阅读说明：本技术 粘合剂组合物 (Adhesive composition ) 是由 L·赫尔伯特 A·D·梅萨纳 K·J·韦尔奇 于 2018-04-21 设计创作，主要内容包括：本发明提供快速固定两部分粘合剂组合物,所述两部分粘合剂组合物包括第一部分和第二部分,所述第一部分含有(甲基)丙烯酸组分和用于所述第二部分的环氧树脂组分的固化体系,所述第二部分含有环氧树脂组分和用于所述第一部分的(甲基)丙烯酸组分的固化促进剂。(The present invention provides quickly fixed two-part adhesive composition, the two-part adhesive composition includes first part and second part, the curing system of (methyl) acrylate component and the epoxy resin ingredient for the second part is contained in the first part, and the second part contains the curing accelerator of epoxy resin ingredient and (methyl) acrylate component for the first part.)

1. adhesive composition, it includes:

(a) part A, it includes:

(i) (methyl) acrylate component；

(ii) in structureAInterior curing accelerator,

Wherein X is C_1-20Alkyl, C_2-20Alkenyl or C_7-20Alkaryl is selected from-OH ,-NH by one or more₂Or the group official of-SH Energyization or X and Y are formed together the carbocyclic ring with 5-7 annular atom；Z is O, S or NX', and wherein X' is H, C_1-20Alkyl, C_2-20 Alkenyl or C_7-20Alkaryl can select for any one of three kinds thereafter by one or more hetero atom intervals or by one or more From-OH ,-NH₂Or the group functionalization of-SH；R is optionally present, but can be occurred on aromatic ring when it is present at most 3 times, and work as In the presence of be C_1-20Alkyl, C_2-20Alkenyl or C_7-20Alkaryl, thereafter any one of three kinds can be by between one or more hetero atoms Every or by one or more selected from-OH ,-NH₂Or the group functionalization of-SH；And n is 0 or 1；And z is 1-3；

(iii) thermoplastic elastomer (TPE)；With

(iv) reactive acid/ester component；And

(b) part B, it includes:

(i) epoxy resin ingredient；

(ii) oxidant；

(iii) plasticizer；With

(v) block copolymer being optionally present.

2. (methyl) acrylate component of composition according to claim 1, part of A is selected from: (methyl) acrylic acid Methyl esters, (methyl) acrylic acid, (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) isopropyl acrylate, (first Base) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) acrylic acid n-pentyl ester, (first Base) the just own ester of acrylic acid, (methyl) cyclohexyl acrylate, the positive heptyl ester of (methyl) acrylic acid, (methyl) n-octyl, (first Base) 2-EHA, (methyl) nonyl acrylate, (methyl) decyl acrylate, (methyl) lauryl ester, (methyl) phenyl acrylate, methyl methacrylate phenyl ester, (methyl) benzyl acrylate, (methyl) acrylic acid 2- methoxyl group second Ester, (methyl) acrylic acid 3- methoxybutyl, (methyl) acrylic acid 2- hydroxy methacrylate, (methyl) acrylic acid 2- hydroxy propyl ester, (first Base) octadecyl acrylate, (methyl) glycidyl acrylate, (methyl) acrylic acid 2- ammonia ethyl ester, γ-(methyl) propylene Acryloxypropylethoxysilane trimethoxy silane, (methyl) acrylic acid-ethylene oxide adduct, (methyl) acrylic acid trifluoromethyl methyl esters, (methyl) acrylic acid 2- trifluoromethyl ethyl ester, (methyl) acrylic acid 2- perfluoro-ethyl ethyl ester, (methyl) acrylic acid 2- perfluoro-ethyl- 2- perfluoro butyl ethyl ester, (methyl) acrylic acid 2- perfluor ethyl ester, (methyl) perfluoroethyl methyl esters, two perfluor of (methyl) acrylic acid Methyl formate, (methyl) acrylic acid 2- perfluoro-methyl -2- perfluoro-ethyl methyl esters, (methyl) acrylic acid 2- perfluoro hexyl ethyl ester, (first Base) acrylic acid 2- perfluoro decyl ethyl ester, (methyl) acrylic acid 2- perfluor cetyl ethyl ester, ethoxylated trimethylolpropane three Acrylate, trimethylol-propane trimethacrylate, dipentaerythritol monohydroxypentaacryande, three propylene of pentaerythrite Acid esters, ethoxylated trimethylolpropane triacrylate, 1,6 hexanediol diacrylate, neopentylglycol diacrylate, Pentaerythritol tetraacrylate, 1,2- butanediol diacrylate, ethoxylated trimethylolpropane three (methyl) acrylate, Propoxylated glycerol three (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, dipentaerythritol monohydroxy five (methyl) acrylate, three (propylene glycol) two (methyl) acrylate, ethoxylated neopentylglycol two (methyl) acrylate, 1, 4- butanediol two (methyl) acrylate, polyethylene glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, fourth Glycol two (methyl) acrylate, (methyl) acrylate of Ethoxylated bisphenol A bis- and their combination.

3. composition according to claim 1, wherein the curing accelerator is selected from

4. composition according to claim 1, wherein the reactivity acid/ester component is (methyl) acrylic acid or (methyl) Acrylic acid derivative, sulfonic acid or sulfonic acid, phosphoric acid, phosphoric acid derivatives and phosphate.

5. composition according to claim 1, wherein the reactivity acid/ester component is phosphate, the phosphate packet Compound containing following formula:

Wherein R¹For H or CH₃, and R²For H or:

6. composition according to claim 1, wherein the reactivity acid/ester component is hydroxyethyl methacrylate phosphoric acid Ester.

7. composition according to claim 1, wherein free radical inhibitors are selected from: quinone, quinhydrones, azanol, nitroxyl chemical combination Object, phenol, amine, amine, quinoline, phenthazine and their combination.

8. composition according to claim 1, wherein free radical inhibitors are selected from: quinhydrones, tert-butyl hydroquinone, phenthazine, Methylnaphthohydroquinone, ethoxy quinhydrones, the alkyl-substituted p-phenylenediamine of N- and their combination.

9. the epoxy resin ingredient of composition according to claim 1, part of B is selected from: cycloaliphatic epoxy resin, ring Oxygen novolac resin, bisphenol A epoxide resin, bisphenol F epoxy resin, the epoxy resin based on bisphenol A/epichlorohydrin, alkyl Epoxides, limonene dioxide, polyfunctional epoxy resin and their combination.

10. composition according to claim 1, the epoxy resin ingredient of part of B is bisphenol A/epichlorohydrin epoxy Resin.

11. composition according to claim 1, the oxidant of part of B is benzoyl peroxide.

12. the method that first surface is bonded to second surface, this method comprises:

Two parts composition according to claim 1 is applied in first surface and second surface to be bonded at least One；

Under conditions of being conducive to solidify two parts composition, the first surface and the second surface are cooperated, and Adhesives are formed between the surface of cooperation.

13. composition according to claim 1, wherein when being mixed part A with part B and being applied at least one substrate When, the composition has at most 5 minutes open hour.

14. composition according to claim 1, wherein the composition is less than 60 DEG C when cooperating the substrate At a temperature of set time of the display less than 90 seconds.

Technical field

The present invention provides two-part adhesive composition comprising first part and second part, the first part contain There is the curing system of (methyl) acrylate component and the epoxy resin ingredient for second part, the second part contains epoxy The curing accelerator of resin Composition and (methyl) acrylate component for first part.Curing accelerator is in structureAIt is interior

Wherein X is H, C_1-20Alkyl, C_2-20Alkenyl or C_7-20Alkaryl, thereafter any one of three kinds can be by one or more A hetero atom interval is selected from-OH ,-NH by one or more₂Or the group functionalization in-SH, Y C_1-20Alkyl, C_2-20Alkenyl Or C_7-20Alkaryl, thereafter any one of three kinds can by one or more hetero atom intervals or by one or more selected from- OH、-NH₂Or-SH group functionalization or X and Y be formed together the carbocyclic ring with 5-7 annular atom；Z be O, S or NX', Middle X' is H, C_1-20Alkyl, C_2-20Alkenyl or C_7-20Alkaryl, thereafter any one of three kinds can be by between one or more hetero atoms Every or by one or more selected from-OH ,-NH₂Or the group functionalization of-SH；R is optionally present, but when it is present can be in aromatic ring It is upper to occur at most 3 times, and be when it is present C_1-20Alkyl, C_2-20Alkenyl or C_7-20Alkaryl, thereafter any one of three kinds can be by One or more hetero atom intervals are selected from-OH ,-NH by one or more₂Or the group functionalization of-SH；And n is 0 or 1；And z For 1-3, condition is when X is H, and z is not 2 and preferably 1.

Background technique

Acrylic pressure-sensitive adhesive compositions are well-known.See, for example, U.S. Patent No. 4,536,546 (Briggs).Although the adhesive based on this technology is by Illinois Tool WorksInc., Chicago, IL is with trade name PLEXUS MA300 and 310 is sold, but unpleasant stink can be presented for it and its processing is toxic, these are all using the aobvious of its purposes Write defect.

Two parts composition epoxy resin is also known, wherein one of described part includes acrylic adhesives. Such as the adhesive composition that U.S. Patent No. 4,426,243 (Briggs) description is prepared by two kinds of different adhesive materials, One kind is epoxy resin and another kind is acrylate adhesive, and the material is incorporated in one by difunctionality component chemical It rises, a functional group of the difunctionality component is epoxy resin and another functional group is acrylate.It is special referring also to Britain Benefit the GB2166447Bth.

No. 2010/0065210 offer anti-sag composition (sag-resistant of U.S. Patent Application Publication No. Composition) comprising: (a) first part comprising: (i) (methyl) acrylate component, (ii) amine catalyst, (iii) The second catalyst being optionally present, (iv) reactivity acid constituents and (v) free radical inhibitors；And (b) second part, packet Include: (i) includes the resin Composition of epoxy group, (ii) peroxide；And (iii) metallic compound, the metallic compound and strong Acid constituents it is compound and substantially not with peroxide reactions.First part and second part there is sufficiently low viscosity be easy to by Pumping equipment distribution.To form this adhesive, first part and second part are mixed, after mixing at once, mixture has Viscosity higher, so that adhesive will not flow after applying it to surface within the open hour (open time) of the mixture It hangs, drip or migrates, and mixed first part and second part solidification.Term " open hour " refers to the mixture of adhesive Pass through the time between solidification.

U.S. Patent Application Publication No. 2014/0235758 provides a kind of adhesive composition, it includes:

(a) first part, which includes:

(i) (methyl) acrylic component, being at least partly somebody's turn to do (methyl) acrylic component includes that (methyl) acrylic acid is different Norbornene ester；

(ii) amine catalyst；

It (iii) is at room temperature the polybutadiene of the ethenyl blocking of liquid form；

(iv) reactive acid constituents；

(v) solid (methyl) acrylic acid zinc salt；

(vi) zinc and/or bismuth complex；With

(vii) free radical inhibitors；With

(b) second part, which includes:

(i) comprising the resin Composition of epoxy group；

(ii) benzoyl peroxide；

(iii) plasticizer；With

(vi) block copolymer being optionally present,

Wherein, when being mixed the first part and second part and being applied at least one substrate, the composition With at most 5 minutes open hour, and when cooperating the substrate, shows be less than at temperatures below 120 °C 90 seconds set times (fixture time), the component cooperated at this time can support 3kg load.

In the situation of anaerobic adhesive compositions, U.S. Patent No. 8,481,659 are provided with the solidification in flowering structure Promotor:

Wherein X is C_1-20Alkyl, C_2-20Alkenyl or C_7-20Alkaryl, thereafter any one of three kinds can be by one or more Hetero atom interval is selected from-OH ,-NH by one or more₂Or the group functionalization of-SH, Y C_1-20Alkyl, C_2-20Alkenyl or C_7-20Alkaryl, thereafter any one of three kinds can by one or more hetero atom intervals or by one or more selected from-OH ,- NH₂Or-SH group functionalization or X and Y be formed together the carbocyclic ring with 5-7 annular atom；Z is O, S or NX', wherein X' For H, C_1-20Alkyl, C_2-20Alkenyl or C_7-20Alkaryl, thereafter any one of three kinds can by one or more hetero atom intervals or - OH ,-NH are selected from by one or more₂Or the group functionalization of-SH；R is optionally present, but can be gone out on aromatic ring when it is present Now at most 3 times, and be when it is present C_1-20Alkyl, C_2-20Alkenyl or C_7-20Alkaryl, thereafter any one of three kinds can be by one Multiple hetero atom intervals or by one or more be selected from-OH ,-NH₂Or the group functionalization of-SH；And n is 0 or 1；And z is 1- 3, condition is when X is H, and z is not 2 and preferably 1.

Nevertheless, it is desirable to provide alternative ingredient in the situation of two-part adhesive composition, it is described Alternative ingredient can help to performance, compared with existing two-part adhesive composition, even if the performance be not it is more excellent, also extremely It is few quite, and as such existing composition, have advantageous, at least comparable or not tightened up supervision label is wanted It asks.

Summary of the invention

The present invention provides a kind of adhesive composition, it includes:

(a) first part, it includes:

(i) (methyl) acrylate component；

(ii) in structureAInterior curing accelerator,

Wherein X is C_1-20Alkyl, C_2-20Alkenyl or C_7-20Alkaryl is selected from-OH ,-NH by one or more₂Or the base of-SH Group's functionalization；Y is C_1-20Alkyl, C_2-20Alkenyl or C_7-20Alkaryl, thereafter any one of three kinds can be by one or more miscellaneous originals Son interval is selected from-OH ,-NH by one or more₂Or-SH group functionalization or X and Y be formed together with 5-7 ring The carbocyclic ring of atom；Z is O, S or NX', and wherein X' is H, C_1-20Alkyl, C_2-20Alkenyl or C_7-20Alkaryl, thereafter appointing in three kinds One kind can be selected from-OH ,-NH by one or more hetero atom intervals or by one or more₂Or the group functionalization of-SH；R is optional In the presence of, but can occur on aromatic ring when it is present at most 3 times, and be when it is present C_1-20Alkyl, C_2-20Alkenyl or C_7-20Alkane virtue Base can be selected from-OH ,-NH by one or more hetero atom intervals or by one or more for any one of three kinds thereafter₂Or-SH Group functionalization；And n is 0 or 1；And z is 1-3；

(iii) thermoplastic elastomer (TPE)；With

(iv) reactive acid constituents；With

(b) second part, it includes:

(i) epoxy resin ingredient；

(ii) benzoyl peroxide；

(iii) plasticizer；With

(iv) block copolymer being optionally present.

When mixing the first part and second part and being applied at least one substrate, the composition has extremely More 5 minutes open hour, and when by the substrate cooperate when, lower than 60 DEG C at a temperature of show consolidating less than 90 seconds It fixes time.

In another aspect, the present invention, which provides, a kind of bonds two tables using two-part adhesive composition of the invention The method in face.

Detailed description of the invention

Fig. 1 describes the bar chart of intersection bonding (cross bond) intensity of measurement Kalix substrate.

Fig. 2 describes the bar chart of adhesion strength of the measurement steel substrate under stretch mode.

Fig. 3 describes the bar chart of adhesion strength of the measurement stainless steel substrate under stretch mode.

Fig. 4 describes the bar chart of adhesion strength of the measurement aluminum substrate under stretch mode.

Fig. 5 describes the bar chart of adhesion strength of the measurement Kalix substrate under stretch mode.

Fig. 6 describes the bar chart of adhesion strength of the measurement steel substrate under tensile peel mode.

Fig. 7 describes the bar chart of adhesion strength of the measurement steel substrate under wedge impact mode.

Detailed description of the invention

Two-part adhesive composition of the invention is suitable for a variety of applications, one of them is for hand-held display group Laminated metallic and/or polymeric material in part.

Therefore, the present invention provides a kind of two-part adhesive composition comprising first part and second part, described The curing system of epoxy resin ingredient of a part containing acrylate component and for second part, the second part contain ring The curing system of oxygen resin Composition and the acrylate component for first part.The combination of part A and part B generate composition, The composition solidifies and forms the material for being suitable for manufacturing laminate (laminates).Therefore, the combination of part A and part B can It is applied to surface to be laminated, and the surface can cooperate with second surface to form laminate.After solidification, the composition exists Adhesives are formed between two surfaces.

Part A

(methyl) acrylate component

Any suitable material containing at least one group with following formula can be used:

Wherein R is selected from H, halogen or C₁To C₁₀Alkyl.

Advantageously, the group is (methyl) acryloxy.Term " (methyl) acryloxy " is for referring to propylene Both acid esters and methacrylate, wherein R is respectively H or methyl.The available quantity of (methyl) acrylate component typically ranges between About 20 weight % of total composition are between about 80 weight %.It is desirable that composition of the invention contains about 50 weight % to about (methyl) acrylate component of 70 weight %.

(methyl) acrylate component can exist in the form of polymer, monomer or combinations thereof.In the presence of with polymer form, (methyl) acrylate component can be the polymer chain of at least one above-mentioned group of attachment.The group can be located at main chain side chain or End position or combinations thereof.Advantageously, at least two such groups may be present, and can be located at end position.(methyl) propylene Acid constituents can have by polyethylene, polyethers, polyester, polyurethane, polyamide, epoxy resin, vinyl esters, phenol, amino resins, base It is (methyl) acrylate-functional groups on the polymer chain, such as this field skill in the polymer chain of the compositions such as the resin of oil Known to art personnel.Polymer chain can have random, block or grafting construction.

The polymer chain can be formed by the polymerization of vinyl monomer.The illustrative example of such vinyl monomer is (first Base) methyl acrylate, (methyl) acrylic acid, (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) acrylic acid is different Propyl ester, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) acrylic acid are just Pentyl ester, (methyl) the just own ester of acrylic acid, (methyl) cyclohexyl acrylate, the positive heptyl ester of (methyl) acrylic acid, (methyl) acrylic acid are just Monooctyl ester, (methyl) 2-EHA, (methyl) nonyl acrylate, (methyl) decyl acrylate, (methyl) acrylic acid ten Dialkyl, (methyl) phenyl acrylate, methyl methacrylate phenyl ester, (methyl) benzyl acrylate, (methyl) acrylic acid 2- first Oxygroup ethyl ester, (methyl) acrylic acid 3- methoxybutyl, (methyl) acrylic acid 2- hydroxy methacrylate, (methyl) acrylic acid 2- hydroxyl third Ester, (methyl) octadecyl acrylate, (methyl) glycidyl acrylate, (methyl) acrylic acid 2- ammonia ethyl ester, γ-(first Base) acryloyloxypropyltrimethoxysilane (γ-(meth) acryloyloxypropyltrimethoxysilane), (first Base) acrylic acid-ethylene oxide adduct, (methyl) acrylic acid trifluoromethyl methyl esters (trifluoromethylmethyl (meth) Acrylate), (methyl) acrylic acid 2- trifluoromethyl ethyl ester (2-trifluoromethylethyl (meth) acrylate), (methyl) acrylic acid 2- perfluoro-ethyl ethyl ester (2-perfluoroethylethyl (meth) acrylate), (methyl) acrylic acid 2- perfluoro-ethyl -2- perfluoro butyl ethyl ester, (methyl) acrylic acid 2- perfluor ethyl ester, (methyl) perfluoroethyl methyl esters, (methyl) Two perfluoro-methyl methyl esters of acrylic acid, (methyl) acrylic acid 2- perfluoro-methyl -2- perfluoro-ethyl methyl esters, (methyl) acrylic acid 2- perfluor Hexyl ethyl ester (2-perfluorohexylethyl (meth) acrylate), (methyl) acrylic acid 2- perfluoro decyl ethyl ester (2- Perfluorodecylethyl (meth) acrylate), (methyl) acrylic acid 2- perfluor cetyl ethyl ester (2- Perfluorohexadecylethyl (meth) acrylate), ethoxylated trimethylolpropane triacrylate (ethoxylated trimethylolpropane triacrylate), trimethylol-propane trimethacrylate, two seasons Penta tetrol monohydroxypentaacrylate (dipentaerythritol monohydroxypentaacrylate), pentaerythrite three Acrylate, ethoxylated trimethylolpropane triacrylate, 1,6 hexanediol diacrylate (1,6- Hexanedioldiacrylate), neopentylglycol diacrylate (neopentyl glycoldiacrylate), pentaerythrite Tetraacrylate, 1,2- butanediol diacrylate (1,2-butylene glycoldiacrylate), three hydroxyl first of ethoxylation Base propane three (methyl) acrylate, propoxylated glycerol three (methyl) acrylate (glyceryl propoxylate tri (meth) acrylate), trimethylolpropane tris (methyl) acrylate, dipentaerythritol monohydroxy five (methyl) acrylate (dipentaerythritol monohydroxy penta (meth) acrylate), three (propylene glycol) two (methyl) acrylic acid Ester, ethoxylated neopentylglycol two (methyl) acrylate, 1,4- butanediol two (methyl) acrylate, two (first of polyethylene glycol Base) acrylate, triethylene glycol two (methyl) acrylate, butanediol two (methyl) acrylate, Ethoxylated bisphenol A bis- (methyl) acrylate.These monomers can indirectly using or it is a variety of be used together, according to circumstances, polymerizable or combined polymerization.

Especially desirable vinyl monomer is (methyl) acrylate monomer, and the alcohol part including wherein ester group contains 1-8 Those of a carbon atom monomer.For example, example is 2-Ethylhexyl Methacrylate, hydroxyethyl methacrylate, methyl Cyclohexyl acrylate, ethyl methacrylate, 1,3 butylene glycol dimethylacrylate (" BDMA "), butyl methacrylate and Methyl methacrylate (" MMA ").

Curing accelerator

The present composition includes curing accelerator, the curing accelerator can about 0.01 weight % to about 5 weight %, reason Think about 0.05 weight % to about 2 weight %, and more desirably about 0.3 weight % to about 0.7 weight % amount exist.

In the present case, curing accelerator can be in any number of forms, such as structureAInterior adduct.These add Closing object can be prepared as follows:

Or

THQ-D (or THQ- glycol) and Ind-D (or Ind- glycol) is isomer mixture, is expressed as follows:

Respectively

StructureAThe curing accelerator covered can be prepared by reactant, and the reactant includes: (a) at least one compound, It selects free structureIThe compound of expression:

Wherein R, Y, Z, n and z are as hereinbefore defined, such as

Wherein R and z are as hereinbefore defined, and (b) at least one compound, select free structureIIThe compound of expression:

Wherein Z " is selected from-O- ,-S- or-NH-；Q is 1-2；R⁶Independently selected from hydroxy alkyl, aminoalkyl or thio alkane Base；And n is at least 1, wherein reaction product includes independently selected from-OH ,-NH₂Or at least two side chain functionalities of-SH.

In addition, as needed, structureIOrIAInterior compound may include

Structure aboveIICompound in, Z " ideally be selected from-O- ,-S- or-NH-；Q can be 1 to 4；R⁶It can be independently Selected from hydroxy alkyl, aminoalkyl or alkylthio；And n is at least 1.It is desirable that by structureIIThe reactant of expression is to shrink Glycerol, as follows:

As described above, reaction product includes independently selected from-OH ,-NH₂Or at least two side chain functionalities of-SH.Reaction Product includes two or three side chain functionalities, such as hydroxy functional group.

It is desirable that structureICompound be based on THQ, indoline or indoles.Therefore, work as structureACompound be based on THQ, When indoline or indoles, it is THQ, the functionalised alkyl of indoline or indoles, is functionalized alkenyl or functionalization alkaryl adduction Object.

Thermoplastic elastomer (TPE)

Thermoplastic elastomer (TPE) should exist at most about 20 weight %, the amount of for example, about 5 weight % to about 15 weight %.

The polybutadiene of ethenyl blocking should be in liquid form at room temperature.The polybutadiene of ethenyl blocking should have low In 0 DEG C of glass transition temperature.Ethenyl blocking can be in (methyl) acrylate ended form, such as (methyl) acrylate The polybutadiene-acrylonitrile copolymer of sealing end, such as HYCAR VTBN, or the polybutadiene of (methyl) acrylate ended, example Such as HYCAR VTB, each from BF Goodrich.The polybutadiene of ethenyl blocking should be at most about 20 weight %, for example, about The amount of 5 weight % to about 15 weight % exists.

Reactive acid/ester component

The present composition includes acid or acid esters.Suitable acid or acid esters includes (methyl) acrylic acid or derivative, phosphoric acid Or derivative, phosphate and sulfonic acid or derivative.

Reactive acid constituents is selected from free radical polymerizable acid monomer, such as olefinic unsaturated monocarboxylic or polycarboxylic acid, Malaysia Acid and crotonic acid.Ideal reactivity acid constituents includes methacrylic acid (" MAA ") and acrylic acid.Reactive acid constituents is also adjusted And slow down the curing time of thermoset composition.The epoxy resin in curing accelerator cured portion B in the A of part, but it is not solid Change reactive ester component, curing accelerator solidification process is generally too quick for very big part or laminate, it is extremely difficult to Manufacture laminate.In addition, excessively rapid curing can cause trouble during curing, such as the excessive heat from heat release curing reaction Amount, and obtains inconsistent or uneven curing, and products therefrom can have undesirable physical characteristic, for example, be bubbled, brittleness or It is smaller than with achievable tensile strength when the solidification of higher measurement rate.Suitable phosphate includes that being expressed from the next It is a little:

Wherein R¹For H or CH₃, and R²For H or by the group of following representation:

Wherein R¹For H or CH₃.Particularly suitable phosphate is hydroxyethyl methacrylate (" HEMA ") phosphate, with quotient Name of an article T-MULZ 1228 or HARCRYL 1228 or 1228M is sold, and is respectively purchased from Harcross Chemicals, Kansas City,KS.It further include that at least one strong acid " reactive hydrogen " group or there is at least one phosphonic acids active hydrogen group (R¹R²POOH), such as the structure of hydroxy-ethyldiphosphonic acid, phosphonic acids and derivative, or there is phosphonic acid functional groups or similar acid strength The oligomeric or paradigmatic structure of functional group.

Reactive acid constituents exists with the about 0.25 weight % to about 15 weight % of composition.It is desirable that when reactivity acid When group is divided into phosphate, exist with about 1.0 to 4.0 weight % of composition.

Free radical inhibitors

In general, part A further includes radical polymerization inhibitor, the premature reaction before mixing with part B is prevented.

A variety of suitable radical polymerization inhibitors are known, and including quinone, quinhydrones, azanol, nitroxyl compound, Phenol, amine, arylamine, quinoline, phenthazine etc..Particularly suitable free radical inhibitors include quinhydrones, tert-butyl hydroquinone (" TBHQ "), (blend of the alkyl-substituted p-phenylenediamine of N-, comes from by methylnaphthohydroquinone, ethoxy quinhydrones, phenthazine and NAUGARD-R Addivant,Danbury,CT).One or more single free radical inhibitors components can also be combined.

Other additives

Part A contains other additive, such as filler, core-shell polymer, lubricant, thickener and colorant. Filler provides volume without sacrificing the intensity of adhesive and can be selected from high or low density fillers.In addition, certain fillers, such as dioxy SiClx can assign rheology modified or smaller particle reinforcer.Commercially available example includes Cab-O-Sil 610 and AEROSIL R8200。

Low density filler is especially envisaged that, because gained final product has the product than being free of filler in addition lower Density, but have and essentially identical strength characteristics when filler is not present.

Core-shell polymer is preferably the graft copolymer of " nucleocapsid " type, or can also be " no shell " cross-linked rubbery particle, Such as acrylonitrile-butadiene-styrene (ABS) (" ABS "), methacrylate-butadiene-styrene (" MBS ") and methacrylic acid Rouge-acrylonitrile-butadiene-styrene (ABS) (MABS).BLENDEX 338 is the ABS powder from GE Plastics.

Part B

Epoxy resin portion B includes epoxy resin ingredient.Epoxy resin may include that cycloaliphatic epoxy resin, epoxy novolac are clear Coating resins, bisphenol A epoxide resin, bisphenol F epoxy resin, the epoxy resin based on bisphenol A/epichlorohydrin, alkyl epoxy Object, limonene dioxide and polyepoxide.

Preferably epoxy resin ingredient is alicyclic, can be from Dow Chemical with trade name CYRACURE UVR-6110 It buys.UVR-6110 has a structure that

It is the liquid epoxies based on bis-phenol with another suitable epoxy resin in this article, such as can be from Dow Those of trade name " D.E.R. " that Chemical is bought.The example of such D.E.R. brand product includes D.E.R.332 (double The diglycidyl ether of phenol A)；D.E.R.330 (low viscosity, undiluted bisphenol a liquid epoxy resin)；D.E.R.383 is (low viscous Degree, undiluted bisphenol a liquid epoxy resin)；D.E.R.354 (standard, the liquid epoxies based on Bisphenol F)；D.E.R.351 (low viscosity, liquid bisphenol A/F resin blend)；D.E.R.352 (low viscosity, liquid bisphenol A/F resin blend)； D.E.R.324 (aliphatic glycidol ether reactive diluent, modified liquid epoxy resin)；D.E.R.323 (aliphatic glycidol Ether reactive diluent, modified liquid epoxy resin)；D.E.R.325 (aliphatic glycidol ether reactive diluent, modification liquid Body epoxy resin)；And D.E.R.353 (aliphatic glycidol ether reactive diluent, modified liquid epoxy resin).It is suitable for Different brands herein are sold based on the liquid epoxies of bis-phenol with trade name EPON, such as EPON Resin 828, Derived from bisphenol-A and epoxychloropropane, and it is purchased from Hexion Specialty Chemicals.

Another suitable epoxy resin ingredient is epoxy-Novolak resin.Epoxy-Novolak resin is epoxychloropropane With the product of phenol-formaldehyde novolaRs.It can much be bought from Dow Chemical with trade name D.E.N..Suitable D.E.N. The example of brand product includes D.E.N.431 (low viscosity semisolid epoxy-Novolak resin) and D.E.N.438 (semisolid ring Oxygen novolac resin).

Other suitable epoxy resin include can be at ambient temperature or at a high temperature of suitable by catalyst or hardening The cured polyepoxide of agent.The example of these polyepoxides includes poly epihydric alcohol and poly- (Beta-methyl glycidyl) Ether, can be by making per molecule contain the compound and appropriate epoxychloropropane of at least two free alcoholic hydroxy groups and/or phenolic hydroxyl group It reacts under alkaline condition, or optionally reacts there are acidic catalyst and then obtained with alkali process.These Ether can be made of acyclic alcohol, for example, ethylene glycol, diethylene glycol and advanced poly- (oxy ethylene) glycol, propane -1,2- glycol and Poly- (oxypropylene) glycol, propane -1,3- glycol, butane -1,4- glycol, poly- (oxygen tetramethylene) glycol, pentane -1,5- two Alcohol, hexane -2,4,6- triol, glycerol, 1,1,1- trimethylolpropane, pentaerythrite, sorbierite and poly- (epoxychloropropane)；By Alicyclic alcohol is made, such as resorcinol, quinite, bis- (4- hydroxy-cyclohexyl) methane, bis- (the 4- hydroxy cyclohexylphenyls of 2,2- Base) propane and bis- (hydroxymethyl)-hexamethylene -3- alkene of 1,1-；And it is made of the alcohol with aromatic kernel, such as N, bis- (the 2- hydroxyls of N- Base ethyl) aniline and bis- (2- Hydroxy-ethylamino) diphenyl methanes of p, p'-.Or it can be made of monokaryon phenol, such as isophthalic two Phenol and quinhydrones, and be made of multicore phenol, for example, bis- (4- hydroxyphenyl) methane, 4,4'- dihydroxy hexichol, bis- (4- hydroxyphenyl) sulfones, 1,1,2,2- tetra- bis- (4- hydroxy phenyl) ethane, 2,2 ,-bis- (4- hydroxyphenyl) propane (further referred to as bisphenol-A), the bis- (3,5- of 2,2- Two bromo- 4- hydroxyphenyls) propane and novolaks, the novolaks are by aldehyde (such as formaldehyde, acetaldehyde, chloral and furfural) and phenol (such as phenol itself) is formed, and phenol replaces in ring through chlorine atom or the alkyl respectively containing at most nine carbon atoms, such as 4- chlorophenol, 2- cresols and 4-TBP.

Poly- (N- glycidyl) compound (Poly (N-glycidyl) compounds) includes for example by by epoxy chlorine Reaction product dehydrochlorination those compounds obtained of propane and the amine containing at least two amino hydrogen atoms, the amine Such as aniline, n-butylamine, bis- (4- aminophenyl) methane and bis- (4- Methylaminophenyl) methane；Isocyanuric acid three-glycidyl Ester；With the N of cyclic alkylidene urea, N'- 2-glycidyl radical derivative, such as ethylidene-urea and 1, acyl in 3- propylidene urea and second Urea, such as 5,5- dimethyl hydantoin.

Epoxy resin derived from oil, such as epoxidised soybean oil, epoxidized castor oil etc. is also applied for herein.

Oxidant

As oxidant, peroxide and perester can be used.Benzoyl peroxide is desirable to select as portion itself Divide the oxidant in B.The commercially available composition containing benzoyl peroxide can also be used.One kind is considered containing 49-50% mistake The peroxide cream of Benzoyl Oxide, 210 Blue of Benox-50 (Syrgis Performance Initiators is come from, Inc., Helena, AR) it is an ideal chose.A kind of peroxide cream being considered containing 54-56% benzoyl peroxide, 108 White of Benox-55 is another ideal chose.Another ideal chose is from R.T.Vanderbilt, Norwalk, CT VaroxASNS, a kind of peroxide cream being considered containing 55% benzoyl peroxide.

Plasticizer

Plasticizer is in the part B in two-part adhesive composition.Plasticizer is equally useful in the A of part.Increase Modeling agent can be any liquid of the flexibility of the reaction module facilitated in composition or soluble compounds and/or can be used as group Close the transport carrier (carrier vehicle) of the other components in object.Example includes aromatic sulfonamides, aromatic phosphate acid ester, alkane Base phosphate, dialkylether aromatic esters, polymeric plasticiser, dialkyl ether diester, polyglycols diester, tricarboxylic ester, polyester resin, Aromatic diester, three ester of aromatics (trimellitate), aliphatic diester, epoxidised ester, chlorohydrocarbon, aromatic oil, alkylether monoesters, cycloalkanes Oil, alkyl monoester, paraffin oil, silicone oil, n-butyl phthalate, diisobutyl phthalate, phthalic acid two are just Own ester, heptyl phthalate ester, di-2-ethylhexyl phthalate, 7c9c- phthalic acid ester (straight chain and branch Change), diisooctyl phthalate, straight chain 6c, 8c, 10c phthalic acid ester, diisononyl phthalate, straight chain 8c- 10c phthalic acid ester, straight chain 7c-11c phthalic acid ester, diisooctyl phthalate, straight chain 9c-11c O-phthalic Acid esters, phthalic acid two (hendecane) ester, diisodecyl glutarate, two 2- ethylhexyl of adipic acid, two 2- ethyl of azelaic acid Own ester, two 2- ethylhexyl of decanedioic acid, n-butyl sebacate, diisodecyl adipate (DIDA), triethylene glycol decylate caprylate, three Ethylene glycol 2 ethyl hexanoic acid ester, two fourth 2-ethoxyethyl acetate of adipic acid, di butoxyethoxyethyl adipate, two fourth oxygen ethoxyethyl groups Formal, dibutoxyethoxy sebacate, tri trimellitate -2- ethylhexyl, three-(7c-9c (straight chains)) benzene three partially Acid esters, three-(8c-10c (straight chain)) trimellitates, triethyl phosphate, triisopropyl phenyl phosphate, tributyl phosphate, phosphoric acid 2- ethylhexyl diphenyl ester, trioctyl phosphate, isodecyl ester diphenyl ester, triphenyl phosphate, tri aromatic ester of phosphic acid synthetic, phosphoric acid Three butoxyethyls, tricresyl phosphate (- chloroethyl) ester, phosphoric acid butyl phenyl diphenyl ester, chlorination organophosphorus ester, tricresyl phosphate base two Phenyl ester, tricresyl phosphate (two chloropropyls) ester, p isopropylbenzoic acid base phenyl diphenyl ester, trixylyl phosphate (trixylenyl Phosphate), tricresyl phosphate and diphenyl phosphate monooctyl ester.

Block copolymer

When in use, block copolymer can be any block of physical property needed for the composition that can promote in research Copolymer.

Butadiene or isoprene and styrene (such as SBS, SIS, SEBS and SB) can be used in block copolymer rubber Block constitute, commercial examples be purchased from Shell Chemical Co. such as KRATON D-1116 and be purchased from Dexco other D grades of elastomers of KRATON, such as VECTOR 2411IP.

It can be used and dissolve in methacrylate/acrylic acid with the glass transition temperature (" Tg ") below about 25 DEG C Other elastomers in ester monomer replace polychlorobutadiene and/or block copolymer rubber.The example of such elastomer is epoxy The homopolymer of chloropropane and its copolymer with ethylene oxide, can buy, acrylate from Zeon Chemicals with HYDRIN Rubber granular material can be bought, polyisoprene rubber, polybutadiene rubber, nitrile rubber and SBR rubber from Zeon with HYTEMP (random copolymer of butadiene and styrene).

In addition, other block copolymers can be styrene maleic anhydride copolymer, it is expressed from the next:

It is 1 to 6 that wherein v, which is 1 to 12, w,；And n is 1 to 50.

Styrene maleic anhydride copolymer is well-known, and some of them are for example purchased from Sartomer Company, Inc., Exton, PA, trade name SMAEF80.Styrene maleic anhydride copolymer indicates styrene and maleic acid The copolymerization product of acid anhydride and the alternating block for being characterized by styrene and maleic anhydride moities.

Amphipathic nature block polymer can be especially desirable.Arkema dealer is designated as the amphipathic embedding of NANOSTRENGTH Section copolymer.This based block copolymer at present can two versions obtain: SBM and MAM.It is reported that SBM copolymer is by polyphenyl second Alkene, 1,4- polybutadiene and a rule poly- (methyl methacrylate) are made.

In addition, it is possible to use the polymerization being made of polymethyl methacrylate (" PMMA ") and butyl polyacrylate (" PB ") Object material.Such polymer material is referred to as polymethylmethacrylablock block butyl polyacrylate block poly-methyl methacrylate Ester copolymer (" MAM ").

According to Arkema, MAM is the triblock copolymer being made of about 70%PMMA and 30%PB.MAM is by individual sheets Section is constituted, and provides the ability of the self assembly under molecular ratios.That is, M assigns polymer hardness and A assigns polymer elasticity Matter.

Rigid polymer segment often dissolves in (methyl) acrylate, however elastic segment is formed in solidification It polymerize (methyl) acrylate and toughness is provided.MAM also enhances engineering properties, and does not damage intrinsic physical property.MAM can be with commodity Name NANOSTRENGTH is bought, and has multiple and different grades, i.e. E-21 and M-52N at present.

Arkema promote NANOSTRENGTH product line as can be miscible with multiple polymers acrylic block copolymers, According to manufacturer, major part is essential industry epoxy resin.Referring also to U.S. Patent No. 6,894,113, wherein plucking at it In wanting, the patent of ' 113 refers to the thermosetting material with improved impact resistance.Impact resistance includes derived from 1% to 80% The anti-impact modifier of at least one copolymer, the copolymer includes S-B-M, B-M and M-B-M block, wherein each block is logical It crosses and is covalently linked to another block or has by being covalently linked to one of block and by another covalent key connection To the intermediary of another block, M is PMMA homopolymer or the copolymer comprising at least methyl methacrylate of 50 weight %, B Not with thermosetting resin and M block compatible and its glass transition temperature (" Tg ") is less than the operating temperature of thermosetting material, and S It is not greater than the Tg of B with thermosetting resin, B block and M block compatible and its Tg or its melting temperature.

Another commercially available example of amphipathic nature block polymer is the known commodity from Dow Chemical Co The polyether block copolymer of FORTEGRA100.Dow describes FORTEGRA100 and uses in amine cured epoxy resin system for design Make the low viscosity toughener of efficient second phase.It is reported that FORTEGRA100 provides the toughness improved and indistinctively influences final The viscosity of coating or composition, glass transition temperature, corrosion resistance, solidification rate or chemical resistance.According to another report, FORTEGRA100 is suitable for being configured to standard bisphenol-A and bisphenol F epoxy resin system, consolidates because it cannot participate in epoxy resin Change reaction.As secondary phase toughening agent, the advantages of FORTEGRA100, is prepared with most telolemma and partial designated volume score When be it is effective, usual 3% to 8% dry volume is it is said that can reach toughening effect.

Other block copolymer includes having that of following general formula comprising both hydrophobicity and hydrophilic fractions or part It is a little:

-[(R¹)_v-(R²)_w]_n-

Wherein herein, R¹It independently is hydrophobicity alkene, such as ethylene, propylene, 1- butylene, 1- hexene, 3- methyl-1-pentene Alkene or 4-methyl-1-pentene or polymerizable hydrophobicity aromatic hydrocarbons, such as styrene；Each R²For hydrophily acid anhydrides, such as maleic anhydride； V is 1 to 12；W is 1 to 6；And n is 1 to 50.

The ratio of hydrophobic patches and hydrophilic fractions in maleic anhydride of styrene block copolymer can be at least 2:1, Such as between 3:1 and 12:1.Hydrophilic fractions in block copolymer should include acid anhydrides, such as maleic anhydride.Block is total Hydrophobic patches in polymers should comprising ethylene, propylene, 1- butylene, 1- hexene, 3- Methyl-1-pentene, 4-methyl-1-pentene or At least one of styrene.It is desirable that block copolymer with the hydrophilic segment comprising maleic anhydride and should include styrene Hydrophobic segment preparation.

With reference to following american documentation literature, they show the amphipathic nature block polymer being applicable in this article, with reference Mode be incorporated herein.U.S. Patent No. 7,745,535 are related to and are claimed amphipathic multi-block copolymer, wherein extremely A few block is molding block (profiled block), and the molding block is by a) hydrophilic middle block and b) hydrophobicity Terminal block composition, the hydrophilic middle block are made of one or more from the following monomeric unit: acrylic acid, methyl The salt of acrylic acid and acrylic acid and methacrylic acid, ester, acid anhydrides and amide；Dicarboxylic acid anhydride；Carboxyethyl acrylates；With third Acrylamide；In hydrophobicity terminal block, segmented copolymer is water-insoluble, nonaqueous dispersion and insoluble or non-dispersible In C_1-3In alcohol.

U.S. Patent No. 7,820,760 are related to and curable adhesive composition epoxy resin are claimed comprising (a) epoxy resin；(b) amphipathic nature block polymer, containing at least one epoxy resin can dissolve each other block segment and at least one (wherein immiscible block segment includes at least one polyether structure to a epoxy resin immiscible block segment, and condition is not The polyether structure of miscible block segment contains at least one or more alkylene oxide monomer list at least four carbon atoms Member)；And (c) at least one curing agent.Amphipathic nature block polymer in the patent of ' 760 is full polyether block copolymer, such as PEO-PBO diblock copolymer or PEO-PBO-PEO triblock copolymer.Amphipathic nature block polymer is made with a certain amount of presence It is proper in the patent of ' 760 when epoxy resin composition, compared to the epoxy resin group of no amphipathic ether block copolymers Object is closed, the adhesion strength of gained cured epoxy adhesive resin combination increases.

U.S. Patent No. 7,670,649 are related to and are claimed curable ambient cure high-solid coating composition, Include (a) epoxy resin；(b) amphipathic nature block polymer, block segment can be dissolved each other (wherein by containing at least one epoxy resin Immiscible block segment includes at least one polyether structure, and condition is that the polyether structure of immiscible block segment contains at least One or more alkylene oxide monomer units) and at least one epoxy resin immiscible block segment；(c) an adequate amount of nitrogenous Curing agent, to be below about 60 DEG C of cured at ambient temperature coating composition.When epoxy resin composition, gained is solid The toughness for changing composition epoxy resin improves.

U.S. Patent No. 6,887,574 are related to and curable fire retarded epoxy resin composition are claimed comprising (a) At least one fire retarding epoxide resin；(b) at least one amphipathic nature block polymer；And (c) curing agent.These components are with appropriate Amount and ratio are present in curable compositions, so that one is cured, Self-Assembling of Block Copolymer formation of nanostructured form, such as Vermiculate glues form.Gained cured product is it is reported that have the high resistance to fracture significantly improved；And permission is in resistance to fracture Fire retarding epoxide resin is used in the application of one problem.

U.S. Patent Application Publication No. 2008/0287595 is related to a kind of composition, it includes (1) can thermosetting resin, Selected from or mixtures thereof epoxy resin, epoxy vinyl ester resin, unsaturated polyester resin, and (2) amphipathic nature block polymer, It is scattered in can be in thermosetting resin.In addition, also provide the fibre reinforced plastics (" FRP ") prepared by the composition, coating and Compound.

International Patent Publication WO 2010/008931 is related to a kind of structural compound, the structural compound Increase the resistance to fracture (toughness) of structural compound using block copolymer-toughened dose.The structural compound includes (i) carbon fibre reinforcement and (ii) thermosettable resin composition；Wherein thermosettable resin composition can thermosetting resin comprising (a) And it is (b) block copolymer-toughened dose at least one.

International Patent Publication WO 2009/018193 is related to curable compositions, cured composition and its formation Method, the composition includes epoxy resin, curing agent, amphipathic toughener and inorganic nano-filler, wherein the toughener The second phase is formed, at least one-dimensional of second phase is in nanoscale.

Block copolymer can be with about 50 weight % of the total weight of adhesive composition, ideally 5 to 40 weight % Amount is in this article.

The Tg of block copolymer should be higher than that about 40 DEG C, such as between about 40 DEG C and about 155 DEG C.

The Tg of polymer is that polymer becomes fragile when cooled or polymer becomes soft temperature when heated.More specifically Ground, Tg limit pseudo- second order phase transformation, and wherein polymer generates glassy structure while cooling, and the property of the glassy structure is similar In those of crystalline material property.Higher than Tg, polymer becomes soft and can be plastically deformed and not broken.Although Tg is retouched once in a while State " softening temperature " for polymer, but polymer lower than Tg at a temperature of start softening and be not uncommon for.This is because due to The property of a variety of non-crystalline polymers, the softening of polymer can occur rather than under single temperature value suddenly in temperature range Occur.Although polymer can start to soften at different temperatures, Tg generally refers to the intermediate point of the range.For present application Purpose, the Tg of polymer refers to the value as measured by ASTM E-1356.

Except lower than Tg at a temperature of become brittle in addition to, and be heated above the temperature phase of its Tg when same polymer Than polymer usually becomes drier and sticky smaller.When individually applying pressure, sticky polymers will compare non-adhesive polymer It is easier to be adhered to surface.It is incorporated to the Tg higher than 40 DEG C and is therefore at this time to dry or only slightly have sticking copolymer Importance will be by becoming readily apparent from discussed below.

Other additives

Part B can contain additional additive, such as filler, lubricant, thickener and colorant.Filler provide volume without It sacrifices the intensity of adhesive and can be selected from high density or low density filler.

Low density filler is especially envisaged that, because gained final product has the product than being free of filler in addition lower Density, and there is substantially the same strength characteristic when with as filler is not present.

Packaging and mixing

Each of part A and part B are with autonomous container, such as bottle, tank, test tube or bucket packaging.

Part A and part B is mixed with the ratio of about 3 to 50 part A and a part of B.Preferably, the ratio of part A and part B Rate is about 5 to 20 part A than a part of B.

The mixing of two parts can use mixing nozzle, have the body input terminal for two kinds of components, execute and be suitble to Hybrid manipulation and binder combination is directly distributed to surface to be bonded.The reality of commercially available mixing and distributor Example bePurchased from ConProTec, Salem, NH.Two parts can also be artificially mixed in alms bowl, bucket etc., but be grasped It is necessary to ensure that mixing is thorough as personnel.As ensuring to mix thorough auxiliary, each section can be prepared with dyestuff or pigment, so that mixed After conjunction, the third color is formed.For example, a part can have weld, and another part can have blue dyes, So that the adhesive composition of completion will be green after mixing.

The present composition is excellent adhesive and sealant.It may be incorporated into being applied to first surface for example to lamination material When piece of cloth in material, second surface will cooperate with first surface and two surfaces will be bonded in one with adhesive curing It rises.Another advantage is not need surface treatment to bond clean substrate.

Term " solidification " refers to the chemical reaction for converting fluid mixture to solid bonding of the invention.Acrylic acid-ring The curing method of oxygen resin binder is well known in the prior art.See, for example, U.S. Patent No. 4,426,243 (Briggs).Chemical reaction between polymer of the curing method for acrylate and based on epoxy resin is to form acrylic acid- Epobond epoxyn.

After mixing, composition solidify in about 15 to 1000 minutes at room temperature and about 60 DEG C at a temperature of about 30 seconds Solidified to 120 seconds.Certainly, shorter curing time can be realized by medium higher temperature conditions.It is desirable that composition is at about 80 DEG C Under solidify in about 200 minutes, then room temperature curing in 24 hours.

Embodiment

Synthesis

THQ- glycidol adduct (referred to as THQ-D or THQ- glycol) is made according to the synthesis flow hereafter described It is standby:

It is burnt to the tetra- neck round bottom of 500ml equipped with condenser, charging hopper, nitrogen purging, magnetic stirring bar and thermal probe [8 grams of glycidol are added in bottle；108mmol] and [14 grams of THQ；108mmol].Flask is placed on to the heating maintained at 60 DEG C 9 hours on plate, persistently stir during this period.Stand overnight reaction mixture at room temperature.100ml deionized water is added, and Reaction mixture is again heated to 60 DEG C.

By the combination of isopropanol/water, then mixture is recrystallized using deionized water, is re-formed wherein observing Solid.Then filtering mixture is collected solid and is dried in vacuo in the baking oven at 50 DEG C.

Formulation

Table 1A and table 1B shows the general preparation parameter and possible component for each of part A and part B.

Table 1A

Table 1B

Ingredient	Part B (weight %)
		Plasticizer	25-35
Oxidant	37
		Epoxy resin	15-25
Colorant	1
		Polyethylene wax	11

The more specific embodiment of part A formulation and part B formulation is set forth below.

Part A

It is initially introduced into KRATON board block polymer and MMA (respectively with its recorded amounts) into container, the material is put It sets about 24 hours at room temperature.Then to cited residual components are fitted into following table in container with institute's recorded amounts, in addition to AEROSIL board silica.Mixture is blended 3 minutes with 3500rpm with auger (auger).Then addition AEROSIL board Silica is simultaneously continuesd to mix 2 minutes with the speed.

Ingredient	Amount/(g)
		MMA	45.95
VERSENE 2201	0.1
		Triphenyl phasphine	0.5
Antioxidant premix	0.05
		BLENDEX 3382	4.5
KRATON D 11553	22
		HYPRO 2000X168 VTB4	13
Microcrystalline wax 1239A	0.4
		Methacrylic acid	10
HARCRYL 12285	1
		THQ- glycol	1.66
AEROSIL 200	1

¹EDTA

²Acronitrile-butadiene-styrene

³- 40% styrene of straight-chain block copolymer and butadiene

⁴The butadiene liquid rubber of methacrylate sealing end

⁵The phosphate of 2-hydroxyethyl methacrylate

Adhesion promotor

Final part A is fitted into nylon box, to be used for meter mix equipment.

Part B

Into container be packed into 20.4g BENZOFLEX 2088,37g dibenzoyl peroxide, 10g PLURACOL V 10, 21g bisphenol A/epichlorohydrin and 11.5g ECONOPOLY 2N1.Mixture is blended 30 minutes with 1000rpm with auger. Last part B is packaged in nylon box and is used for instrument mixing apparatus.

Mixing

Part A and B are mixed into 10:1 mixture with MIXPAC nozzle sets, are used for two parts.After mixing, composition is aobvious Work (or open) time less than 5 minutes is shown.

Performance

It is viscous that part A/part B mixed preparing object intersection is assessed on the substrate made of steel, stainless steel, aluminium and Kalix Tie power, tensile bond strength, T peel adhesion strength and/or wedge impact adhesion strength.

It is surface-treated with 1 " × 0.5 ", 30mil tack line bonding test piece (coupon) and not.

Cure profile of the mixed composition after being applied to required substrate is exposed to temperature 20 minutes of 80 DEG C, then It is exposed to room temperature about 24 hours.

The adhesive intersection adhesion strength of Kalix substrate is shown in Fig. 1 and is reported in lower Table A.It comments at these In estimating, p-TDEA is used as control, and is referred to as in figure and compares.

Table A

Steel substrate is shown in Fig. 2 in the adhesives intensity under stretch mode and is reported in following table B.

Table B

Stainless steel substrate is shown in Fig. 3 in the adhesives intensity under stretch mode and is reported in following table C.

Table C

Aluminum substrate is shown in Fig. 4 in the adhesives intensity under stretch mode and is reported in following table D.

Table D

Kalix substrate is shown in Fig. 5 in the adhesives intensity under stretch mode and is reported in following table E.

Table E

Steel substrate is shown in Fig. 6 in the adhesives intensity under tensile peel mode and is reported in following table F.

Table F

Steel substrate is shown in Fig. 7 in the adhesives intensity under wedge-shaped impact mode and is reported in following table G.

Table G

Here, with a variety of promotors in the amount evaluation part A formulation in such as foregoing embodiments.By in above-described embodiment Part B formulation is used like that.Following table H is shown for part B formulation and the part A with each of different promotors Color observed by each of formulation, and after part A formulation is mixed with part B formulation observed by Color.In love in institute it is worth noting that, although the color through mixed part A and part B changes in all cases Only a kind of change is predictable (such as blue solution is added to yellow solution and generates green final product) in condition.Containing In the part B of THQ glycol, the color change through mixed part A and part B generates blood red.

Table H

In lower Table I, promotor and its gel used in the part A formulation mixed with part B formulation are shown Time and Exotherm Time (time to exotherm) (respectively as unit of minute), and record the maximum reached during heat release Temperature.Herein, it is seen that only the part A formulation with THQ glycol shows gel time more than 5 minutes and 4 minutes or less Exotherm Time, and when mixing with part B formulation, that is assessed realizes all promotions of gel time and Exotherm Time Agent minimum maximum temperature achieved.Gel time can be considered the open hour, ideally larger for end user, Because it allows end user more flexible when manufacturing component, the component may be larger in dimension or crisscross in design It is complicated.Shorter Exotherm Time section is preferably, so that just quickly there is heat release once solidification.Whether this is considered as fixation Time or formed proper level adhesion strength time allow end user increase component manufacture handling capacity.Finally, putting Lower maximum temperature achieved is converted into safer environment during heat, and wherein end user implements its trade and reduces damage The possibility of the substrate of bad bonding.

Table I