P2 are each properly placed on size as 100.0mm × 25.0mm × 3.0mm
The first test sample (substrate) end.Die cutting KF-A-P1 and KF-A-P2 are each bonded to the test sample at this time.
The sample (being shown in Table lattice) of the first test sample including makrolon, glass and steel is prepared in this way.Then, will still protect
The peeling paper stayed on die cutting KF-A-P1 and KF-A-P2 removes.Thus provide at this time with KF-A-P1 or with KF-A-P2
First test sample.
Die cutting KF-B-P1, KF-B-P3 and KF-B-P4, which do not cover side and be individually placed upon, is bonded to the first test sample
Die cutting KF-A-P1 on, thus die cutting KF-B-P1, KF-B-P3 and KF-B-P4 is each bonded to die cutting KF-A-P1.
In the same manner, die cutting KF-B-P2 does not cover side and is individually placed upon the die cutting KF-A-P2 for being bonded to the first test sample
On, thus die cutting KF-B-P2 is each bonded to die cutting KF-A-P2.In KF-A-P1 and KF-B-P1 or KF-A-P1 and KF-
After B-P3, KF-A-P1 are contacted with KF-B-P4 and KF-A-P2 with KF-B-P2, must then be carried out in most one hours with
The bonding of second substrate.
For the preparation further bonded, die cutting KF-B-P1, KF-B-P2, KF-B-P3 and KF-B-P4 are still retained in
On last peeling liner be each removed, thus make die cutting KF-B-P1, KF-B-P2, KF-B-P3 and KF-B-P4 each sudden and violent
Dew.In modification is tested, the die cutting KF-A-P1 of no peeling liner is placed on again on exposed die cutting KF-B-P1, by
This obtains die cutting sequence KF-A-P1/KF-B-P1/KF-A-P1.Then again will at this time remaining peeling liner from die cutting KF-
It is removed on A-P1, thus make die cutting KF-A-P1 exposures and the first test sample/KF-A-P1/KF-B-P1/KF- can be generated
The bonding (being shown in Table lattice) of the second test samples of A-P1/.
Alternatively, for die cutting KF-B-P1 and KF-B-P2, also sample is prepared using component B1 and B2.For this purpose, match somebody with somebody
The first test sample of standby KF-A-P1 and outfit KF-A-P2 each by uniform and thin spray component B1, thus make component B1 equal
It is even to be distributed on the surface of KF-A-P1 or KF-A-P2, but do not cover surface.Alternatively, KF- is thinly brushed with component B2
A-P1 and KF-A-P2.After sprinkling or brushing, it must then be carried out in most one hours viscous with the second test sample
It closes.
Alternatively, for die cutting KF-A-P1 and KF-A-P2, also sample is prepared using liquid component A1, A-P1 and A-P2
Product.For this purpose, liquid component A1, A-P1 and A-P2 are each brushed of the size with 100.0mm × 25.0mm × 3.0mm
On the end of one test sample, so as to which at least area of 25.0mm × 12.5mm is covered by each component.Wait five minutes until
The evaporation of the solvent of component A-P1 and A-P2.Then component B1 by uniform and thin is sprayed on A1, A-P1 and A-P2, thus component
B1 is evenly distributed on the surface of A1, A-P1 and A-P2, but does not cover surface.
It substitutes as further, after the solvent evaporates thinly brushes component B-P1 on A-P1.Similarly, molten
Component B-P2 is thinly brushed on A-P2 after agent evaporation.Again, five minutes are waited until the solvent of component B-P1 and B-P2
Evaporation.After sprinkling or brushing, it must then be carried out in most one hours and the bonding of the second test sample.
As other replacements of die cutting KF-A-P1 and KF-A-P2, sample is prepared using adhesive KM-A-P1.Its quilt
The end of the first test sample with size 100.0mm × 25.0mm × 3.0mm is placed on, thus the adhesive is bonded to this
End and the covering at least area of 25.0mm × 12.5mm.The thickness of adhesive KM-A-P1 is about 0.5mm.Then by component
B1 is sprinkled upon on KM-A-P1 uniform and thinly, and component B1 is thus made to be evenly distributed on the surface of KM-A-P1, but does not cover table
Face.Alternatively, adhesive KM-B-P1 present in the layer of about 0.5mm thickness is placed on KM-A-P1 in this way,
So that two kinds of adhesive are bonded to each other.It must then be carried out in most one hours and the bonding of the second test sample.
For measuring the bonding of tensile shear strength
On the chemical reactivity adhesive system of the sample prepared as described in decline, the respective quilt of the second test sample
One end is concordantly placed, and thus obtains overlapping compound in each case as described in DIN EN 1465.Overlap length is respectively
12.5mm.Overlapping area is respectively 300mm2.It will be made of the test sample of the first test sample/reaction adhesive system/second
Overlapping compound be placed on desk.Each the weight of 2kg is placed in the second test sample.At room temperature, it is described multiple
Object is closed to be exposed under the permanent compression of the weight each self-sustaining a) 10 seconds and in the second test series for b) 60 seconds (added
Press the time).Then the weight is removed.Then each by the compound 23 DEG C and 50% relative humidity under store it is 24 small
When.During this period, occur in adhesive system the curing reaction progressively carried out and each adhesive system and each test sample it
Between generate the adhesion strength gradually enhanced.Therefore, bonding at any time gradually enhancing, due to pressure sensitive adhesion act on and substantially beyond
Green strength.Then tensile shear strength is measured.
Measure tensile shear strength
The tensile shear strength of measure overlapping bonding gives the information of the shear strength of the gluing product of two-sided gluing.Institute
Measure is stated to be carried out using cupping machine according to DIN EN 1465.Test speed is 10mm/ minutes.It is all measurement weather by
In the room of control in 23 DEG C and 50% relative humidity under implement.
As a result
Push out test
Glue failures of the A=between stamping parts and test sample.
Cohesion failures of the C=in stamping parts compound.
The material damage of MB=test samples.
N.b.=is undeterminate.
Tensile shear strength is tested
Glue failures of the A=between stamping parts and test sample.
Cohesion failures of the C=in stamping parts compound.
The material damage of MB=test samples.
N.b.=is undeterminate.
These are the results show that using reactive adhesive system according to the present invention, and two substrates (test sample) are in room
The intensity of the lower intensity for carrying out far being more than typical pressure-sensitive adhesive after of short duration pressing time of temperature bonds.
Reactive adhesive system according to the present invention allow improve bonding and simultaneously improvement workability.It need not
Two components are mixed before the adhesive is set.
Claims (30)
1. reactive adhesive system, including
(i) the first adhesive components A of at least one, including at least one reactive monomer or reaction resin (a) and freely
Base initiator (c)；With
(ii) the second adhesive components B of at least one, including at least one reactive monomer or reaction resin (a) and activation
Agent (b) or including activator (b),
Wherein activator (b) includes each having selected from manganese (II) complex compound, iron (II) network of following compound as ligand
Close object or cobalt (II) complex compound：The derivative of one of porphyrin, porphyrazine or phthalocyanine or these compounds,
Wherein the first adhesive components A and/or the second adhesive components B further comprise polymer film-forming agent matrix (d),
And wherein the first adhesive components A and the second adhesive components B exist with form membrane.
2. reactive adhesive system as described in claim 1, wherein activator (b) include manganese (II) phthalocyanine, iron (II) phthalein
Cyanines or cobalt (II) phthalocyanine.
3. reactive adhesive system as claimed in claim 1 or 2, including other backing, peeling paper and/or peeling liner.
4. reactive adhesive system, including two or more first adhesive as described in one of claim 1-3
Component A or the second adhesive components B and optionally other backing, peeling paper and/or peeling liner,
Two of which or more the first adhesive components A or the second adhesive components B each alternately exist.
5. the reactive adhesive system as described in claim 1,2 or 4, wherein
(A) the first adhesive components A includes
(i) radical initiator (c) of at least one reactive monomer (a) of 20-80 weight % and 2-30 weight %；Or
(ii) the polymer film-forming agent matrix (d) of 20-80 weight %, 20-80 weight % at least one reactive monomer (a) and
The radical initiator (c) of 2-30 weight %；And
(B) the second adhesive components B includes
(i) activator (b) of 0.1-5 weight %；Or
(ii) activator (b) of at least one reactive monomer (a) of 20-80 weight % and 0.1-5 weight %；Or
(iii) the polymer film-forming agent matrix (d) of 20-80 weight %, at least one reactive monomer (a) of 20-80 weight %
With the activator (b) of 0.1-5 weight %.
6. reactive adhesive system as claimed in claim 5, wherein
At least one reactive monomer (a) of first adhesive components A including (i) 40-60 weight % and 8-15 weight % from
It is reacted by the polymer film-forming agent matrix (d) of base initiator (c) or (ii) 30-50 weight %, at least one of 40-60 weight %
Property monomer (a) and 8-15 weight % radical initiator (c).
7. reactive adhesive system as claimed in claim 5, wherein
Second adhesive components B includes the activator (b) of (i) 0.5-2 weight %；Or at least one of (ii) 40-60 weight %
The activator (b) of reactive monomer (a) and 0.5-2 weight %；Or the polymer film-forming agent matrix of (iii) 30-50 weight %
(d), the activator (b) of at least one reactive monomer (a) of 40-60 weight % and 0.5-2 weight %.
8. the reactive adhesive system as described in claim 1,2 or 4, wherein, if it is present
(i) reactive monomer (a) includes at least one representative chosen from the followings：Acrylic acid, acrylate, methacrylic acid, first
Base acrylate, diacrylate, dimethylacrylate, triacrylate, trimethyl acrylic ester, the third of higher functionality
Olefin(e) acid ester, the methacrylate of higher functionality, vinyl compound and/or the oligomeric or polymerization chemical combination with carbon-carbon double bond
Object；And/or
(ii) radical initiator (c) includes peroxide；And/or
(iii) polymer film-forming agent matrix (d) includes thermoplastic polymer, elastomer and/or thermoplastic elastomer (TPE).
9. reactive adhesive system as claimed in claim 8, wherein
Reactive monomer (a) includes at least one representative chosen from the followings：Methyl methacrylate, methacrylic acid, methyl-prop
Olefin(e) acid cyclohexyl ester, methacrylic acid tetrahydro furfuryl ester, methacrylic acid 2- phenoxyethyl acrylates, two (ethylene glycol) methyl ether first
Base acrylate, methacrylic acid 2- hydroxyethyls ester, methacrylic acid 2- hydroxy-propyl esters, methacrylic acid 4- hydroxybutyls
Ester and/or ethylene glycol dimethacrylate.
10. reactive adhesive system as claimed in claim 8, wherein
The peroxide is α,α dimethyl benzyl peroxide.
11. reactive adhesive system as claimed in claim 8, wherein
The thermoplastic polymer is thermoplastic polyurethane.
12. reactive adhesive system as claimed in claim 8, wherein
The peroxide is diisopropyl phenyl hydroperoxides, to terpane hydroperoxides and 1,1,3,3- tetramethyl fourths
Base hydroperoxides.
13. reactive adhesive system as claimed in claim 8, wherein
The thermoplastic polymer is hemicrystalline thermoplastic polymer.
14. reactive adhesive system as claimed in claim 8, wherein
The softening temperature of the thermoplastic polymer is less than 100 DEG C.
15. reactive adhesive system as claimed in claim 13, wherein
The glass transition temperature of the hemicrystalline thermoplastic polymer is no more than 25 DEG C.
16. reactive adhesive system as claimed in claim 13, wherein
The glass transition temperature of the hemicrystalline thermoplastic polymer is no more than 0 DEG C.
17. reactive adhesive system as claimed in claim 11, wherein
The softening temperature of the thermoplastic polyurethane is less than 80 DEG C.
18. the reactive adhesive system as described in claim 1,2 or 4, wherein
At least one first adhesive components A includes the mixture of following component：Thermoplastic polyurethane, methacrylic acid 2- benzene oxygen
Base ethyl ester, methacrylic acid 2- hydroxyethyls ester, methacrylic acid 2- hydroxy-propyl esters, ethylene glycol dimethacrylate and
Cumene hydroperoxide.
19. the reactive adhesive system as described in claim 1,2 or 4, wherein
At least one first adhesive components A includes the mixture of following component：Thermoplastic polyurethane, methacrylic acid 2- benzene oxygen
Base ethyl ester, methacrylic acid 2- hydroxyethyls ester, ethylene glycol dimethacrylate and cumene hydroperoxide.
20. the reactive adhesive system as described in claim 1,2 or 4, wherein
At least one first adhesive components A includes the mixture of following component：Phenoxyethyl methacrylate and hydrogen mistake
Cumene oxidation.
21. the reactive adhesive system as described in claim 1,2 or 4, wherein
At least one second adhesive components B includes the mixture of following component：Thermoplastic polyurethane, methacrylic acid 2- benzene oxygen
Base ethyl ester, methacrylic acid 2- hydroxyethyls ester, methacrylic acid 2- hydroxy-propyl esters, ethylene glycol dimethacrylate and
Iron (II) phthalocyanine.
22. the reactive adhesive system as described in claim 1,2 or 4, wherein
At least one second adhesive components B includes the mixture of following component：Thermoplastic polyurethane, methacrylic acid 2- benzene oxygen
Base ethyl ester, methacrylic acid 2- hydroxyethyls ester, ethylene glycol dimethacrylate and iron (II) phthalocyanine.
23. reactive adhesive system as claimed in claim 1 or 2, wherein
Reactive adhesive the component A and/or B of form membrane have 20-200 μm of layer thickness.
24. reactive adhesive system as claimed in claim 1 or 2, wherein
Reactive adhesive the component A and/or B of form membrane have 40-60 μm of layer thickness.
25. reactive adhesive system as claimed in claim 1 or 2, wherein
Reactive adhesive the component A and/or B of form membrane have 50 μm of layer thickness.
26. the reactive adhesive system as described in claim 1,2 or 4, wherein
Reactive adhesive component A and B have pressure-sensitive adhesive property.
27. reactive adhesive system as described in one of claim 1-26 for be bonded include metal, timber, glass and/
Or the purposes of the material of plastics.
28. for manufacturing the method for the reactive adhesive system as described in one of claim 1-26, wherein this method includes
The following steps：
1. by ingredient dissolving and/or Fine distribution in one or more solvents and/or water；
2. mixed dissolution or Fine distribution ingredient；
3. it is coated with peeling liner or peeling paper, back lining materials or pressure-sensitive with the mixture of the dissolving according to step 2 or the ingredient of distribution
Adhesive；
4. the evaporation solvent and/or water；With
5. optionally the reactive adhesive component is wound into a roll；
Wherein described ingredient includes
(A) at least one reactive monomer (a), radical initiator (b) and polymer film-forming agent matrix (d)；Or
(B) at least one reactive monomer (a), activator (b) and polymer film-forming agent matrix (d)；
And optionally other additive and/or auxiliary substance.
29. method as claimed in claim 28, wherein the solvent is acetone.
30. utilize the complex of the reactive adhesive system bonding as described in one of claim 1-26.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102013222278.5 | 2013-11-01 | ||
| DE201310222278 DE102013222278A1 (en) | 2013-11-01 | 2013-11-01 | Reactive 2-component adhesive system |
| PCT/EP2014/071172 WO2015062809A1 (en) | 2013-11-01 | 2014-10-02 | Reactive 2-component adhesive system |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105705601A CN105705601A (en) | 2016-06-22 |
| CN105705601B true CN105705601B (en) | 2018-06-01 |
Family
ID=
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4898899A (en) * | 1987-12-25 | 1990-02-06 | Toagosei Chemical Industry Co. | Adhesive composition |
| JPH02263880A (en) * | 1989-04-04 | 1990-10-26 | Daiabondo Kogyo Kk | Adhesive composition |
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4898899A (en) * | 1987-12-25 | 1990-02-06 | Toagosei Chemical Industry Co. | Adhesive composition |
| JPH02263880A (en) * | 1989-04-04 | 1990-10-26 | Daiabondo Kogyo Kk | Adhesive composition |
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